United States Department of Commerce

Technology Adm nistration

National Institute of Standards and Technology

NIST Special Publication 865 LI '.^^i^..^

NIST Workshop on Gas Sensors:

Strategies for Future Technologies

Proceedings of a Workshop Held in Gaithersburg, Maryland

September 8-9, 1993

Steve Semancik, Editor

QC

100

U57

NO. 865

1994
Jhe National Institute of Standards ana lecnnology was established in 1988 by Congress to "assist industry

in the development of technology . . . needed to improve product quality, to modernize manufacmring processes,

to ensure product reliability . . . and to facilitate rapid commercialization ... of products based on new scientific discoveries." NIST, originally founded as the National Bureau of Standards in 1901, works to strengthen U.S. industry's

competitiveness; advance science and engineering; and improve public health, safety, and the environment. One of the agency's basic functions is to develop, maintain, and retain custody of the national standards of measurement, and

provide the means and methods for comparing standards used in science, engineering, manufacturing, commerce,

industry, and education with the standards adopted or recognized by the Federal Government.

As an agency of the U.S. Commerce Department's Technology Administration, NIST conducts basic and applied

research in the physical sciences and engineering, and develops measurement techniques, test methods, standards, and

related services. The Institute does generic and precompetitive work on new and advanced technologies. NIST's

research facilities are located at Gaithersburg, MD 20899, and at Boulder, CO 80303. Major technical operating units and their principal activities are listed below. For more information contact the Public Inquiries Desk, 301-975-3058.

Office of the Director

• Advanced Technology Program

• Quality Programs

• International and Academic Affairs

Technology Services

• Manufacturing Extension Partnership

• Standards Services

• Technology Commercialization

• Measurement Services

• Technology Evaluation and Assessment

• Information Services

Materials Science and Engineering

Laboratory

• Intelligent Processing of Materials

• Ceramics

• Materials Reliability'

• Polymers

• Metallurgy

• Reactor Radiation

Chemical Science and Technology

Laboratory

• Biotechnology

• Chemical Kinetics and Thermodynamics

• Analytical Chemical Research

• Process Measurements^

• Surface and Microanalysis Science

• Thermophysics^

Physics Laboratory

• Electron and Optical Physics

• Atomic Physics

• Molecular Physics

• Radiometric Physics

• Quantum Metrology

• Ionizing Radiation

• Time and Frequency'

• Quantum Physics'

Manufacturing Engineering Laboratory

• Precision Engineering

• Automated Production Technology

• Intelligent Systems

• Manufacturing Systems Integration

• Fabrication Technology

Electronics and Electrical Engineering

Laboratory

• Microelectronics

• Law Enforcement Standards

• Electricity

• Semiconductor Electronics

• Electromagnetic Fields'

• Electromagnetic Technology'

• Optoelectronics'

Building and Fire Research Laboratory

• Structures

• Building Materials

• Building Environment

• Fire Safety

• Fire Science

Computer Systems Laboratory

• Office of Enterprise Integration

• Information Systems Engineering

• Systems and Software Technology

• Computer Security

• Systems and Network Architecture

• Advanced Systems

Computing and Applied Mathematics

Laboratory

• Applied and Computational Mathematics^

• Statistical Engineering^

• Scientific Computing Environments^

• Computer Services

• Computer Systems and Communications^

• Information Systems

'At Boulder. CO 80303. ^Some elements at Boulder, CO 80303.
NIST Special Publication 865

NIST Workshop on Gas Sensors:

Strategies for Future Technologies

Proceedings of a Workshop Held in Gaithersburg, Maryland

September 8-9, 1993

Steve Semancik, Editor

Process Measurements Division

Chemical Science and Technology Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

Issued December 1994

U.S. Department of Commerce

Ronald H. Brown, Secretary

Technology Administration

Mary L. Good, Under Secretary for Technology

National Institute of Standards and Technology

Arati Prabhakar, Director
National Institute of Standards

and Technology

Special Publication 865

Natl. Inst. Stand. Technol.

Spec. Publ. 865

147 pages (Dec. 1994)

CODEN: NSPUE2

U.S. Government Printing Office

Washington: 1994

For sale by the Superintendent

of Documents

U.S. Government Printing Office

Washington, DC 20402
Abstract

This Proceedings issue describes a Workshop on gas sensing held in Gaithersburg, MD,

September 8-9, 1993. Future gas sensors with improved response characteristics, higher

reliability, and lower cost can be expected to have increased application in diverse areas, including environmental monitoring, process control, and personal safety. This Workshop

brought together gas sensor manufacturers, present and potential users, and researchers to explore ways to incorporate research discoveries and emerging technologies more efficiently

into new, high-performance sensors. The Proceedings includes publications on invited and

contributed presentations, reports on discussions of Emerging Technologies and

Commercialization and Standards issues, and reports summarizing breakout sessions on gas

sensing for Process Control in Manufacturing, Indoor Air Quality and Personal Safety,

Outdoor Environmental Monitoring and Site Remediation, and Automotive and Other

Transportation.

iii

EXECUTIVE SUMMARY

NIST WORKSHOP ON GAS SENSORS: STRATEGIES

FOR FUTURE TECHNOLOGIES

September 8-9, 1993

National Institute of Standards and Technology

Gaithersburg, MD 20899

Motivation

Advances in materials, electronics, microfabrication, and the understanding of transducing

chemistry are creating opportunities for developing new generations of gas sensors with

improved performance and lower cost. Such improvements can be expected to greatly

increase the application of gas sensors in wide-ranging areas including personal safety,

process control and environmental monitoring. While the market potential is large, workers

in this field often recognize a time lag for incorporating new discoveries into sensing

products. This Workshop, entitled Gas Sensors: Strategies for Future Technologies, was

held as a timely attempt to identify and discuss the barriers connected with developing and

commercializing new gas sensor devices suited to an expanding range of compositional

monitoring applications. Most other forums on sensor development and use have centered

around research conferences and highly specific application areas. A unique feature of this

Workshop was that it provided an open environment with broad participation focused both

(1) on promising technologies for creating reliable devices, and (2) toward exposing

weaknesses in the chain of research, development, commercialization and application that can negatively impact domestic competitiveness in the field of gas sensing. Chemical gas

sensing is at a relatively young stage in its development, especially in comparison with

other technologies, such as integrated circuitry or even certain kinds of physical sensors

(including accelerometers). While strategies for accelerating development were focused on,

it was not the intent of this first NIST Gas Sensor Workshop to produce a detailed roadmap

for the field.

Workshop Organization

To comprehensively examine various perspectives on relevant issues, this two-day

Workshop encouraged direct interactions between gas sensor manufacturers, present and

potential users, and researchers. The Workshop included a collection of 12 invited

presentations selected to describe not only differing gas sensing technologies and

measurement needs, but also to represent the viewpoints held at the various types of

institutions and agencies in attendance. Contributed papers were presented in a poster

session held on the afternoon of the first day. A special (off-site) poster session was also

arranged for those who wished to display gas sensor product information.

Two types of discussion sessions were held during the second day. Cross-cutting,

application-oriented Breakout Groups, of manageable size for interactive discussion, were

held in 4 areas: Process Control in Manufacturing (Chaired by John Steichen of Dupont),

Indoor Air Quality and Personal Safety (Chaired by Jarell Wenger of Johnson Controls),

Outdoor Environmental Monitoring and Site Remediation (Chaired by Barry Wise of

Batelle Pacific Northwest Laboratories), and Automotive and Other Transportation

V
(Chaired by Galen Fisher of General Motors Research and Development Center). Within

these sessions various sensing approaches were compared for a related class of gas

measurement problems. Participants were encouraged to move between the various

sessions, and a significant fraction did so. The second type of discussion had more of a town-meeting format, and also served as the closing session of the Workshop. Two

primary themes were focused on in the latter discussion: The Role of Emerging

Technologies in Gas Sensing, and Commercialization and Standards Issues.

During the first day a representative of the Advanced Technology Program made an

informal presentation outlining the operation and direction of this funding component of

NIST. Attendees were also offered an opportunity to tour 8 sensor-related facilities at NIST. The Workshop was attended by approximately 135 persons from 30 states, as representives of small companies, large companies, federal agencies, government

laboratories and universities.

Summary of Presentations and Discussion Sessions

The Workshop explored approaches for incorporating research discoveries and emerging

technologies into the production of high-performance sensors (as distinguished from

larger, more costly monitoring instruments). A variety of sensing schemes were presented,

and their relative merits, suitability and shortcomings for certain categories of use were

discussed. In considering benefits and limitations of various sensing technologies,

markets, operational specifications, manufacturability, calibration and standards issues were addressed.

The invited speakers represented 2 small companies, 4 large companies, 2 agencies, 2

government laboratories and 3 universities. Among the gas sensor types discussed were

thermal, surface acoustic wave, electrochemical, infrared, fiber optic, semiconducting

oxide, catalytic gate and solid electrolyte. Existing commercial devices received attention as did novel concepts for new device development. In certain cases, instruments and sampling

methodology were described in monitoring situations where sensors have not yet made

inroads. Gas and vapor chemical monitoring problems were defined for 5 major areas including environmental testing and restoration, waste management, industrial safety,

chemical processing and automotive emissions. Implications for these and other

applications were addressed briefly when the first invited speaker discussed world market

projections. Details for all of the invited presentations can be found in articles published in

this volume.

The conclusions reached in the application-oriented Breakout Groups are summarized

briefly below (and described more fully in the Chairpersons' reports found in the Breakout

Groups section of this volume). While all Breakouts were given a base level of guidance

for discussions, the Discussion Leaders and groups of participating individuals created a unique environment in each of the 4 areas. The open discussion of Emerging Technologies

centered on new device concepts, micromachining, neural networks, and packaging and

telemetry, while that on Commercialization and Standards was primarily concerned with a range of business, regulatory, and technical topics (see also articles in the text).

Process Control in Manufacturing .

Discussion in this Group indicated that several factors have limited the use of sensors, thus

far, for industrial process control applications. First, the area of process control is so

vi
diverse that it is difficult to define performance requirements. The level of secrecy that

surrounds certain industrial processes further compounds the task of problem definition.

Also, since chemical production lines cannot usually serve as test beds, sensors must be

proven reliable before they will be applied. The importance of this point is underscored by

the high installation cost that can occur for incorporating sensors into many types of

chemical process lines, even if the sensors themselves are inexpensive. Once installed to serve process control functions, the sensors should have an extended life without

significant maintenance.

The Process Control Group made a number of suggestions to guide sensor development

for their field. Their primary suggestions included:

concentrate on those measurements where traditional techniques are not

available or reliable, or where there is a specific need for low-cost monitoring

Key areas identified:

rugged sensors for combustion and incinerator control

sensing of fugitive emissions (not necessarily for "process

control") of species such as methyl isocyanate, phosgene, vinyl

chloride and HF

real-time detection of low-level moisture

involvement by NIST in coordinating and guiding sensor development through

efforts aimed at:

acting as a clearing-house to make available to the sensor community information on the "real" gas sensing needs and

operating conditions for control of industrial processes

creating, through increased funding, an effective development

bridge between sensor researchers and sensor manufacturers

effectively matching players to produce demonstrations of

performance and payoff in real world applications

The Group agreed that this NIST-sponsored Workshop was an important first step in their

recommended involvement for NIST in advancing sensors into process control

applications. Additionally, members of the Group have been instrumental in helping to found a Process Chemical Sensor Forum, made up of industrial representives, which will

meet periodically at NIST-Gaithersburg to voice measurement needs.

Indoor Air Quality and Personal Safety

This Breakout Group considered sensing issues relating to indoor air quality (lAQ),

industrial hygiene and general health and safety. Unlike the Process Control Group, this

Group indicated that attainment of low ($100's) or very low ($10's) cost sensors was

critical to opening up extremely large commercial and residential markets in future years.

vii
Minimal calibration and long term reliability were emphasized as essentially mandatory

attributes.

Within this session, species and concentrations of gases to be monitored were identified in

the areas of lAQ (including SO2, CO, O3, CO2, radon, chlordane, SF6, selected

refrigerants and tobacco smoke), industrial environments (including O2, CO, H2S and

freon) and hospitals, health and safety (including halothanes, NO, anesthesia gases,

ethylene oxide and formaldehyde). The differing sensing situations presented for industrial

hygiene and lAQ applications were described, respectively, as a case involving the

detection of a (relatively) limited number of harmful compounds, compared to the

measurement of hundreds of potential compounds, including volatile organics, at a 100-

fold or higher sensitivity level. For certain applications, sensitivities ~ lO's ppb are

required.

The Group felt that insufficient technological development represented the major

impediment to sensor commercialization at this time. The exceptions which have seen

significant deployment for lAQ are devices for monitoring CO2, and more recently CO. It was indicated that integrated units measuring total volatile organics, CO2, relative humidity

and temperature could have a major impact in the heating/ventilation/air conditioning

market, assuming they could be produced at a low enough price (estimates ranged from

below $300 to $30). Other commercialization hurdles exist in these application areas, besides price. Reliability is extremely important and false alarms cannot be tolerated.

Insurance issues and regulatory policies can also strongly influence acceptance.

The primary suggestions to accelerate sensor development in the Indoor Air Quality and

Personal Safety area were:

to increase investment in several technological areas (including surface

acoustic wave and non-dispersive infrared) that hold higher levels of

promise, in order to move across the "gap" from research scale to prototype products (while funding approaches such as the NIST ATP

program were identified, it was felt that additional mechanisms for

funding development might be required for small companies)

to develop methods by which users could interact more directly with

researchers to influence development directions and to help establish

testing guidelines

Outdoor Environmental Monitoring and Site Remediation

The structure of this Breakout Discussion fell into 3 main sections relating to applications,

specific issues for environmental sensing, and promising research directions. The Group

identified and discussed stack emissions and fugitive emissions as 2 areas of major market

potential. Environmental and safety concerns may dictate that detection for each of these

classes could soon require continuous monitoring capabilities. The monitoring and cleanup

of waste sites represents another sizeable challenge for sensor development. Volatile

organics must be measured to screen sites and determine the effectiveness of remediation

procedures. Hydrogen and other gases must be monitored in connection with nuclear waste

storage and the identification of vapors above test-well water can be useful in locating

groundwater contamination.

viii
It was agreed that a number of important issues exist for environmental measurements.

Among those expressed were (1) determining whether the measurement is for

characterization, monitoring or screening, (2) protecting against the effects of fouling and

corrosion, (3) dealing with unknown and uncontrolled backgrounds, (4) increasing efforts to develop properly-suited and reliable active coatings, (5) being aware that a wide range of sensor costs can be tolerated for varying environmental applications, (6) the shortage of

reliable performance data in existence for environmental sensing systems, (7) developing

methods for eliminating or correcting for sensor drift, (8) accomplishing sensor portability

for the many applications that would require or benefit from this characteristic, (9) using

concurrent engineering in developing cost-effective packaging, and (10) making reliable

baseline data available for naturally-occurring chemicals in various environments.

The Environmental Breakout Group identified several research and development areas which should receive concerted efforts. The broad range of specific chemical measurements

in environmental and remediation situations requires a significant materials research effort to develop and tailor selective coatings for marriage with existing and new detection

schemes. Since response characteristics are often nonlinear, nonlinear and multivariate

calibrations must also be developed by those working in chemometrics and pattern

recognition. Widespread utility of new sensors will depend on their reliability, cost, and in

certain cases, on their size. Efforts on developing streamlined manufacturing processes to reproducibly fabricate batches of integrated, miniature sensors could be rewarded by

creating devices that would be accepted in the marketplace more rapidly. The Group also

indicated that further development of fiber optic-based sensors would permit the power of

spectrophotometry to be applied in many application areas and that biological sensors would also play an important role for certain environmental measurements.

The Group concluded that the largest barriers to environmental sensor commercialization

related to:

insufficient development of active films

a lack of adequate support for the final development stage

uncertainty about potential market size for a given device.

Automotive and Other Transportation

Gas sensor needs for the automotive industry dominated the discussion in this Breakout

Group. These needs are being imposed by the 1990 Clean Air Act as well as other new

rules connected with the EPA and California Air Resources Board.

Current legislation was discussed which calls for auto on-board diagnostics (OBDs) by

1996. OBDs would make a driver aware when any component affecting emissions is not

functioning properly. Monitoring of the catalytic converter, which converts hydrocarbons,

CO and NOx to CO2, H2O and N2, is one of the sensing problems receiving considerable

attention in this regard. A dual or multiple O2 sensor approach is often used now, but a more direct method would be preferable. It was also pointed out that more stringent

emission standards slated for the years ahead will probably make converter monitoring even more complex and require gas sensors of high sensitivity. The report of this Group

includes a brief table on detection specifications for certain target gases and considerable

attendant discussion dealt with the operational demands under which measurements must

ix
be performed. Among the conditions and requirements are operation over a wide

temperature range, under-car spatial constraints, 12V DC compatibility, response times in

the 10-20 second regime, and survivability (preferably without a service recalibration) for

100,000 miles.

Several proposed sensing solutions for the demanding task of automotive exhaust

measurement were presented by representatives from 3 companies. Following the brief

presentations, the Group debated the advantages and shortcomings of the various

technologies. A dual calorimetry method was described for measuring CO, hydrocarbons,

NOx and SO2 with response times of several seconds. It was pointed out that this approach

requires sufficient oxygen to oxidize CO and hydrocarbons, and that CH4 sensitivity may

be low. A nondispersive infrared approach with a 10 m equivalent pathlength was

presented as a possible low-cost method for monitoring hydrocarbons, CO2, CO, NOx,

SO2 and ozone. Concerns for this approach centered on stability and durability of the

system under operating conditions. The third approach described in this session utilized a group of solid state and electrochemical devices, sometimes combined with selective

membranes, in order to measure various oxidizing and reducing gases.

While considerable challenges exist for sensor developers in meeting the requirements for

low, transitional-low and ultra-low emission vehicles (LEVs, TLEVs and ULEVs) in this

country, it was explained that a somewhat lower level of interest in lean burn engines seems to exist elsewhere in the world. Many participants in the Group felt that considerable

materials research to develop better sensing films will be paralleled by efforts aimed at improving catalytic converters in order to meet rapidly-approaching domestic emissions

control deadlines.

General Comments

Participants at this first NIST Workshop on gas sensors felt it a rather unique and

diversified forum which served a number of useful functions including defining a range of

gas sensing problems, presenting a variety of existing and developing technologies and

directly addressing problems encountered in commercialization (see also the

Commercialization and Standards report in the Discussions section). The Breakout

Sessions, while concerned with differing application areas, showed a high degree of

commonality when it came to identifying barriers and challenges to successfully producing,

marketing and using gas sensing devices. Each of the sections below indicates a major

barrier, and then lists expressed actions for overcoming that barrier.

• Limitations in reliability and sensing function. Issues here go

to the heart of the transduction process and require cross-cutting research on a number of fronts. Basic studies at NIST and other government

laboratories and universities should provide foundational information on improved and new active materials, sensing mechanisms and new sensing

concepts. To provide increased reliability and utility at acceptable costs,

standard methods of (micro)fabrication and packaging should be

developed and employed to the maximum extent. Schemes for low power

operation are required for deployment in many applications. Effective

signal processing routines must also be developed to provide recognition

and calibration functions.

X
• Existence of a substantial "development gap" between

promising research results and creation of a successful gas

sensor product. The problem of connecting the research world and the

real world is nothing new, but successful channeling between these

sectors in the area of gas sensing is expected to be particularly fruitful.

Contact and communication are key elements of a solution here, and the

need to create effective mechanisms for researcher-manufacturer

interactions and partnering was widely voiced. Cooperative research and

development agreements (CRADAs) and guest worker and exchange

programs should be continued and expanded. Funding sources targeted at such programs could catalyze increased inter-institutional activity.

• Product inertia and hesitance of sensor companies to invest

into new technologies and markets. The push forward from

existing product lines into new technologies and markets often ties

considerable risk with the potential for substanial profit. In gas sensing,

the costs of R & D, production scale-up and marketing can be larger than

in other fields, and manufacturers often feel it necessary to share the costs of high risk development. Insufficient funding of the high risk

development regime was among the problems most universally expressed

at the Workshop. Attendees felt that a focused sensor competition through

the NIST Advanced Technology Program could provide one important source of support for this area in the years ahead. The need for

information on existing and projected markets in a range of application

areas was also expressed.

• Uncertainty concerning the methods and value of existing sensor performance demonstrations. Manufacturers seek effective

and rapid procedures for certification of their sensor products so that they can be used in regulated and personal safety applications. Users on the

other hand, demand reliable performance specifications under conditions

appropriate for judging whether a device will meet their particular

monitoring need. Many participants indicated they now see the need for

application-oriented test beds to properly evaluate sensing devices. They

also expressed a potential role for NIST, possibly in an oversight

position, in proving the capabilities of sensing technologies and in

providing a nonbiased base of performance data.

It is worth noting that while it is unlikely that anyone would complain about using a small,

reliable, low-cost sensor, there were a number of expressed situations where users

indicated they could tolerate larger and considerably more expensive devices or systems. In those many cases where size, power requirements and cost are crucial, emerging

technologies, such as micromachining (see also the Emerging Technologies report in the

Discussions section), hold the potential to have great impact. A key element in developing

future generations of high performance gas sensor devices is the well-coordinated

integration of active materials with new structures and intelligent electronics. Well-matched

active film/electronics combinations and the use of clever operating modes can amplify the

inherent response characteristics of sensing materials and also make possible selfcalibration and reset features critical for many applications that will require user-friendly sensors. Developers should therefore keep an eye to new enabling techniques and

discoveries. However, they should also incorporate proven technologies, such as remote

telemetry, in order to benefit in situations where harsh conditions or wide deployment are encountered.

xi
Finally, gas sensor development was represented at this Workshop as an extremely broad

technological challenge with the potential for great commercial and societal reward.

Success, however, requires the assembly of varied resources and a mixture of talents. The

National Institute of Standards and Technology heard the messages delivered by sensor

users, developers and researchers during this 2-day meeting, and is reassessing its role in an effort to more effectively provide financial, technical, informational and partnering

support in the field of gas sensing.

xii
Acknowledgments

The organizers wish to thank all attendees for their participation in this Workshop. Special

thanks go to the invited speakers, both for their excellent presentations, and for the cameraready manuscripts they provided for this volume. Those who led discussions and took

responsibility for developing reports on their sessions are owed a great debt of gratitude as well. The organizers also wish to acknowledge the assistance and support given by the

Conference Program and Facilities staff at NIST in coordinating logistics for the Workshop.

Disclaimer

The views, conclusions, and recommendations expressed at this Workshop and those reported

in this Proceedings are not necessarily those of the National Institute of Standards and

Technology.

Certain commercial equipment, instruments, or materials that have been identified in this

document are included in order to specify experimental procedures adequately, or to demonstrate a type of equipment. Such identification is not intended to imply

recommendation or endorsement by the National Institute of Standards and Technology, nor

is it intended to imply that the materials or equipment identified are necessarily the best

available for the purpose.

xiii

Proceedings of the NIST Workshop on Gas

Sensors: Strategies for Future Technologies

Table of Contents

Abstract iii

Executive Summary v

Acknowledgments xiii

Disclaimer xiii

Table of Contents xv

I. Invited Papers 1

Solid-State Gas Sensors: World Markets and New Approaches to Gas Sensing

Marc Madou 3

Gas Sensing for Industrial Safety and Health

Alan A. Schneider and Joseph D. Jolson 9

Gas Sensor Needs in Environmental Testing

David Friedman 15

Gas Sensing in the Automotive Environment

Joseph Giachino and Julie Konrad 21

Chemical Gas Sensors and the Characterization, Monitoring, and Sensor

Technology Needs of the U.S. Department of Energy

Glenn J. Bastiaans; William J. Haas, Jr.; and Gregor A. Junk 25

Thermal Microsensors for Environmental and Industrial Controls

Ulrich Bonne 31

NIST Programs and Facilities in Gas Sensing and Related Areas

Steve Semancik and James R. Whetstone 39

Gas Sensor Technology at Sandia National Laboratories: Catalytic Gate, Surface

Acoustic Wave and Fiber Optic Devices

Robert C. Hughes, D. J. Mareno, M. W. Jenkins, and J. L. Rodriguez 47

XV
Microchemical Sensing Based on Temperature-Programmed Methods

Kensall D. Wise, J. L. Gland, and J. W. Schwank 53

Amperometric Electrochemical Gas Sensors: Description and Applications

Joseph R. Stetter 61

Gas Phase Sensing in the Chemical Industry: Today's Practiced Technology

Kevin Hool, Robert Bredeweg, Del Lefevor, Mark LaPack, and Larry Wright ... 65

Development of Differential Mode and Solid Electrolyte Gas Sensors

Qinghai Wu, Wei Peng, Henrique do Santos, and Chung-Chiun Liu 71

II. Poster Summary Abstracts 75

Surface Acoustic Wave Sensor (SAW) System Technology

R. Andrew McGill and David L. Venezky 77

Surface Acoustic Wave Gas Sensor Technology at Sandia National Laboratories

James Wiczer 78

Selection of Polymer Coatings for SAW Chemical Microsensors

R. Andrew McGill, Michael H. Abraham, Jenik Andovian-Haftvan, Chau My Du,

Valerie Diart, Gary S. Whiting, and Jay W. Grate 79

Real-Time Neural Network Analysis of Chemical Sensor Arrays: One Step Closer

to Artifical Olfaction

Paul K. Clifford and Michael G. Dorman 80

Application of Olfactory Neural Networks to Processing Sensor Information

T. McAvoy and D. Pan 81

Second Order Devices: The Coming Revolution in Sensors

Barry M. Wise 82

Sensor Technology for Advanced Combustion Control and Monitoring

Instrumentation

M. A. Richard, O. W. Bynum, D. R. Sheridan, P. H. Mark, G. C. Morrison, and

L. T. Brewer 83

New Semiconducting Mixed Oxide-Based Solid-State Gas Sensors for Carbon

Monoxide and Hydrogen

A. M. Azad, L. B. Younkman, and S. A. Akbar 84

Research and Technology for Tin Oxide Gas Microsensor Arrays

R. E. Cavicchi, S. Semancik, G. E. Poirier, J.S. Suehle, and M. Gaitan 85

xvi
Micro-Hotplate by CMOS Technology With Application for Gas Sensors

Michael Gaitan, John S. Suehle, Richard E. Cavicchi, and Steve Semancik 86

Properties of Ultrathin SnOj Gas Sensors

G. E. Poirier, R. E. Cavicchi, and S. Semancik 87

Solid State Sensors Based on Semiconducting Metal Oxides With SurfaceDispersed Metal Additives: Modeling of the Mechanism of Response Formation

Valeriy Sukharev, Richard Cavicchi, and Steve Semancik 88

Gas Sensor Research Facilities in the NIST Process Measurements Division

S. Semancik, R. E. Cavicchi, and G. E. Poirier 89

Calibration Mixtures for Gas Sensor Development and Evaluation

Gerald D. Mitchell and William D. Dorko 90

NIST Humidity Standards and Calibration Facility

Gregory Scace, James Whetstone, and Peter Huang 91

HI. Breakout Group Reports 93

Gas Sensors for Process Control in Manufacturing

John Steichen and Gary W. Kramer 95

Indoor Air Quality and Personal Safety

Jarrell Wenger P. E. and Andy Persily 99

Gas Sensors in Outdoor Environmental Monitoring and Site Remediation

Barry M. Wise and Franklin R. Guenther 103

Gas Sensors for the Automotive and Other Transportation Industries

Galen B. Fisher and Kenneth G. Kreider 109

IV. Discussion Sessions 115

The Role of Emerging Technologies in Gas Sensing

Richard E. Cavicchi and Steve Semancik 117

Commercialization and Standards Issues

James R. Whetstone and William C. Lyndon 121

xvii
V. Appendices 125

A. Final Program 127

B. Participants List 131

C. Laboratory Stops 137

D. Advanced Teclinology Program 139

xviii
I. Invited Papers

1

Solid-State Gas Sensors: World Markets and New Approaches to Gas Sensing

Marc Madou

Microfabrication Applications

3680 Bryant Street

Palo Alto, CA 94306

A short review of the world market for solid state gas sensors is presented. It is pointed out

that there is a sizable sensor industry manufacturing rather imsatisfying products. New

approaches are urgently needed in the industrial world. Some new approaches are described. We report on new types of silicon and ceramic based amperometric electrochemical gas sensors. These new devices feature relatively dry and dry triple points resulting in very fast response

times. The relatively dry triple point devices form a class of sensors having characteristics somewhere between a solid state sensor and a wet electro-chemical cell. The dry triple point sensors are truly solid state in nature and open up the new field of gas electrochemistry. Also

attempts at introducing micromachining techniques in the construction of solid state gas

sensors are analyzed.

World Markets for

Solid State Gas

Sensor Markets

Based on Schroder [1], Yamazoe [2] , Harmer [3] and Tschulena [4] the 1990 total sensor market was $15 billion and is expected to grow further

to $36 billion by the year 2000. The US has a 39 % share of that market. Western Europe 38 %

and Japan 23 % . The most details on the sensor market product make-up are provided by the Japan Electronic Industry Development

Association [2]. This organization found the gas

sensor share of the total Japanese sensor market

to be rather small i.e. 6 % ( 66 million gas

sensors were actually produced in Japan in 1989

(with a dollar value of $207 million)). Using this same percentage world-wide we estimate that the 1990 total gas sensor market was about $0.9

billion. Among the various types of gas sensors, zirconia based oxygen sensors, semiconductor

type gas sensors and humidity sensors make up

90 % of the total.

Three major markets currently exist for solid

state gas sensors: the toxic and combustible

gas sensor market, the automotive market and

the energy conservation market (e.g. all drying operations). True solid state gas

sensors are not used in the biomedical arena and we have not included any biomedical

market figures here. Each of the three

identified markets accounted for over $100

million in sales for 1990 in the United States alone, including the sensors and the electronic

systems such as signal processors, displays

and alarms to which they are attached.

Toxic and Combustible Gas

Monitoring. In the US solid state gas

sensors are mainly used in enviroiunental

monitoring and control applications in industry. Applications for the home market

are not yet wide spread. In Japan the home

market is at least as big as the industrial market due to the prevalent use of gas, often piped into homes in outdated gas supply

lines. This necessitated the mandatory use of

domestic gas detection systems. The US gas

sensor market is concentrated mainly around

chemical sensors used primarily in the petroleum, petrochemical, mining, and

semiconductor industries. In the first three

industries, the most common gases monitored

include hydrogen sulfide, carbon monoxide,

chlorine, methane, and flammable

hydrocarbons. The most important gases monitored in the semiconductor industry are phosphine, arsine, and silane. The prevalence

of hazardous and combustible gases in the petroleum industry is so high and the danger

for workers so great that the impetus to develop chemical sensors for monitoring their presence is strong. Government regulations

have further stimulated monitoring

requirements. Back in the 1960's semiconductor sensors were heralded as the replacement for electrochemical sensors for these type of applications; however the electrochemical gas sensor sales figures (some

with a growth rate of 30 % /year) suggest the opposite. The latter is probably due to the

3
slow rate of improvements in the selectivity

of solid-state gas sensors and the superior

selectivity of electrochemical sensors brought on the market by companies like Neotronics

and City Technology [5]. With respect to true solid state gas sensors the major innovations

imder way are in the area of applying

micromachining technology to their manufacture (see below) with the promise to improve the power requirements. The

selectivity and sensitivity factors still lack

detailed appUcations.

For the past few years the overall market for toxic and combustible gas sensors has been

stagnant due to the collapse of oil prices and

the current recession. The 1990 market for small solid gas sensors and sensor systems in the toxic and combustible gas arena is some

$120 million in the United States. Broken

down by product, the US market for these chemical sensors comprises about $25

million for hydrogen sulfide monitoring

equipment, $20 million for total hydrocarbon

monitoring equipment, $12 million each for carbon monoxide and oxygen deficiency

monitoring systems, and small percentages

for systems to monitor a myriad of other

gases. When the oil business and the industry as a whole recovers, this market is likely to return to its previous 10% annual growth rate. New business developments in this area will probably wait until advances in sensor

fabrication technologies lower unit costs to the point that home air monitoring is economically feasible.

Non industrial applicatons are only begirming

to emerge, e.g. gas sensors for places where

bottled gas is used (RV's, boats, mobile

homes, etc.). The aspect of home safety,

climate control in buildings and smart

kitchens seems to be piu-sued much more

agressively in Japan and Europe than in the US.

Automobile Combustion Control.

The automotive market is another major

development area for solid state gas sensors. Demand for reliable sensors in this business

is quite high, which justifies the high

development costs and the complex

fabrication processes required to reduce unit

costs. Once developed to the technical and

economic specifications of the auto makers,

these sensors are finding wider use in industrial applications which, by themselves,

would not justify high development costs.

The chemical sensor of greatest interest to auto makers is the oxygen sensor, used to optimize the combustion process in the

engine. The value of precise combustion

control rose significantly after the price

gasoline increased in 1974 and the US

government began to regulate fuel efficiaicy

in cars. As a result, a cheap oxygen sensor made from zirconia oxide was developed.

Such sensors, commonly known as lambda

sensors, are used in most automobiles sold

today. They are extremely durable, long-lived, accurate and sensitive. Their major drawback

is that they do not operate below 300°C, and

therefore caimot be used for the many possible

room-temperature applications of oxygen

sensors.

The market size for automotive oxygen

sensors is difficult to assess because most of

them are produced captively by automobile

manufacturers. Oxygen sensors (including some electronics) cost about $20.00 each; the

total 1990 US market for automobile oxygen

sensors alone was between $100 million to $120 million.

Several factors will make solid state oxygen

sensors a very attractive business opportimity

in the next few years; govenunent regulations

in California soon will require the installation of two oxygen sensors per car, amperometric

and universal oxygen sensors i.e. a sensor measuring lean and rich gas mixtures are becoming industrially acceptable; and more

and more countries will require the use of

oxygen sensors in their cars.

Energy and Drying Operation

Markets. Humidity sensors can make drying

processes much more efficient. The energy

savings generated by humidity sensors could

be very large. Indeed drying was estimated to consume from 1.2 to 1.8 quads (1 quad=10l^

BTU) of energy per year in the US in 1980

(about 6 % of the total energy use in that year). The market for humidity sensing in the US is about the same size or larger than the

total toxic gas sensor market ($120 million).

Of major significance is the fact that few of

the solid state humidity sensors manufactured

up to now satisfy the need for an inexpensive

device. But industry makes do with what is available.

The situation depicted for the humidity

sensors summarizes the state of affairs for solid state gas sensors in general (the zirconia oxygen sensor, being very reliable and robust,

is probably the only exception); none of the current solid state gas sensors are very good

but industry needs are so strong that application enginea"s make do with the rather imperfect devices available. Despite R&D

4
efforts world wide, no major improvements on any of the solid state gas sensors can be

reported today. There is an urgait need for better sensors to be developed to break

through this stagnation of the technology. In what follows we are illustrating some

approaches attempted by the author over the

last four years. New Approaches to

Gas Sensing

From Wet to Dry Triple

Points

(a)

We have attempted to make faster responding

gas sensors by innovative methods of

exposing the triple points to gas media. The

intent was to make the liquid path through

which the gas must diffuse to reach the triple

point as short as possible or even do away

with it completely. We believed that in this manner it is possible to create gas sensors

that combine some of the positive

characteristics of both electrochemical and

solid state gas sensors. Three sensors are described; two belong to a class we have

called Back^eUTM (Figures 1 (a) and (b)) and one is a so-called gas electrochemical cell involving only air as the ionic medium

(Figure 2).

-Relatively wet triple points : Two

versions of the back cell sensors were

investigated: sensors using a porous ceramic

substrate and sensors based on a silicon substrate with micromachined pores. The

ceramic alumina is a porous tile with average pore size of 3 ^im (see Figure 1 (a)). The

metal electrodes (sensing; Pt, counter; Pt and

reference electrode; Ag/Ag20) are deposited onto the substrate by sputtering. Hence the electrodes are porous as well. A thin layer of

NafionTM or a hydrogel is then deposited over the metal electrodes and the gas to be

detected is only allowed to reach die sensing

electrode from the back of the porous

ceramic. An alternative method of attaining a porous substrate is through silicon micromachining. A silicon micromachined

substrate is shown schematically in Figure 1 (b). In this configuration only the sensing

electrode is porous, consisting of several hundred micromachined holes. The details of

the microfabrication procedure are explained

elsewhere [6].

Microporous working electrode

Silicon substrate

(b)

Fig. 1 (a) Back cell sensor in the porous

ceramic substrate; (b) Back cell with a silicon micromachined substrate

METAL COAT . GATE METAL TIPS

, (CATALYTK: MATERIAL) / (CATALYTC MATERIAL)

FIEL0OF2X 10^/em*TPS

(ADDRESSED SEPARATB.Y) ^^^^^ ^^^^^^^

I<5>1

AJ THERMOMIQRATIONVJ/

Fig. 2 Submicron gas sensor

5
Although the back-cell sensors are generic and

can be used for a wide variety of gases, we

shall only describe its use here as a fast oxygen sensor. Oxygen is detected amf)erometrically on the Pt sensing electrode by applying a potential more negative than

-0.5 V vs. the Ag/Ag20 reference electrode. At this potential , O2 is electrochemically

reduced at the sensing electrode according to the reaction

02 + 2H20 + 4e- 40H- (1)

The response of this sensor to a step change

in oxygen concentration from 0 to 100 %

exhibits a 90 % response time of 300 msec. That response time is extremely fast compared

to other amperometric sensors (typical response time 30 to 90 seconds). This fast response is due to the fact that a gas does not need to diffuse through a thick layer of

electrolyte to reach the triple points where

they react. In other words the triple point is almost dry (as water is involved in the

reaction, gas probably still diffuses through a few monolayers of water to react at the

metal). The recovery of the sensor back to baseline upon a step change in oxygen

concentration from 100 % to 0 % is slightly

slower than the initial response - 400 msec. We believe that recovery is slower because some O2 dissolves into the Nafion

electrolyte, and must diffuse out (a slower

process than the diffusion into the pore) for the sensor to return to baseline.

The calibration curve of current vs. concentration for this sensor fits a linear least- squares fit with r2= 0.993. The reason for

this linearity is unclear as there is no bulk

diffusion through a liquid phase in this sensor, except possibly through a few

monolayers of water right at the metal

electrode. By varying the bias and the pore

sizes we are attempting to understand the behavior of this sensor better.

In addition to fast response time, the back cell 02 sensors demonstrated good reproducibihty

and reliabihty, and a reasonably long sensor

life through the use of a water reservoir attached to the front side of the sensor. As the Nafion elecfrolyte requires water to be

functional, this reservoir provides sufficient moisture.

- Dry triple points : We also have been studying the detection of

gases by ionization in a device made up of

closely spaced metal electrodes (Fig. 2). The

sensing electrodes are large numbers of field- emitter cones, all connected m parallel on a Si

chip. Various steps are required to produce

these cones initially produced for high- vacuum field emitters. Details on the

fabrication of these field emitters can be found

from reference [7]. A conducting layer \ery

close to the cones, termed the "gate", was

used as the counter electrode. In most of our

experiments the cones and counter electrode had a Pt surface exposed to the atmosphere

Care was taken in keeping the sensors as di-y as possible so that in this case we could truly

speak about dry triple points.

Figure 3, curve 1, depicts a typical curve showing the current/voltage response for an

array of about 10,000 cones in parallel where

the cones (the tips) are biased negative in the presence of 1 torr HCOOH. No observable

current is measured wdth the tip positive.

I I I • o«iicv*nciarniTH coliicto* xiaATivi O CATI CuMHImT with COLLICrOM rOliTlvf coiLlcion cumint mm collictoh roiitivi

-QAII

CONI

OAII-Tlf raTIHflAL — •

Fig. 3 Collector current and gate current as a

function of tip potential showing formation

of formate ions

We consider one experiment to be of

particular interest. We introduced a screen as a

residual charge collector about 2 mm over the gate and applied first a positive then a negative voltage between the screen (collector) and the gate. None of the current flowed to the screen with the screen negative; with the

6
screen positive, a substantial fraction of the

current flowed to the screen (curve 3). In other words, some of the charges normally attracted to the gate also found their way to the

collector (actually the gate and collector

currents, curves 2 and 3, add nicely up to curve 1). We interpret this phenomenon as follows: because only a positive screen bias can attract charges, the emitted charged species are likely to be dominantly negative electrons or ions. Moreover the screen expaiment

estabUshed that the observed currents are not

leakage currents over the Si02 surface between the electrodes. Our contention is that negligible ionization occurs in the gas phase,

and that we are observing ion production at the tip surface. These observations suggest

the possibility of gas electrochemistry at dry

triple points. This could lead to a new

generation of sensors as well as a new

generation of instruments with these cones as

ionizers.

From thick to thin film and

Micromachining in Solid

State Gas Sensors

that the application of IC techniques could

improve the state of the art dramatically here;

if one could make a thin film with the same

sensitivity as the thick film, one can be

certain that micromachining the heater elements will further improve reproducibility

and the absolute power budget needed to heat

the thin film. In micromachined solid state gas sensors such thermal efficiency and a low

power budget is obtained by thermally

isolating the heater element.

Fig. 4 Structure of a Taguchi gas

sensor

The use of a ceramic tube in a classical Taguchi sensor (Fig. 4) maximizes the

utilization of the heater power, so that all the power is used to heat the tin oxide (as opposed to a flat configuration with the tin oxide on one surface, where some of the power is wasted). It also simplifies the form

of the heater wire, which can be a coil inserted

into the tube. The tin-oxide paste is applied on the outside of the ceramic body over thick film resistance measuring pads and is sintered

at high temperature. The sintering stabilizes the intergranular contact where the sensitivity

of the gas saisor resides. It is clear to some

extent why the sensor is designed as it is. It is also clear, noting the messy procedures, how

the problems with the Taguchi sensor arise.

The structure shown in Fig. 4 is a design ill suited for mass production as it involves

excessive hand labor. Coating a cylindrical

shape with a thick film paste is obviously more difficult than coating a planar structure. The problems with the thick film structure are mainly in the area of reproducibility : compressing and sintering a powder, the deposition of the catalyst (e.g., the size of

Palladium crystallites and how close they are

to the intergranular contacts), the use of

binders and othCT ceramics (e.g for filtering) are all very difficult to control. It is obvious

The use of the intergranular contact potential as the resistance-detatnining parameter is required for maximum sensitivity. When

making thin films, attention has to be paid to making the films thin enough for the extraction of electrons to have a significant

effect on the overall film resistance (see Fig.

5). Obviously thickness control becomes a key factor here. In Fig. 5 the depletion region

is shown , and the conductance is proportional

to the thickness of the remaining conductive

oxide. It has proven to be very difficult to make a thin film as sensitive as the ceramic

type thick films. <2>

Ohmi

Approx 200 nm

AdtortMd Oxygen Q- Q- 0"

Daplstad (ot Elactrons)

Conducting Region

Contacts

- Thin Film Semioondut

SubttrM*

Fig. 5 Thin-film n-Type Semiconductor Gas

Sensor

7
To retain the sensitivity of a thick film and

the power efficiency of a micromachined

device an ideal combination would be to put a

thick film on a micromachined sensor

structure. This author found it very difficult though to apply a thick film onto a thin,

micromachined membrane without breaking

the thin thermally isolated membrane

substrates (only laboriously repeated

applications of ink slurry drops and

subsequent heating to drive of the solvent worked).

Thin-film are probably the only possible film

that can be deposited on thin thermally

isolated membranes without breaking them. A

problem with thin film sensors is that the

resistance often is not controlled by the bulk

electron density, but by grain boundaries in the films. In principle grain boundaries should

be avoided ~ single crystal films should be

used for easy interpretation. But thin (5000 A)

single crystals are not obtainable in the usual

crystal growing tecliniques, and evaporated or

sputtered films inevitably have grain

boundaries. Again intergranular contact

resistance is involved in determining the

resistance of the film, and, because oxygen

cannot directly reach the intergranular contact

(as it does in the powder case) it must diffuse

in and out at the grain boundary. This makes

for long time constants. Blocking the grain

boundaries completely (gold deposition was

used in one attempt) is a solution if an

effective block to O" diffusion can be realized.

The major obstacle to more rapid progress with thin film micromachined sensors is that the sensitivity of thin films to gases is not

yet very well imderstood. Except for the case of the thin-film H2S sensors, micromachined

Taguchi sensors have not yet replaced their commercially available counterparts. The

currently available devices, already small and

inexpensive, will only be replaced quickly

when newer technology is improving upon

the existing product in terms of

:

>Reproducibihty

>Cost

>Sensitivity >Response time

>Concentration Range

> Specificity

>Reversibility

>Stability

>Power consumption

At this time the best course for progress in the Taguchi sensor area is to optimize thin film technology for the oxide semiconductor, use planar devices (reproducibility and cost) and concentrate on implementing less powerconsuming microheater elements (power

efficiency). The introduction of micro

technologies could easily bring the power

requirements down by a factor of 10 as we

have seen. These devices will cost more that the planar ceramic devices but they will outperform them in terms of power needs and

reproducibility.

From the above example it is clear that microfabrication cannot be pushed as a generic

solution for obtaining all of the desirable

characteristics in a sensor. For example,

poisoning of metal oxide sensors, the humidity effect, or of sensors in general that depend on catalysis is a major issue that will not be resolved by implementing

micromachining technology by itself.

Back-CellTM jrade mark by TSDC

Nafion^^: Trade mark by Dupont

References:

[2] Yamazoe N., Sensors and Actuators B,

6(1992) 9-15.

[3] Harmer A.L., Report of "European

Research on Advanced Sensors", for the Department of Trade and Industry, pp. 350, 1991.

[4] Tschulena G., "Sensor Markets in Europe." Battelle Conference on Sensor

Industry in Europe, Geneva, Sept. 1989.

[5] Gibbs, T.K., "Electrochemical

Technology in Industry a UK Status Report." Ed. by Tait S.J.D., SCI Electrochemical

Technology Group, 1991.

[6] Maseeh, F.; Tiemey M.J.; Chu, W.S.;

Joseph, J. ;Kim, H.-O.L.; Otagawa, T., Proc.lnt.Conf.on Solid-State Sensors and

Actuators, 359 (1991).

[7] Spindt, C.A., Holland, C.E., and Stowell,

R.A., 1984; Journal de Physique,

Compendium C9, Supplement to Volume 45,

No. 12, pp. C9-269, C9-278.

8
Gas Sensing for Industrial Safety and Health

Alan A. Schneider and Joseph D. Jolson

Mine Safety Appliances Company

Instrument Division

P.O. Box 427

Pittsburgh, PA 15230

Sensors and instruments which are to be used in the industrial

world must be capable of running without trouble for periods of

many months. This means near zero maintenance, low zero drift

with no false alarms, ruggedness, operation by workers with

minimal training, along with many other criteria which may be

specific to the particular application. Gas sensing technologies and instrument designs are discussed as they meet or fall

short of these criteria, including electrochemical sensors,

infrared, catalytic sensors, GC, IMS, semiconductor sensors, and

portable and permanent instruments.

Introduction

Today's user of industrial gas sensing instrumentation is demanding

much better performance. In the

area of industrial health and safety, agencies like OSHA have insisted that gas sensing move out of the

laboratory and into the work place.

In the area of process control,

much better gas sensing instruments

are required to satisfy modern production needs. No longer are chemists alone performing gas analyses;

rather, the average worker now has

access to instruments which display

gas concentrations automatically

and tell him whether those concentrations are outside acceptable

limits. Employers and employees

alike are insisting that these instruments function reliably.

The ideal industrial gas sensing

instrument should exhibit the following characteristics:

Wo false alarms. This is one of the

most important criteria. No

matter how good the instrument, it will not be in use

very long if it is plagued by

false alarms.

Near zero maintenance. An instrument which requires complicated or frequent maintenance

will certainly be quickly replaced by on that does not.

Sensor life at least one year. Even

two-year minimum lives are

being demanded in some cases

today.

Stable zero with no negative drift.

Zero stability is required for

user confidence and to prevent

false alarms. Displays showing negative numbers for gas

concentrations invite distrust

of the instrument.

Fast response. Response times of

less than two minutes are generally required for industrial

safety and health measurements. Less than fifteen seconds is preferred.

9
Low span drift. Under a known concentration of gas, minimal

drift of the output of an instrument with time is important, but less so than drift

of the zero signal with no gas

present. Users expect some

drift in span which can be

corrected by recalibrating,

but are much less tolerant of

zero drift.

Low Cost. Tolerable cost for a sensor is in the range of $100.

Desirable cost for a simple

instrument is $500. For a more complex instrument, users

expect higher costs.

Fails gently with plenty of warning. Failures of sensor and

instrument are tolerable, but

the user should have plenty of

warning. The user would like

to see the instrument continue

to operate after failure, with

reduced specifications.

Rugged. The instrument must tolerate abuses typical of the industry to which it is sold.

No adjustment at turn-on. An unhappy user is one who must wait

five minutes for the unit to

warm up and then must adjust

the unit before use.

Operable by untrained workers. It

is usually not an instrument

technician who will be operating most instruments.

Very fast calibration . Five minutes

is a very long time for an instrument technician who must

calibrate 300 instruments.

Easy sensor replacement with no

adjustments. Complicated setup

procedures after sensor replacement can lead to errors.

Highly selective or broad-band as

desired . Normally the user

wants to see only the gas in

which he is interested without

interference from other gases.

At times a broad range is desired, i.e., for a class of

chemicals

.

Broad range of sensitivity . Desirable is a sensor which can

accommodate several decades of

change in concentration.

Stable over temperature^ pressure

and humidity . Sometimes a difficult task, but expected by

the user.

Sensing Technologies

Some of the sensing technologies

with which the authors have had

some experience are:

electrochemical sensing for such

gases as CO, H2S, Clj, NO, NO2, O2,

ethylene oxide, and HCN;

non-dispersive infrared for a variety of gases;

photoacoustic infrared;

pelement combustible gas sensors;

gas chromatography using photoionization and flame ionization detectors ; ion mobility spectroscopy for explosive vapors, drug detection, and

chemical warfare agents; and

semiconductor sensors for a wide

variety of gases.

Electrochemical sensors. An electrochemical sensor typically uses

two or three electrodes, one of

which, the sensing electrode, allows diffusion of the gas of interest to the sensing catalyst. In

its simplest and most common form,

the gas is oxidized or reduced at

the sensing electrode and the resulting current is measured. This

10
type of cell, an amperometric cell,

produces a current which is directly proportional to the partial pressure of the gas outside the cell.

Another type of electrochemical

cell is the potentiometric cell

which produces a logarithmic signal, similar to a pH sensor.

An example of a common amperometric

cell is the CO cell, which is used

industrially at the rate of tens of

thousands per year. It uses an acid

electrolyte with a sensing, counter

and reference electrode. A potentiostat holds the working electrode

at a fixed potential with respect

to the reference electrode. The

following equations represent the

reaction scheme:

CO + HjO = CO2 + 2H'^ + 2e' Sensing

^Oj + 2H"^ + 2e" = H2S Counter

CO + = CO2 Overall

Figure 1 shows the output of this

sensor over the range of 0 to 1200

ppm CO.

0 20 40 60 80 100 120

CO Concentration, ppm

Figure 1. Linearity results for

twenty 3-electrode CO cells. The

solid line represents a least

squares fit to the data. The error

bars represent the desired goal of

±5% nonlinearity

.

Figure 2 shows the response of a

typical CO amperometric sensor.

Fifteen seconds to 90% is quite

good in most industrial applications.

Some advantages of electrochemical

sensors include:

a two year life;

inexpensive;

fairly selective;

rugged

;

fails gently;

can be compensated for temp.

;

ppm sensitivity;

fairly stable zero;

stable span;

inexpensive; and

low power (microamperes)

.

Some limitations include:

liquid electrolyte; and

somewhat limited temp, range.

110

90

0 10 20 30 40 50 60 70 80 90

Time After CO Exposure, sec Figure 2. Typical response for a 3-

electrode CO cell. (a) 100% of

final value, (b) 97% of final value

(25 ± 8 seconds) and (c) 90% of

final value (15 ± 7 seconds)

.

Infrared Sensors. There are three

types of infrared technology in

common use for gas sensing: (1)

dispersive infrared, (2) non-dispersive infrared, and (3) photoacoustic infrared.

The most common dispersive technol11
ogy in use today is Fourier transform infrared (FTIR) . It is expensive, requires a technician, but is

very selective and sees many compounds . Non=dispersive infrared (NDIR) uses

filters to select one wavelength

for one compound. It is less expensive than FTIR, easy to use, but

its sensitivity is limited to 10 or

100 ppm,

Photoacoustic infrared is similar

to NDIR, but uses a microphone as a

detector in a closed cell which is

repetitively filled by a pump. Its

sensitivity can be as small as 0.1

ppm, and it is characterized by a

very stable zero. Its signal is

generated as the gas in the closed

cell is illuminated by a chopped,

single-wavelength source; the gas

expands, creating pressure waves at

the chopping frequency which are

detected by the microphone.

Some advantages of infrared instruments are:

very selective;

very low zero drift, especially photoacoustic;

low span drift using source

degradation compensation;

wide range.

Some limitations are:

high power (tens of watts);

moderate cost ($2000-$10, 000) ; can fail abruptly.

Pelement combustible gas sensors.

Pelement combustible gas sensors

use a hot wire covered by a high

surface area ceramic impregnated

with a catalyst. This sensing element is combined with a compensator

element with no catalytic activity.

The two are used in a bridge circuit at high temperature (typically

>300C) . As the sensing element

sees a combustible gas its resistance changes, creating an imbalance in the bridge. The compensator corrects for differences in

thermal conductivity and for shifts

due to other gases such as water

vapor

.

Some advantages are:

detects all combustible gases

but doesn't discriminate;

stable;

long life (more than 2 years)

;

wide temperature range;

inexpensive (sensor $200, instrument $1000)

;

generally fails gradually;

rugged ; and

requires no maintenance.

Some limitations are:

high power (several watts)

;

typically narrow range; and

signal first incrases then

decreases with increasing

gas concentration - cannot be used at high concentrations .

Gas Chromatography. This wellknown technique uses a column to

separate compounds which are detected by electron capture (EC) , photoionization devices (PID) , or

flame ionization devices (FID)

.

GC can see many compounds very effectively when operated by a

trained technician. It can also be

configured to operate without an

attendant for a few set compounds.

Its advantages are:

versatility;

high sensitivity; and

certified technique for many

gas analysis schemes.

Its limitations are:

slowness

;

maintenance required;

high power (tens of watts)

;

high cost.

Ion Mobility Spectroscopy. IMS is

the technique of choice for chemical warfare agent detection because

of its high sensitivity (10"^'

grams /cm^) . Compounds in the incoming air stream are ionized and

12
these ions are then accelerated

though a field. Ions are detected

by an electrometer, and ion mobility in air is calculated by time-off light measurement.

IMS has been used for explosive

vapor detection, for drug and drug

precursor detection, and for industrial pollutants such as HCl.

j Its advantages are its extreme sen1 sitivity and speed.

Its disadvantages are its high power, expense, and its cross sensitivity to many compounds. In fact,

a large response from compound A

can be completely suppressed in the

presence of compound B of much

higher electron affinity.

Semiconductor Sensors. Semiconductor sensors use a film semiconductor such as polycrystalline tin oxide. Resistance change of this

heated film is measured as gases

adsorb on the surface.

Such devices are very inexpensive

($20) , have good sensitivity for

some gases (i.e. HjS) . They can see

a very broad range of gases.

Semiconductor sensors use moderate

power (ca. 1 watt), are not very

selective (many see water vapor)

,

and are limited in that the zero

signal is not very stable.

fined-space applications.

The second photograph shows a disposable alarm for CO labeled CRICKET. It will operate for one year

with only a weekly operational

check. It has two gas alarm levels

which are indicated by different

audible alarms. It is used in steel

mills and coal mines.

The third photograph is of a MODEL

6000 permanent instrument. It can

receive inputs from multiple sensors, display them locally with

alarms, and communicate with a central data collection console over a single twisted pair of wires. It

is used in a variety of industries.

Figure 3. Portable gas sensing device.

Commercial Instriiments

Some examples of commercial gassensing instruments are shown in

the following photographs. The

instrument labeled PASSPORT is a portable device which can accommodate up to five sensors. As shown

it incorporates a combustible sensor, and three electrochemical sensors for O2, CO and HjS. Its rechargeable battery will run 10

hours. In is used in many con13
Figure 5. Instrument for receiving,

displaying, and communicating

multiple sensor outputs.

14
Gas Sensor Needs in Environmental Testing

David Friedman

Office of Modeling, Monitoring Systems and Quality Assurance

Office of Research and Development (RD-680)

U.S. Environmental Protection Agency

Washington, DC 20460

The paper reviews the multiple roles EPA plays in environmental monitoring methodology, discusses a number of applications for innovative gas sensor technology in the environmental field, describes what EPA

is doing to facilitate innovation and explains how companies and other organizations with new technologies can obtain EPA's assistance in commercializing their new products

With respect to innovation in environmental

monitoring methodology, the Administration and the Agency are strongly committed to fostering and promoting

innovation in monitoring technology. The Environmental

Protection Agency (EPA) plays several key roles in this regard.

This paper will review the multiple roles EPA plays in environmental monitoring methodology, discuss a number

of applications for innovative gas sensor technology in the environmental field, review what EPA is doing to facilitate innovation and how innovators can obtain EPA's assistance

in commercializing the new products.

EPA'S ROLES IN ENVIRONMENTAL MONITORING

METHODOLOGY

Evaluator

Many potential customers are wary of using a new

technique without some assurance that the technology does

the job it is marketed to do. EPA serves as a neutral evaluator of new technologies. The Agency conducts or oversees evaluation studies and publishes performance data

that assist innovators in breaking down market place

acceptance of new ideas and approaches.

Facihtator

EPA's regulations have, in the main, served as the

driving force behind the development of the environmental

monitoring marketplace in the United States. The air, water, and hazardous waste regulatory programs have, over

the years, served as a catalyst for advancing the state-of-theart in environmental monitoring technology. The regulatory

programs have continuailly added new compounds to the

Hsts of chemicals of concern, have lowered the levels of concern for existing compounds to reflect new toxicological

information, and have issued many regulations establishing

monitoring requirements. These requirements have had the

effect of establishing a market for innovation.

A second manner in which EPA serves as a facilitator of new technology is by bringing the developer and user communities together. For example, EPA sponsors forums

such as the annual Waste Testing and Quality Assurance

Symposium that highlight new monitoring technology and

serve as a way of both informing a large audience about new developments and encouraging them to use new, more

cost-effective tools.

Innovator

As an innovator itself of innovative approaches to environmental monitoring, EPA has an active research

program to advance the state-of-the-art not only at our

three monitoring research laboratories but also at our

regional laboratories. EPA conducts innovative research

both on ideas generated internally, and through Federal

Technology Transfer Act Cooperative Research and

Development Agreements, assists outside organizations in bringing their innovations to market.

Enabler

The final role that I want to briefly highlight is that of an enabler. In several of EPA's regulatory programs,

methods must have prior EPA approval before they can be

used for complying with regulatory monitoring

requirements. For example, the drinking water, ambient

air, and certain parts of the hazardous waste programs have

such requirements. In cases where EPA approval is needed,

15
it is clear that EPA plays a critical and pivotal role.

In order to facilitate innovation in monitoring

methodology, EPA is exploring changing its approach to methodology specification by moving to a system whereby

EPA establishes performance specifications for the measurement rather than approving specific methods for conducting the analyses. Such a change would remove EPA

from the approval business and allow people to use new

methodology as soon as its becomes available. This does

not mean that EPA would no longer publish monitoring

methods. EPA would still publish methods, but the methods would serve as guidance rather than as requirements.

APPLICATIONS FOR GAS SENSORS IN

ENVIRONMENTAL TESTING

Air Monitoring

Fugitive emissions

As part of the Agency's efforts to prevent or reduce

air pollution, EPA regulations [1] require facilities to monitor on a monthly schedule pumps, tanks, valves, piping,

and other potential sources of leaks of volatile hazardous

air pollutants to detect product or raw material leakage. If such leakage is detected, then action needs to be taken to correct the problem. Current regulations require

monitoring using EPA Reference Method 21. Method 21

is a procedure for using a portable VOC detector to screen

for organic emissions. The method establishes performance

standards rather than requiring a specific instrument of

measurement technology.

Current approaches are to manually go from valve to

valve, fitting to fitting, pump to pump and check for leaks.

If rugged sensors could be developed that could be

permanently install at each monitoring location with the sensors then being remotely interrogated by computer,

several benefits would accrue. From an environmental

protection standpoint, a much earlier indication of seal

failure would be obtained. The facility would also benefit

both from reduced product/raw material loss, and by

eliminating the expensive labor involved in conventional

monitoring.

For this application, it is necessary for the detector to be able to discriminate concentrations of 500 ppm higher

than background levels. Thus one could attack the problem

with either specific or nonspecific sensors. If compound

specific sensors were developed, it might be easier to discriminate between source and background.

Odor monitoring

A portable odor meter is needed for evaluating

potential air emissions from such facilities as dredging

operations, wastewater treatment plants, and waste management sites. Often the Agency receives complaints

from citizens about noxious odors that frequently do not show up on typical air monitoring equipment.

A field deployable monitor (i.e., ideally less than 10 pounds and less than 1 cubic foot) is needed that can sell for less than $5000. Such devices could then be set up

around potential sources and used to monitor for odors. If such devices were available, it is conceivable that regulatory

and permit officials might then estabhsh objective standards

for noxious odor emissions. Given the subjective manner

in which odors are determined today, such standards have

not been developed.

Mercury monitoring

Several states have found widespread mercury

contamination in their water bodies and believe that the contamination results from mercury present in the ambient

air. This appears to be an emerging problem and will require extensive ambient monitoring to resolve the issue. To cost-effectively conduct the monitoring necessary to resolve this issue, field deployable monitoring devices for use in monitoring ambient air for mercury are needed.

Spill monitoring

When an accident occurs and chemicals are spilled, on-site personnel require portable, quick response

instruments to monitor what is happening. For these

situations, we need rugged, easily used, easily deployed

devices that can sit in storage (for example in a emergency

response vehicle) and then be put into operation relatively

quickly by the emergency response personnel.

It would probably be ideal if sensors for the more common volatile organics could be developed that could be

plugged into a universal "counter". In addition, for screening purposes, sensitive, broad spectrum sensors would

be needed.

The required sensitivity for the sensors would be a function of the specie's toxicity and hazard potential. EPA

has a toxicological data base called IRIS [2] that can be

used to determine an appropriate sensitivity for hazardous

substances of interest.

Environmental Monitoring

In the environmental monitoring arena several applications for rugged, sensitive, low cost, species selective gas sensors come to mind.

16
Ambient Air Monitoring

Ozone formation in the troposphere poses a significant threat to human health and to the environment. Through

the State and Local Air Monitoring Stations (SLAMS) and

the National Air Monitoring Stations (NAMS) continuous

monitoring is conducted for several species important to assessing ozone formation. These include:

- NOx

- VOC

- SOx

In addition, recent advances in continuous monitors

are cdlowing EPA to expand the monitoring to include

specific organic compounds which are known precursors to ozone. For further information on species and

concentrations of interest see 40 CFR 58 [3] Monitoring,

however, is expensive and the number of monitoring

stations for which resources are available is much less than

would be desirable. New types of stable, rugged, sensitive, selective gas sensors would thus find a ready market.

Mobile Source Monitoring

Automobiles, trucks, and busses comprise a major

source of contamination to the air. Currently automotive

emissions are controlled through a system of

premanufacturing certification and periodic vehicle

inspection and maintenance. The annual or semiannual

inspections are time consuming and expensive. A problem

can develop that leads to high emissions and the vehicle could operate for many months before its scheduled

inspection. Alternative procedures under development can

reduce the cost of testing but cannot operate in a real time

mode. The vehicle still has to go to the detector. Onboard

instruments for identifying out of specification performance

can hold a key to this problem. Because of the need for such devices to be small, rugged, and inexpensive solid state sensors may be the ultimate solution.

Thermal treatment system monitoring

Thermal treatment is both a primary means by which

toxic wastes are destroyed and by which resources, in the form of heat value, are recovered. However, incinerators,

boilers, and furnaces pose a hazard if hazardous chemical

emissions are not adequately controlled.

Many thermal treatment units operate in a batch mode

or intermittent mode. Because of the constantly changing

operating conditions, it is very difficult to ensure that emissions remain under established control limits. In order

for the public to have confidence in thermal treatment as a means of waste disposal, continuous monitoring of stack emissions will be necessary. Proper sensors able to respond

to mercury, organohalogen compounds, or polyaromatic

hydrocarbons might serve as rugged, low maintenance

alarms to alert the treatment unit operator to out of control

conditions.

Undergroimd Storage Tank Monitoring

Groundwater contamination resulting from leaking

underground storage tanks (e.g., gasoline, fuel oil, solvents)

has historically been a major source of environmental

contamination. To prevent future problems, changes in tank design and monitoring have been instituted in recent

years. Underground storage tanks are now equipped with

double walls and interstitial zone monitoring for early leak

detection. In addition, monitoring of the vadose zone around the tank is also used to detect leakage. Monitors

for use in these applications need to be able to perform for many years without servicing while buried in the ground or between the tank walls. Sensors could either be ones

sensitive to organic compounds in general or to specific

products.

Site Characterization

EPA has looked at the issue of how to cost-effectively

monitor to detect ground water contamination and has

found that the presence of volatile solvents often serve as early indicators of contamination. When ground water becomes contaminated with volatile solvents, the volatile organics tend to move through the vadose zone. Therefore,

monitoring the soil gas can serve as a convenient and

effective means of monitoring ground water at contaminated sites.

The technology needed is akin to that needed for the underground storage tank problem with the exception that

site monitoring might require a larger array of sensors than

might a tank installation.

Personal Exposure Monitoring

Personal exposure monitoring for either worker

protection or for exposure assessment studies are additional

promising applications of sensors.

In the personal protection arena, compact, light weight

devices that persons working in hazardous environments

can wear to monitor exposure to toxic chemicals is one area

that you might consider. A second, similar application, is exposure measurement. Here the issue is not whether a

permissible exposure level is being exceeded. Instead, we

need to be able to assess a person's exposure as they go

about their normal activities as a means of determining risk.

In the personal protection application, multitoxicant

sensitivity may be usable, while compound selective detectors might be needed for risk assessment detectors.

17
OPPORTUNITIES FOR COOPERATIVE

DEVELOPER/EPA EFFORTS

For developers of new monitoring technology, dealing

with EPA can be a daunting task. Many organizations

within EPA have responsibilities in this area. For example,

the various EPA regulatory program offices all have units who are responsible for measurement technology used in implementing the programs under their authority. The

Office of Research and Development's three national

monitoring research laboratories (i.e., EMSL/CIN,

EMSL/LV, and AREAL/RTP) also play major roles in the method development and approval process. EPA recently

issued a brochure that describes the method approval

process used in each of EPA's regulatory programs and

gives key contact persons. I have a limited number of these

booklets with me and will be happy to give you one if you

see me after the session.

In a nutshell, where you enter into EPA with new

technology depends on the method's state of development.

Those of you with technologies that are ready for the marketplace should contact the appropriate EPA office shown in the brochure.

If your product is in an earlier stage of development,

then you have more options. The Office of Research and

Development, our regional laboratories, and, in some cases, regulatory program offices may be able to help you develop

and evaluate new monitoring technology. Cooperative

Research and Development Agreements (CRADA) under

the Federal Technology Transfer Act offer industry an

effective mechanism for working with EPA scientists to speed up the development process. EPA can assist you

with technical advice, can conduct joint research with you, and can help by in conducting field evaluations of new

technologies. In this latter regard, EPA can often help in identifying appropriate sites for conducting real world tests of new monitoring method evaluations, can help ensure that the evaluation study is designed and conducted properly,

and can therefore ensure the credibility of the resulting

data.

The Agency's Innovative Technology Council (ITC)

has issued brochures that describe which EPA organizations can assist with various environmental technologies and the procedures for entering into a working relationship with

EPA. In addition to the previously mentioned Monitoring

Methods Approval Brochure [4], the Council has issued

Accessing EPA [5] which describes the interests and role of

each major EPA office in encouraging the development of

innovative technologies and lists the office's Innovative

Technology Advocate. The brochure Federal Technology

Transfer Act Program [6] presents an overview of the CRADA process. The Council is also developing a catalog

which describes appropriate EPA organizations that are

interested in establishing CRADA's with technology

innovators.

In addition, the ITC is conducting a study to identify

innovative monitoring technology needs and expects to issue a report within the next four months. This report will present information on monitoring problems for which

innovative solutions are needed and for which the Agency

feels a successful innovator will find a ready and profitable

market. The report will describe the problem, likely users

(i.e., purchasers) of the technology, and what properties the innovation will have to possess in order to be a commercial

success.

Finally, it is important to mention the Administration's new Environmental Technology Initiative. In his State of

the Union speech. President Clinton outlined a new

initiative to accelerate environmental protection while

strengthening America's industrial base. The focus of this initiative will be to harness the energies of EPA and other

federal agencies to stimulate and accelerate the development, use, and export potential of innovative

solutions to environmental problems. Environmental

monitoring methodology is one of the areas that has been

targeted for emphasis.

The Administration has proposed to allocate $36

million in FY 94 with a total of almost $1.8 billion over

nine years to this initiative. Much of the money will be

used to fund joint efforts with other federal agencies and

the private sector. This program is designed to harness the

expertise, facilities, and abilities of the DOE, the DOD and

the other federal agencies to this effort. Therefore, you

might want to consider establishing a three way partnership

when your technology may also be of interest to these other

agencies. • ^

This paper covers a number of subjects in order to give you the reader:

1. an appreciation for EPA's multiple roles and

responsibilities with respect to fostering innovation

in environmental monitoring technology,

2. an appreciation for the variety of environmental

monitoring problems for which gas sensor technology might offer a potential solution, and

3. a better understanding of how to approach EPA

for assistance in helping you to commercialize

innovative solutions to monitoring problems.

Time did not permit covering these subjects in detail. For further information on any of these areas, please contact the individuals listed in the brochures mentioned or,

if you have a problem in finding the correct individual the

18
author maybe reached at 202-260-3535/FAX 202-260-4346.

REFERENCES

[1] Code of Federal Regulations, Title 40, Part 61, US

Government Printing Office, Washington, DC 20402-

9328

[2] U.S. Environmental Protection Agency, 1993. Integrated Risk Information System (IRIS) Online.

Office of Health and Environmental Assessment,

Environmental Criteria and Assessment Office,

Cincinnati, OH 45268.

[3] Code of Federal Regulations, Title 40, Part 58, US

Government Printing Office, Washington, DC 20402-

9328

[4] Monitoring Methods Approval Brochure, US

Environmental Protection Agency, Office of Modeling,

Monitoring Systems and Quality Assurance (RD-680),

Washington, DC 20460, EPA/600/F-93-011, February

1993

[5] Accessing EPA, US Environmental Protection Agency,

Technology Innovation Office (OS-llOW),

Washington, DC 20460, EPA/542/F-93/002, June 1993

[6] Federal Technology Transfer Act Program, US

Environmental Protection Agency, Office of

Environmental Engineering and Technology

Demonstration (RD-681), Washington, DC 20460,

EPA/600/F-92/028, July 1992

19

Gas Sensing in the Automotive Environment

Joseph Giachino and Julie Konrad

Electronics Division

Ford Motor Company

Dearborn, MI

The task of meeting lower emission standards, achieving improved diagnostics of emissions and not impacting customer requirements for performance requires the development of improved emission

gas sensors. This paper reviews the status of oxygen sensing, requirements for onboard exhaust

sensing, and exhaust gas sensing needs.

INTRODUCTION

Many modem internal combustion engines are computer

controlled to meet efficiency, performance and emission

requirements. As an example, a typical Ford Electronic

Engine Control (EEC) system contains these powertrain

sensors:

Exhaust Gas Recirculation (EGR) Valve Position Sensor

Air Charge Temperature (ACT) Sensor

Crankshaft and/or Camshaft Position (CPS) Sensor

Mass Airflow (MAP) Sensor

Vehicle Speed (VSS) Sensor

Throttle Position (TPS) Sensor

Cylinder Knock Sensor

Heated Exhaust Gas Oxygen (HEGO) Sensor

The first six sensors are used in control of air, fuel and

spark inputs, while the knock sensor and HEGO are used

to determine engine response to these inputs. [1]

The HEGO primarily measures the equilibrium level of

exhaust gas Oxygen. This equilibrium Oxygen level in the

exhaust gas stream is used as an indirect measurement of

air/fuel ratio. EXHAUST GAS EMISSION

Because of the favorable emission reduction of ThreeWay-Catalysts (TWC), most automotive control systems

use stoichiometry (where all the carbon and hydrogen are combusted) for the feedback control reference point.

Fortuitously, this corresponds to the "switch-point" of the

HEGO sensor. The theoretical ratio of air mass to fuel mass for stoichiometry is 14.7 lbs. of dry air to 1 lb. of

typical gasoline. The common term used in the automotive

industry to denote normalized air to fuel ratio is lambda

(A). Lambda is defined as

A = air/fuel

air/fuel at stoichiometry

Therefore, a A of 1 denotes stoichiometry, a A > 1 denotes

a lean condition (excess air) and a A <1 denotes rich (excess fuel).

Air/Fuel Ratio Control

At the core of stoichiometric emissions control algorithms

is the primary feedback gas sensor located in the exhaust

pipe. This is the one sensor in the system in which it is imperative to have absolute accuracy. Adaptive routines in engine control strategies trim the output signal to compensate for drifts in the system, allowing for slight

shifts in the feed forward sensors and actuators (intake air mass, fuel request vs. actual, engine and intake

temperatures). These adaptive routines reference the

emission gas sensor, and optimize the entire system to the

exhaust gas sensor output. Our ability to lower emissions

is limited by the accuracy of the feedback exhaust gas

sensor.

The key to air fuel ratio control is the exhaust gas oxygen

sensor. There are two basic types of oxygen sensors in use

today; Zirconium Dioxide (Zr02) and Titanium Dioxide

(Ti02). [2]

The most common is the Zr02 sensor which consists of a thimble-shaped section of Zr02 with thin Platinum

electrodes on the inside and outside of the thimble. The

inside is exposed to atmosphere and the outer section to the exhaust stream. There is a voltage output proportional

to relative partial pressure of Oxygen in the exhaust gas

21
compared to that in ambient air. The potential difference

is described by the Nernst equation,

E = ICrin[PR,f/P„,3,]

2e

where K is the Boltzman constant, T is the temperature in degrees Kelvin, e is the electronic charge and the

respective Ps are the partial pressures.

The Titania sensor relies on the fact that the electrical

resistivity of Ti02 changes orders of magnitude upon

exposure to Oxygen. The change in resistivity is dependant on the temperature and partial pressure of Oxygen.

The Oxygen sensor is used as an indicator of stoichiometry

for controlling catalyst input for lowering emissions. Such

a system can minimize the emissions of HC, CO and NOx.

The reason oxygen has been used is that these sensors are

accurate, durable and a good indicator of the desired

control point. These are the driving forces that now

require the development of HC, NOx and CO sensors. REQUIREMENTS FOR ONBOARD EXHAUST GAS

SENSING

Meeting lower emission standards and achieving improved on board diagnostics of emission systems may require the

development of improved emission gas constituent

sensors. Emission challenges include meeting increasingly

stringent governmental requirements designated

Transitional Low Emissions Vehicle (TLEV) to Ultra Low

Emission Vehicle (ULEV) levels. Constituents legislated

in these phases include Hydrocarbons (HC), Carbon

Monoxide (CO) and Nitric Oxides (NOx). Meeting these

levels may require improved control of the air/fuel ratio and spark. To optimally achieve this control, sensors that can measure constituent gases may need to be developed.

There is presently a requirement in California that the

driver be notified when his vehicle is exceeding emission

limits and that the failed component be identified. Many

states are considering similar legislation.

Exact sensor requirements to meet these regulations may

vary based on individual powertrains and strategies. All

such sensors will have to be durable over the life of the

vehicle.

Durability Needs in Exhaust Gas Sensors

Exhaust gas sensor life is mandated by law to be 100,000

miles in the vehicle environment. This forms the basis for

durability testing. Durability tests are not limited to temperature cycling, but add all environmental conditions

which could occur during vehicle life. The sensor must

survive abnormal system conditions such as extended rich

or lean conditions due to failure of other emissions

related components.

The preferred method to prove exhaust gas sensor

durability is with engine dynamometer stand, because it delivers all potential causes of sensor failure. This system

is capable of cycling all environmental variables, and can be semi-automated to facilitate the 2000+ hours required

for full durability prove-out. Variables to be manipulated

during such testing include, but are not limited to the

following:

Gas Temperature: (200 - 900°C) Normal exhaust temp.

Gas Velocity: 10-40{/min.

Air/Fuel Ratio Cycling: .9 1.1 A (normal control frequencies as well as edended

exposure) Excess Unburned Hydrocarbons and Oxygen:

(by inducing engine misfire)

consider as a full unburned cylinder, Vzd Thermal Shock: 5°C liquid water in 350°C sensor

(water condensation in exhaust stream during

vehicle restart) Pressure Shock: Peak 1000 K Pa

(from induced engine back fire) Gas Contaminants: Silicon, Sulfur, and trace Lead

from multiple test fuels

Packaging integrity tests include contaminant entry into

the sensor housing (ie. water) and exhaust/sensor sealing

especially with designs requiring a reference chamber.

The other Major criteria for an exhaust gas sensor is selectivity.

Selectivity Criteria for Exhaust Gas Sensors

Exhaust gas sensors selectivity is especially demanding

considering the multitude and magnitude of interference gases present in the exhaust stream. Before a single

constituent sensor can be seriously considered for emissions control or diagnostic applications, selectivity

tests would need to show promising results. Also when

sensing reducing agents oxygen might be the limiting

reactant. Externally supplied oxygen would increase the

complexity and cost, reducing overall system viability.

Selectivity is tested by maintaining the concentration level of the measured constituent while ramping each

interference gas through its vehicle exhaust range. The

change in sensor output is considered its selectivity error due to the ramped interference gas at that particular

signal level. Feedgas emissions levels corresponding to the

relative air/fuel mass ratio (lambda) for a representative

engine are shown below. Hydrogen is approximated at one-third the amount of Carbon Monoxide.

22
lambda HC CO 02 NOx C02

(ppm) (%) (%) (ppm) (%)

can meet the environment (i.e. resistive, surface wave) but can not meet tlie selectivity.

u.y / u.4iy2 131U 17.164

0.98 824 1.053 0.4903 1363 17.220

0.99 774 0.820 0.5539 1388 17.323

1.00 754 0.595 0.6733 1544 17.323

1.01 733 0.531 0.7519 1588 17.323

1.02 708 0.402 0.8496 1597 17.323

1.03 679 0.324 0.9496 1626 17.286

An example selectivity test for a hypothetical Hydrocarbon

(propylene) sensor to Carbon Monoxide would be to monitor signal output for the following conditions:

HC CO

(ppm)

02

(%)

NOx

(%)

C02 H2

(ppm) (%) (%)

754 1.298 0.6733 1544 17.323 3.90

1.053 - " "

" 0.820 " " "

" 0.595 " - - "

0.531

0.402 " " "

- 0.324 " " -

"

Other component characteristics that must be addressed

are:

Accuracy

Repeatability

Time response

Component to component variability

Output stability

These requirements may vary depending on the particular

system. All components will need to be able to be

manufactured with a high volume robust process.

Exhaust Gas Sensing Needs

The successful implementation of any of these

technologies will depend on developing the appropriate

sensing element and package for the automotive

environment. Packaging is the most crucial part of having

a sensor that is capable of existing in the environment.

Unfortunately, it is all too often the last thought in the

development process. Most successful developers for the

automotive industry realize that the package development

must be developed simultaneously with the sensing

element and the electronics.

The challenge is great and so are the rewards for those

that can produce the next generation of exhaust gas

sensors. ACKNOWLEDGEMENTS

The authors would like to thank Dr. Allan Kotwicki, Ford

Electronics Division for his contribution in developing

many of the test procedures and his discussions on sensor development.

REFERENCES

1. J. Paulsen and J. Giachino "Powertrain Sensors and

Actuators: Driving Toward Optimized Vehicle

Performance" 39th IEEE Vehicular Conf. Vol. II 1989 P., 174

2. E. M. Logothetis "Automotive Oxygen Sensors" in N. Yamazoe(ed) Chemical Sensor Technology, vol. 3, Tokyo:

Kodansha/Amsterdam: Elsevier, 1991, pp 89-104

3. H. N. Norton, "Sensor and Analyzer Handbook",

Prentice-Hall inc., Englewood Cliffs, NJ, 1982

To continue to optimize the performance of automotive

engines it will become necessary to measure the individual gases in the exhaust emission. In particular HC, NOx, CO

levels will have to be known to optimize the emissions of

internal combustion.

Many techniques [3] exist for gas sensing, including

electrometric gas sensors (such as Zr02 sensor), resistive gas sensors (such as Ti02 sensor), thermal conductivity

cells, heat of combustion sensors, chemiluminescence, gas chromatography, absorption spectrometry, nondispersive

infrared absorption and surface acoustic wave.

To date none, other than Zr02 and Ti02, have been

successfully adapted to the on vehicle environment. Some

can meet the selectivity requirements (i.e. chromatography,

spearometry) but can not meet the environment. Others

23

Chemical Gas Sensors and the Characterization, Monitoring, and Sensor Technology

Needs of the U.S. Department of Energy^

Glenn J. Bastiaans*, William J. Haas, Jr., and Gregor A. Junk

Analytical Instrumentation Center

and Ames Laboratory, U.S. Department of Energy

Iowa State University, Ames, IA 50011

The Office of Technology Development within the Dept. of Energy (DOE) has the responsibility of

providing new technologies to aid the environmental restoration and waste management (ERAVM)

activities of the DOE. There is a perception that application and judicious development of chemical

sensor technologies could result in large cost savings and reduced risk to the health and safety of

ERAVM personnel. A number of potential gas sensor applications which exist within DOE ERAVM

operations will be described. The capabilities of several chemical sensor technologies and their potential to meet the needs of ERAVM applications in the present or near term future will be

discussed.

In 1989, the U. S. Department of Energ>' (DOE)

committed to rapidly bringing all operating facilities into compliance with applicable laws and regulations

and to cleanmg up the contaminated sites and facilities by the year 2019 [1]. The Office of Environmental

Restoration and Waste Management (EM), within

DOE, is responsible for fulfilling this commitment.

Within EM, the Office of Environmental Restoration

(ER) has jurisdiction for an estimated 3700 hazardous

waste sites at DOE facilities; the Office of Waste

Management (WM) is responsible for management of

approximately 100 million gallons of high-level

radioactive waste in 327 tanks and more than 14

million 5

5 -gallon drums of various waste forms

including radioactive waste. The Office of Technology

Development, also within EM, is responsible for providing new technologies to ER and WM, when

needed, so the commitment can be fiilfilled.

The current emphasis in ER is on assessment of the nature and extent of contamination so there is great

interest in characterization, monitoring, and sensor

technologies. In the fiiture, these technologies will also

*This work was sponsored by the Characterization, Monitoring, and Sensor Technology Integrated Program, Office of Research and Development, Office of Environmental Restoration and Waste management, U.S. Department of Energy, under contract @-7405-ENG-82.

'Person to whom correspondence should be addressed

be needed for remediation and post-closure monitoring.

WM is focusing on ensuring adequate, permitted

storage capacity for existing waste, much of which will have to be processed before disposal. Characterization,

monitoring, and sensor technologies will also be

required before and during the processing and following

disposal.

Characterization and monitoring are typically

accomplished by taking samples of air, water, soil, waste, and waste process material, and sending them to analytical laboratories for analysis. Although this practice is effective, it is expensive and timeconsuming, in part because transportation and

maintenance of sample integrity and identity are

necessary. Some radioactive samples cannot be

shipped off site. Because of the large size of the DOE

commitment mentioned above and the projected enormous characterization and monitoring costs, there

is a perception that application and judicious

development of chemical sensor technologies could

result in large cost savings and reduced risk to the

health and safety of personnel.

Within the Characterization, Monitoring and Sensor

Technology Integrated Program (CMST-IP), chemical

sensors are defined as the components of

characterization and monitoring systems that produce

different, measurable, and reproducible responses when

exposed to different levels of specific chemicals or

classes of chemicals. In addition, the following criteria are believed to be applicable to chemical sensors:

25
Field deployable

Selective detection of analyte

Adequate sensitivity for application

Capable of unattended operation

Capable of long-term and continuous operation

Real time response

Inexpensive.

Activities to support the characterization and

monitoring efforts of the DOE have been organized to focus upon five critical problem areas:

Remediation of High-Level Waste Tanks

Containment of Existing Landfills

Characterization, Treatment, and Disposal of Mixed

Waste

Migration of Contaminants

Decommissioning and Final Disposal

Table 1 summarizes the potential sensor applications

within each of these problem areas.

Table 1 Remediation of High Level Waste Tanks

Tank Safety Issues Monitoring of Headspace Gas Concentrations

Hydrogen; N7O; NH:^; Organics

Characterization, Treatment, and Disposal of Mixed Waste

Waste Stream/Process Monitoring

Waste Streams During Processing

Waste Effluents (e.g. OfF-Gas Monitoring for VOCs; PICs; Metals

Containment of Exisitng LandHlls

In Situ Determination of Contaminants Beneath Landfills

Organics; Metals

Migration of Contaminants

Location, Type, and Concentration of Subsurface Contaminants

Chlorinated Hydrocarbons

Petroleum Hydrocarbons

Explosives; Pesticides; Herbicides

Decommissioning and Final Disposition

Long Term, Post Closure Monitoring

Organics

Other applications for gas sensors may arise in response

to needs for monitoring or characterizing a wide variety

of chemicals in the air and in the headspace over

different types of samples. Some of these needs may

derive from legislative mandates such as:

Clean Air Act

Safe Drinking Water Act

Resource Conservation and Recovery Act

Clean Water Act

Toxic Substances Control Act

State and Local laws

Chemical gas sensors are not the only technology with

the potential to meet DOE needs for characterization

and monitoring. Currently large number of samples are

collected in the field and sent to central laboratories for

analysis. While this practice is expensive, it may be

expected to continue indefinitely. It is also possible to build analytical laboratories into trailers which can be

field deployed on site. Samples would still need to be

taken, but sample transport and disposal would be

simplified.

Field deployable instrumentation presents the strongest

competition to chemical gas sensors. For example,

conventional optical spectrometers, gas chromatographs,

and mass spectrometers are all being adapted for field deployment. This route to field assay may be the most

expeditious in the near fixture although the deployment

of large numbers of these instruments may be cost

prohibitive.

26
The chemical gas sensor technologies which have the

potential to meet DOE characterization and monitoring

needs may be classified into at least three categories:

Fiber Optic

Piezoelectric Mass

Electrochemical

Two reports discussing these categories have recently

been produced under DOE sponsorship [2,3].

Fiber Optic Sensors

Chemical sensors that employ fiber optics exist in several forms [4-6]. The simplest types determine an

anal>te through observation of an intrinsic spectroscopic

property' of the analvte. In these sensor types, the

optical fibers serve only as light guides. The

spectroscopies commonly emplo>ed are optical

absorption, fluorescence, Raman, and surface-enhanced

Raman. Other spectroscopies beginning to be

investigated for sensor applications include infrared,

near-infrared, and ultraviolet reflection. Surface

plasmon resonance is attracting commercial interest for biosensor applications.

A more sophisticated class of fiber optic sensors employs recognition chemistry'. A chemical layer acts as a transducer or indicator in conjunction with an

optical fiber. The layer may either be placed at the

distal end or on an unclad portion of the optical fiber. The recognition chemistry may be reversible or

irreversible. Presently these chemistries are deployed by

coupling polymers, indicators, or combinations of the two, to detect such things as metal ions, ammonia.

hydrogen ion, oxygen, carbon dioxide, and

hydrocarbons. Sensors for all these analytes have been

demonstrated with different levels of success and work

is continuing. Enzymes can also be coupled to the

chemical layers to provide additional sensitivity.

Sensors based on irreversible recognition chemistries use reagents rather than indicators. Such sensors respond only to a single analyte exposure unless

additional reagent is released or otherwise delivered to regenerate the sensor. Such a reagent-based fiber optic sensor for trichloroethylene has already been field demonstrated.

Antibodies are also in the category of irreversible recognition chemistry. The highly selective binding of

an antibody can be coupled with an optical sensing

scheme to quantify the antibody/antigen interaction. Commercial immunoassay systems already employ such

schemes. Fiber optic immunoassay techniques for

clinical and other applications have been under

development, for example, by Ciba Coming Diagnostics

(Medfield, MA).

Considerable development work is in progress. Prototype systems that employ a variety of

spectroscopic techniques are being evaluated for environmental monitoring, and commercial devices are

available for selected applications. Issues of stability

and selectivity remain to be solved. Internal calibration

capability is a significant advantage of some fiber optic sensors [7]. Table 2 provides a rough indication of the current state of the technology.

Table2.

Analytes Estimated Dynamic Range

Trichloroethylene (TCE) Low ppb to ppm

Polvnuclear Aromatic Hydrocarbons < 1^ Tens to Hundreds of ppm

Hydrocarbons Tens to Hundreds of ppm

There is a great need to develop improved recognition

chemistries for fiber optic and other types of chemical

sensors. The development of sensor coatings that have

greater selectivity and sensitivity is expected to be a dominant research direction. For irreversible indicating

chemistries, development of systems to continuously

dehver reagents is possible and is presently an area of

active investigation.

Specific sensors will become available for some priority

analytes but the development of a large number of

highly selective indicators or coatings is not likely in the near term. Development of sensors which can determine

compounds as a class is clearly possible. Such sensors would indicate, for example, that a certain class of

contaminants is present and could measure the total

27
concentration. In the short term, it should also be useful

to deploy sensors that are capable of indicating

concentrations to only within an order of magnitude of

the actual value for various chemical classes. Such

sensors could provide valuable data on trends and

significant concentration changes.

Among the recognition chemistries needed by DOE, but

not yet available, are indicators for a variety of volatile organic compounds and some volatile explosives. If suitable recognition chemistries were developed,

chemical sensors for these materials could be available

in three to five years.

The establishment of an extensive field testing program

is also needed. Too few field tests are currently being

performed. An important aspect of such field testing is the packaging of the sensors for field use. A related issue is obtaining measurements that are representative

of the material of interest. If a fiber is simply placed in the environment or material of interest, the sensor response depends on location. If the sensor is reversible,

it can be moved to profile the environment. Otherwise,

sensors must be placed at a number of different locations.

Piezoelectric Chemical Sensors

Piezoelectric chemical sensors are a special class of

piezoelectric mass sensors, small electronic devices

which quantitatively respond to the amount of mass

deposited or sorbed on their surface. When such devices

are coated with materials that selectively sorb a

particular chemical or class of chemicals, they function as chemical sensors [8-10].

Piezoelectric chemical sensors currently exist as bulk

acoustic resonators (BARs) and acoustic wave guides

(AWGs). The BARs are made from thin piezoelectric

crystals or thin layers of piezoelectric material on a

supporting substrate. BARs operate with acoustic wave

propagation perpendicular to the surface and are commonly referred to as quartz crystal microbalances

(QCMs), thin film resonators (TFRs), quartz crystal

resonators, and piezoelectric resonators. The AWGs are made from the same materials as BARs but involve

acoustic wave propagation parallel to the surface. Various AWG types are surface acoustic wave (SAW),

flexural plate wave (FPW), Lamb wave (LW), and

shear horizontal (SH) acoustic plate mode (SH APM)

devices.

Piezoelectric chemical sensors are under development at many laboratories; some are being commercially

produced in limited quantities for a number of

applications. A prototype system for VOCs is being

field tested. Information on some known developers and

potential suppliers of piezoelectric chemical sensors for various applications is given in Table 3.

Table 3. Developers and potential suppliers of piezoelectric chemical sensors. Developer/Supplier Application

Microsensor Systems

Bowling Green, KY

SAW detectors with gas chromatographs, for industrial hygiene and

environmental control

Femtometrics

Costa Mesa, CA

SAW sensors for the measurement of ozone and detection of air borne

particulates

Amerasia Technology Inc. Westlake Village, CAPrototype SAW sensors for the detection of explosives such as TNT and

RDX

Universal Sensors

Metaire, LA

BARs with and without coatings for R&D use and for several sensing

applications

Xsensor

Delft, Netherlands

Manufactures SAWs, FPWs, and their support electronics in integrated

circuit form

Vaisala

Finland

SAW devices as dew point sensors

Ciba GeigySwitzerland SAW sensors for internal process control applications

Sandia National Laboratories (DOE)

Albuquerque, NM

SAW detectors, used with a gas chromatograph to measure VOCs

Ames Laboratory (DOE)

Ames, lA

BARs and AWGs for gaseous species (combustion gases, formaldehyde)

28
Current piezoelectric chemical sensors can measure

vapor concentrations (e.g. for VOCs) in the range of 10

ppm or higher; this sensitivity is thought to be adequate

for many DOE needs. In selected applications, the

sensitivity and/or selectivity of piezoelectric chemical

sensors has been enhanced by the addition of a

concentration and/or separation stage for treatment of

sample material before it is exposed to the sensor. Such

i work is in progress, for example, at Sandia National

Laboratories, Albuquerque, NM and Microsensor

Systems, Inc., Bowling Green, KY.

The inabilit>' to selectively determine a single chemical

in the presence of interfering chemicals is a current

limitation of piezoelectric, and most other types of

chemical sensors. Selectivity improvements are being

sought through sample pretreatment to remove

interferents and through pattern recognition analysis of

the responses from piezoelectric sensor arrays in which

each array element has a different coating.

At Iowa State Universit}' (Analytical Instrumentation

Center and Ames Laboratory') thin film resonator (TFR) measurement systems are being developed in a

field deployable form. Support electronics for the TFRs

in the form of oscillator and mixer circuits have been

developed as customized integrated circuits on a single

chip. The small size and low power requirements of the

TFRs and their support circuitry should make

deployment of sizable arrays of these sensors quite

feasible.

As in the case of fiber optic chemical sensors, major

research will be directed to finding sensor coatings that

will interact selectively with specific chemicals. Some

coatings may be found via Edisonian experimentation

based on known chemical interactions. Advances should

also be made in the ability to predict interactions

between coatings and species of interest via

computational and other models founded on the rapidly

increasing understanding of such interactions.

Additional development of arrays of piezoelectric

chemical sensors, for which coating requirements are

less demanding, is expected; new coatings and improved

pattern recognition methods will also be sought. Also in the near term, efforts will be made to produce and

couple more sophisticated sample treatment systems

(chromatographs, etc.) with highly sensitive but not

necessarily very selective sensors. Such chemical sensor systems would be both highly sensitive and selective.

Improvements in packaging for field deployment and

optimization of the support electronics and noise

reduction techniques are needed. Such improvements,

addressed most efficiently by interdisciplinary teams of

scientists and engineers, will certainly advance the

application of piezoelectric chemical sensors.

Electrochemical Sensors

Electrochemical sensors determine analytes through

measurements of their influence on the voltage, current, or conductance of an electrochemical cell [11-13]. For

gas sensor applications, the most common types of

electrochemical sensors are the semiconductor metal

oxide sensor, which operates on the basis of changes in conductivity, and amperometric sensors.

Selectivity of response with semiconductor metal oxide

sensors is obtained by mixing the oxide with a variety of

dopants and by operation at different elevated

temperatures. Amperometric gas sensors normally

include a membrane where gases come into contact with

the electrolyte of an electrochemical cell.

Electrochemical sensors exist and/or are under

development for the measurement of gases such as CO,

CO2, H2, SO2, hydrocarbons, and chlorinated

hydrocarbons. Improvements in selectivity and

sensitivity may be required for many potential DOE

applications.

Business Opportunities

A number of federal programs have been created to encourage private sector development of new

technologies and the transfer of technologies developed

in government laboratories. Cooperative Research and

Development Agreements (CRADAs) require the private

sector to provide in-kind matching funds to collaborate

with government laboratories. Within the DOE, a program known as the Partnership for Global

Competitiveness has been implemented to streamline the

process of establishing CRADAs. Funding authority

has been delegated to selected DOE contractors and the

legal process has been standardized.

Three other programs provide grants for the

development of commercializable technologies and do

not require participation of government laboratories or

contractors. These programs are:

29
Program Research and Development Announcements

(PRDAs)

Research Opportunity Announcements

Small Business Innovation Research (SBIR) Program

These programs often focus on specific areas. Details

and application procedures are published in the Federal

Register and Commerce Business Daily.

The transfer of existing technology is encouraged by

other programs as well. Within the Office of

Technology Development of the DOE there is a Technology Integration Program designed for this purpose. Contact can be made via the following toll- free telephone number:

Technology Integration Program

Matt Cain

800 845-2096

A second program is the American Alliance for Environment and Trade. Its mission is to foster public/private partnerships for national technology

development and applications. Contact may be made by

calling:

American Alliance for Environment and Trade

Sheila Conway

303 279-2700

Finally, there is a mechanism for locating technology

experts and special technical facilities within the federal

laboratories. The Locator of the Federal Laboratory

Consortium for Technology Transfer is the designated

point of contact for all the federal laboratories.

Inquiries can be made by calling:

Locator of the Federal Laboratory Consortium for Technology Transfer

800 775-7445

REFERENCES

[L] U. S. Department of Energy. 1991. Environmental

Restoration and Waste Management Five-Year Plan:

Fiscal Years 1993 - 1997. FY? DOE/S0089P

(Available to the public from the National Technical

Information Service, U. S. Department of Commerce,

5285 Port Royal Rd., Springfield, VA 22161).

[2.] "Chemical Sensors Technology Development Planning

Workshop", Ed. G.J. Bastiaans, Wm.J. Haas, G.A.

Junk, IS-5093 UC-900. (Available to the public from

the National Technical Information Service, address

above)

[3.] "Literature Search, Review, and Compilation of Data

for Chemical and Radiochemical Sensors Task 1 Report", Hazardous Waste Remdial Actions Progran,

DOE/HWP-130. (Available through National

Technical Information Service, address above)

[4.] Wolfbeis, Otto S., Ed. 1991. Fiber Optic Chemical

and Biochemical Sensors. Vol. 2. CRC Press: Boca

Raton, FL.

[5.] Norris, John O. W. 1989. Current Status and

Prospects for the Use of Optical Fibres in Chemical

Analysis. A Review. Analyst (London),

114(ll):1359-72.

[6.] Seitz, W. R. 1988. Chemical Sensors Based on

Immobilized Indicators and Fiber Optics. CRC Crit. Rev. Anal. Chem., 19:135.

[7.] .Jones, T. P., S. J. Coldiron, W. J. Deninger, and M.

D. Porter. 1991. A Field-Deployable Dual

Wavelength Fiber-Optic pH Sensor Instrument Based

on Solid-State Optical and Electrical Components.

Applied Spectroscopy, 45:1271.

[8.] McCallum, John J. 1989. Piezoelectric Devices for Mass and Chemical Measurements: an Update: A

Review. Analyst (London), 114(10): 1173-89.

[9.] Ward, M. D., and D. A. Buttry. 1990. In Situ

Interfacial Mass Detection with Piezoelectric Transducers. Science, 249(4972): 1000-7.

[10.] Bastiaans, G. J. 1988. Piezoelectric Transducers in Chemical Sensors. Edmunds, T. E., Ed.; Blackie: London, U.K., pp 295-319.

[11.] Meyerhoff, M. E., D. M. Prantis, H. S. Yim, N. A.

Chaniotakis, and S. B. Park. 1989. New Anion- and

Gas-Selective Potentiometric Sensors. Chemical

Sensors and Microinstrumentation (ACS Symposium

Series 403). Royce W. Murray et al., Eds.; American

Chemical Society: Washington, DC, pp 26-45

[12.] Madou, M. J., and S. R. Morrison. 1989. Chemical

Sensing with Solid State Devices. Academic Press

Inc.: Boston.

[13.] Wang, K., Bakker, E., Morf, W. E., Rusterholz, B., Spichiger, and Simon, W. 1991. Characterizationi of

Sodium-Selective Optode Membranes Based on

Neution lonophores and Assay of Sodium in Plasma.

CHn. Chem. 37(8), 1350-1355.

30
Thermal Microsensors for Environmental and Industrial Controls

Ulrich Bonne

Honeywell Technology Center

Bloomington, MN 55420

This review of thermal microsensors for gases focuses on the measurement of the physical state variables, physical gas properties, and concentrations of select species of interest. The impressive

diversity of demonstrated sensing functions, the challenges of quantifying sensor stability, designing

for low variability, and packaging for environmental ruggedness are discussed. The importance of

thin-film stress control, metallization feature size selection, and characterizing the sensor environment

as part of the specifications are pointed out, and quantified for several examples. The paper concludes

with recommendations for the development of standard physical property data for thin films of

common sensor construction materials and thermophysical gas-mixture properties so that the

affordability of microsensors, their small size, and low power consumption can more predictably lead

to successful applications and satisfied customers.

INTRODUCTION

To review all gas sensors for environmental and

industrial control, within the frame of this workshop,

would be a formidable task. This paper focuses instead on the discussion of the subset of thermal microsensor

R&D and manufacture, from the points of view:

(1) the needs we try to meet, (2) the opportunities

offered by and recent progress of micromachined

sensors, and (3) the challenges we are facing.

The purpose of the sensors R&D work at Honeywell

Technology Center (HTC) is to serve the needs of

Honeywell's three main controls businesses: Home

and Building Control, Industrial, and Space and

Aviation Systems. Stable and low-cost gas sensors are needed by all of them. Examples are sensors for flow,

pressure, humidity, oxygen, VOCs (and "fugitive

emissions" in general), CO, NOx, and gaseous fuel properties as needed for combustion (stationary and

automotive) and emissions control. One may group

these sensors according to what they sense:

1. (Composition-independent) physical state, such as pressure, temperature, velocity, (i.e. flow) or even

liquid level;

2. (Composition-dependent) physical properties, such

as thermal conductivity, density, viscosity, specific

heat, compressibility factor, and dew point (of

hydrocarbons, water, . . .); and

3. (Zhemical species or groups of species, such as metal oxide sensors for O2, CO, combustibles;

NDIR/UV (nondispersive infrared/ultraviolet) sensors for CO2, CO, H2O, hydrocarbons, NO [1], and others. The following limited discussion addresses the role of

thermal microsensors within these groups and characterizes their performance and Umitations.

DISCUSSION

The first set of thermal microsensors developed at HTC (and now manufactured at Honeywell's Micro

Switch Division) were flow sensors (i.e. hot film

microanemometers) featuring up- and downstream

sensing elements that were separate from the heater. Heater and sensors were and are still positioned on a

thin membrane of silicon nitride to enhance the sensor's sensitivity to about thirtyfold that of a soUd

silicon structure [2], while simultaneously reducing the

power input to the heater to a few milliwatts.

Whether front-etched or back-etched, the thermal

isolation provided by the membrane quickly led to a

proliferation of sensors, as shown in Fig. 1. Their

purposes range from the direct measurement of flow

and differential pressure [2]; thermal conductivity and

specific heat [3]; absolute pressure [4]; and of course, temperature, to sensing oxygen [5]; dew point; NOx

31
Flow and Differential Pressure Sigh

Thermal Conductivity

Pt V / ZrO,

Si

Sn02

Oxygen

Si3N4

Si

VOC, NO2. NO

Si

Absolute Pressure

\/ //////////

Si3N4

zzzx

Si

Fig. 1. On the microbridge sensor flexibility.

[6,7]; and combustibles by incorporating special films

into the structure. For the first group, the permalloy or platinum thin films are fully passivated within layers

of silicon nitride to suppress any possible chemical

reactions between the metal film and the constituents

of the surrounding gases. The structure of the second

group of sensors is such that the environmental gases can react with either the special films (Sn02 or WO3

for NOx or combustibles, or Zr02 for O2) or with the

metal catalyst directly (see Gall and others [8,9]).

The following subsections highhght the performance

of some of these sensors (Subsection A), discuss

generic challenges that are common to most

(Subsection B), and review their use in correlation to

fiarther outputs of interest (Subsection C).

A. Performance ofSome Thermal Microsensors

Thermal flow microsensors of the design described

above feature at least 10 times greater sensitivity to low flows than conventional anemometers. Fig, 2

shows data of such a sensor taken for three different gases, stretching over three orders of magnitude.

Compensation for the noticeable composition effect

has been developed and consists of incorporating a correction factor into the output that depends on

thermal conductivity, specific heat, temperature, and

Prandtl No. [3]. The effect of the latter can be

neglected in most applications.

Also, thermal conductivity, k, and specific heat, Cp, can be measured with such microbridge sensors, as outlined in Fig. 3. Each time after energizing the

heater, k is obtained from the steady state signal, while

Cp is obtained from a combination of the transient

signal and k. Fig. 4 shows how well the sensor signals can be calibrated with known values of k(T,p) for

various gases. Microconvection can influence those

readings if not properly allowed or compensated for, as shown in Fig. 5 in which the plotted groups of 50

readings each were taken while holding the plane of

the sensor membrane in one of the six possible

orthogonal space orientations.

As an example to represent the special-film sensor group. Fig. 6 shows the results obtained with a thin

film of tin oxide sensor [7] operated at about 200°C.

The cross sensitivity of such thin film sensors to water

f IN Ib/h

0

3

CL

ZDO

00o

10

STDCOND 15°C. 101325bar UB COND 22.i°<Z. 995 7mbor

• 22.32°C Methane

o 22.55°C Nitrogen o 22.27°C High Vise. Nat. Gas

SM1S12XX.013. WBFIowl4.BAS 30-JUL-91 J I I_|J I \ l—U i I LJ- 0 0

2 10 3 — m^, MASS FLOW IN g/h

Fig. 2. Microbridge sensor output vs. mass flow for three gases. 32
lUUl k\UkM rVMkU fpcrq rwgg< wrc<r<

SENSOR SENSOR

HEATER

0 0.01 IN.

a. Sensor chip cross section

B9306S5-03a

Data Bank

dT/d2

Sansor

''I h

-AT.

l-TMlra to Output

Eqs. (1). Calibration

Corv»rt»r #1 -k— Convertar K

Equationt Equatiant

pAH

Z

b. Electronics block diagram

7

>Z

K

3

0.O

cro

M

Z

LU

9 12 15 18 21 24 27 30 TIME IN mS B830655-O0c

c. Sensor output vs. time for three gases

7 > 6 z

5

-

GAS: METHANE

0 25

PRESSURE IN PSIG

12 15 18 21 24 27 30 TIME IN mS B83065S-3d

d. Sensor output vs. time for three pressures

Fig. 3. On the measurement of k and Cp.

a:O

on

a:

3

2

1 -

0

-

-1

-2

-3

1

\

1 r

DUK8C2302.D12. UKDemSl 2.BAS

0.5 - P in a-tm - 1.7 -1.6 - .T in °C ^ 41

MBCompU.BAS lO-MAY-91

\ I L

I ® © ® 5)

o CH4

N

2 40 50 60 70 80 90 100 110 — k, THERMAL CONDUCTIVITY IN |j. cal/(sKcm)

Fig. 4. Thermal conductivity determination error for several pressures, temperatures, and pure gases (std. error = 795 ppm).

10

tn

1—

Q.

h-q

GOz

u

00

2 o

CLo

o

=>_^a <<! |>>b^,<^| |t>>

gas

in C 26.79932

UK6C21At DAT. HVALTvZ9.BAS 27-FZB-92

\ \ I 0 50 100 150 200 250 300 — n, SAMPLE NUMBER

Fig. 5. Influence of sensor orientation and natural convection on output stability (y axis amplification = 100).

40

111 30 o

z

</) 20

CCa

5 10 I0

0.1 8830655-06

J I I I

200°C J I I I L

1 10 NOj CONCENTRATION IN PPM100

Fig. 6. Tin oxide thin-film sensor output sensitivity to NO2 Concentration, in Air[7]. 33
vapor is small relative to that of the traditional thickfilm sensors, as pointed out by Schierbaum et al. [6].

B. Performance Limitations

To characterize the performance of thermal sensors, we suggest the following minimum set of parameters,

which represent both challenges and limitations:

• Sensitivity to the parameter of interest, and

quantified (cross) sensitivity to others;

• Noise level, in relative units of sensor reading (not

full scale);

• Gravity-Zacceleration-driven microconvection

effects;

• Stability (low drift) under normal service life and/or

during exposure to high temperatures (accelerated

life test);

• Cost of trimming/calibration, electronics

(monolithic, hybrid or separate), and packaging;

• Unit-to-unit variability.

The following paragraphs examine just three of

these—stability, variability and packaging—stiU in the context of thermal microsensors

Stability—The importance of this aspect of sensor performance cannot be emphasized enough. Achieving

stable operation requires materials selection to achieve

satisfactory adhesion, stress control, and lack of soUdsolid interdiffusion during high-temperature

processing and/or operation. An understanding of the

mechanism or mechanisms causing output signal drift

is the first step in finding a solution or means of

stability improvement. Figs. 7 and 8 provide a few

examples of our experience with microbridge sensors.

Gaa Rvn 5 Wafer 7 SsnBors SHSFIS ond 2-Gn6

SO

0 0 B

-50

->-RU-15

-•-RU-16

-x-RD-lS —RD-16 -o-R RET-IS -»-RH-15 -•-R RET-ie -*-RH-16 ^RT-15

NO, OF TEMPERATURE CYCLES FROM -20 TO lOOC.

Fig. 7. Sensor resistance change due to temperature

cychng, showing changes that are barely outside of the

noise level.

Fig. 7 shows that the rate of change in the resistance

element of the microbridge used slows with the

number of thermal cycles, indicating a less than linear,

possibly logarithmic, dependence on the number of

cycles. Results of accelerated life tests of similar sensor structures support that view, as shown by the

resistance change data plotted vs. log of time in Fig. 8 [3], where each point represents an average of

ten samples. Similar log(time) dependencies are well

known for the rate of mechanical stress annealing vs. time, and the depoling of piezoelectric ceramics (such

as PZT (lead zirconate titanate)) vs. time. Both are based on the rearrangement of some grain or domain

structure. The challenge here is to elucidate the underlying

mechanism. Thermal coefficient of expansion (TCTE)

mismatches clearly play a role. One might try to quantify that by postulating stable behavior (after

annealing out residual fabrication stresses) if the

thermal excursions the sensor is subjected to, do not cause the incurred strains to exceed the elastic limit of

the weakest member, which often would be the thin

film of sandwiched metal like platinum. Measurement of the resistance stability of a number of

platinum thin-film-based elements of microsensors at 20°, 180°, 250°, and 350°C show, however, that not all sensors behave alike (Fig. 9), so that some allowance

needs to be made for "individual" effects, beyond

those one may identify as average behavior. There is clearly room for more study here.

Sensor Variability—Means to minimize variability

may require some hard cost-performance tradeoffs. Cost reduction requires small feature and chip size, yet some of the low-power and low-cost (wafer real estate)

z, CLOCK TIME IN hours

Fig. 8. Microbridge heater accelerated life test results.

34
Sensor 19-24

ax

ID

-IDO

-200

-D-RSU —RD R RET -^RT -^RP

i^:;—-_ ^

ID 100 1000

Sensor 19-3

SK-fl From ICR CdLouLotod 20 Deg G RoaLotaToo

4000

2000

-1000

-o-fU niRD -^R RET

-•-RT 250°C

1000 Tl»e - Htxr®

a. 20°C c. 250°C

Sensor 19-6

3i,ft Frm ICR CoLcuLotad 20 Dag C RasLoto-Ds

3ci<a TerparaUre IflO De^^eee C

IDDD

-1000

180°C

-o-PU, --fn , , rr RREF.^SH, .-r^RT

1

b. 180°C

IDD 1000 Tuna - Hor^

Sensor 22-12

0

-2000

-WOO

-8000

-60tB

-IQOOO

-12000

-14000

^

350°C

R R£r,-»-/W, , r1-W

0-25-188

d. 350°C

10 100 TUno - Ho\ra

1000

Fig. 9. Sample of 1250-hour life tests with microbridge flow sensors at the indicated temperatures. Each graph

shows data obtained for one chip with six different thin-film Pt elements.

benefits may entail unacceptable electrical variability,

pressure dependence of thermal response due to nonuniform rather than uniform temperature field

effects, high current densities (leading to electromigration), and heat transfer variabiUty.

We recently measured sensor heater losses and

electrical resistance of four bonded flow sensor chips

vs. ambient temperature and heater temperature rise, see Fig. 10. The covered temperature range was 35° to 100°C for the heater rise and 20° to 73°C for the

ambient temperature. The results showed an averaged

one-standard deviation of ±0.357% to 0.358% for the

resistance variability, but only ±0.08% to 0.11% for

the thermal conductance variability. While the sample

size was clearly not large enough for sweeping

conclusions, the data do warrant a closer look to clarify why the electrical properties are about four

o

>z

o

CL00

UJ

cr<

QLLdX

H-of

\

40 50 60 70 80 90 1 00 1 1

- AT, HEATER TEMP. RISE IN °C

Fig. 10. Heat dissipation or thermal responsivity of

microbridge sensors vs. heater input and ambient

temperature.

35
times more variant than the thermal ones. The heater

film width was 5 )im; in another sensor design, with a 2-jim heater film width, the resistance variability was

measured to be ±12%. Feature size, rather than film

thickness uniformity, may therefore be the governing

influence here. Additional small-size penalties may

surface in terms of reduced thermal responsivity.

Packaging—The concern about survival of such

microsensors with thin (approximately 1 jim) membranes in a real-world environment needs to be

addressed. In gas flow situations, encounters with

particles more than 300 jim in average diameter is conceivable. Solutions we have found to be useful are based on either mounting the sensor in a protected

(tortuous path) bypass [10] or trapping particles larger

than a given size [11]. In both cases the sensors survived passing the specified load of particles representative

of likely exposure during its specified service life.

C. Sensor Output Correlations

Having developed the capability to sense k and Cp, we

explored the merits of using them to correlate with

other gas properties of interest, Yj, (indicated in Fig.

3

as converter #2 equations, similar to those developed

earlier[I7]) such as density, p, relative density (= specific gravity), p/pov viscosity, T], higher heating value,

AH, compressibihty factor, Z, octane number of gase- ous fuels, Nmon» critical compression ratio, Rcc, and

others. Figs. 1 1 through 15 provide a few examples in- volving a set of over 70 natural gases, with a range of

physical properties indicated in tlie caption og Fig. 14. Fig. 1 1 presents the result of fitting relative density to k and Cp for the above set of gases, augmented by the

addition of the corresponding set of peak shaving

>

<o

u

UJ

CL

Q-O

.9 -

HV78PT7,0AT KV77PKS7.DAT HVlnR? BAS 6-MARI I

\ ,5 .6 .7 .8 .9 1

t q^, ACTUAL SPECIFIC GRAVITY

Fig. 11. Comparison between actual and computed

specific gravity of 78 natural gases and 77 peak

shaving gases (maximum correlation error = ±0.33%.

gases. The achieved correlation uncertainty was only

±0.33% or <±0.1%, with and without the set of peak

shaving gases, respectively. Figs. 12 through 15 pre- sent error plots of viscosity, heating value, compressibility [12], and octane number [9], respectively.

AH these rely on the absolute accuracy of the k and Cp

sensor calibration (e.g. with pure gases) and on

accurate algorithms for the computation of the k and Cp

of gas mixtures to develop the Yi(k,Cp) algorithm. For

properties of gas mixtures that are nonlinear, the

accuracy of the Yi(k,Cp) algorithm is compromised if such gas mixture properties cannot be predicted

accurately (accurate measurement of a large set of gas mixtures is possible but expensive). Such gas mixture

properties are being developed [13] but need further

support.

CONCLUSIONS

From our experience with thermal microsensors, we

conclude and might recommend the following.

• Stresses in microsensor thin films should: - Be kept within the elastic limits to minimize one

source of sensor drift; - Be evaluated on the basis of the relevant phase

diagram for possible phase changes.

The study of possible phase change- and

diffusion-driven changes in thermally stressed

thin films, such as in thin-film Zr02-based O2

sensors, should be supported to make such

sensors available in microstructure versions.

• In striving for low-cost manufacturing, ways for reducing chip-to-chip variability —to the point

where costly individual trimming and calibration

crO

DC

102 104 106 108 110 — n, ACTUAL VISCOSITY IN fjipoise

Fig. 12. Viscosity determination error for 78 natural

gases (std. correlation error = 687 ppm).

36
900

Hj^Q [N Btu/ft^(60 F) 1000 1100 1200

o

a:

cr

<>

UJ

-4 -

— H^^, ACTUAL H.HTG.VALIN MJ/rTT^(l 5<^C)

Fig. 13. Heating value determination error for 78

natural gases (std. correlation error = 0.13%)

16 1 7 M [N g/mol

13 19

o

O

-J<

o

o

-1

P in psio. T in iz = z(mb)-z(ge:rg)

• 600 4,66 -

o 600 35.66

° 600 66 66 o 1000 4.66 ^ 1000 35 56

^7 iOOO 66.56 o

o "fSOO 4.66 A

° 8500 35.66

* 1500 66 66

CriticlS.BAS, ComprslS.BAS, MB78COGL15.U15 20-OCT-91 J I \ I \ \ I I

i .54 .56 .58 .6 .62 .54 .66 .68 .7 .72

I — G, IDEAL SPECIFIC GRAVITY (Z| = 1)

Fig. 14. Error in microbridge compressibility factor

relative to the 13-component equation of GERG, using

a two-pressure-term correlation (range of gases:

AH: 17%; Ati: 7%; AM:20%;ACO2, AN2: 3%;Appc:

2.3%).

can be eliminated—should be investigated.

Required feature sizes should be established only

after trading off performance,sensor and trimming

costs, and variabilities.

• The accuracy and consistency of available

thermophysical properties of gases, and especially

of their mixtures, need to be improved. These are needed for calibration of sensors of k, Cp, T], p, Z

and others.

• The use of exposed gold wire bonds for environmental gas microsensors may lead to

M IN g/rr-.ol 19

O

CC

01Ul

crUl

CDz>

UJ<o

o

<

t

.54 .56 .58 .6 .62 .64 .66 .68 .7 .72

G, IDEAL SPECIFIC GRAVITY (Z:=1)

Fig. 15. Motor octane number (Nmon) error (std.

correlation uncertainty = ±0.6%).

unacceptable drifts, especially in harsh

environments. Other, passivated means of

contacting the sensor need to be developed.

• Interesting gas sensors that might be reviewed at future workshops are those based on zeolites [14],

thick-film O2 sensors [15], and NDIR sensors based on selective, uncooled IR detectors [16]. ACKNOWLEDGEMENTS

I thank David Nielsen, David Zook, Robert Higashi,

Dave Kubisiak, Em Satren and Barrett Cole for their stimulating discussions, experimental data, and

suggestions that contributed to this paper, and Steve

Semancik for inviting us to participate in this Workshop.

REFERENCES

[1] H. Meinel and T. Just, "Measurement of NO^

Exhaust Emissions by a New NDUV Analyzer,"

AIAA 14th Aerospace Sciences Meeting,

Washington, DC, January 1976, pp. 76-137.

[2] P.J. Bohrer, R.E. Higashi, G.B. Hocker and R.G.

Johnson, "A Microtransducer for Air Flow and

Differential Pressure Sensing Apphcations,"

Workshop on Micromachining and Micropackaging of Transducers, Case Western Reserve

University, Cleveland, OH, 7-9 November 1984.

[3] U. Bonne, "Fully Compensated Flow

Microsensor for Electronic Gas Metering,"

Int'l.Gas Research Conference, Orlando, FL, 16-

19 Nov. 199i, Proceedings, Vol. IH, p.859.

[4] S.D. James, R.G. Johnson and R.E. Higashi, " A

Broad Range Absolute Pressure Sensor," IEEE

37
Solid State Sensor and Actuator Workshop,

Hilton Head, Is., SC, 6-9 June 1988, Book of

Abstracts, p. 107,

[5] N.A. Foss and G.B. Hocker, "Integrated Sensors

and Controls," Sensors, 5, 21 (Apr. 1993).

[6] K.D. Schierbaum, S. Vaihinger, W. Gopel, H.H. van den Vlekkert, B. Kloeck and N.F. Rooij,

"Prototype Structure for Systematic

Investigations of Thin-Film Gas Sensors,"

Sensors and Actuators, B, 3, (1991).

[7] B. Cole, HTC, Private Communication,

September 1992.

[8] M. Gall, 'The Si-Planar Pellistor: A Low-Power

Pellistor Sensor in Thin-Film Technology,"

Sensors and Actuators, B4, 533, (1991).

[9] C. Vauchier, D. Chariot, G. Delapierre, and A.

Accorsi, "Thin Film Gas Catalytic Sensor,"

Sensors and Actuators, B5, 33 (1991).

[10] T. Ohnstein, R.G. Johnson, R. Higashi, D.

Bums, J. Holmen, E. Satren, G.M. Johnson, R. Bicking and S.D. Johnson, "Environmentally

Rugged, Wide Dynamic Range Microstructure

Airflow Sensor," IEEE SS Sensor and Actuator

Workshop, Hilton Head, SC, 2-7 June 1990.

p. 158.

[11] U. Bonne, "Safe Channel Design for Sensor

Chip Microbridges," European Pat. No.: EP

0522 575 Al, assigned to Honeywell, 13 Jan. 1993.

[12] U. Bonne, "Determination of Compressibility

Factor and Critical Compression Ratio with Si- Based Microstructure Sensors," 7th IGT

Symposium on Gas Quality Measurements,

Chicago, IL, 12-14 July 1993.

[13] J. Kestin and W.A. Wakeham, Transport

Properties ofFluids, CINDAS Data Series on

Material Properties, Vol. I-l, Hemisphere, New

York, 1988, and W.A. Wakeham, A.

Nagashima and J.V. Sengers, Eds.,

Measurements of the Transport Properties of

Fluids, Blackwell Scientific Pubs., Oxford, UK,

(1991).

[14] C.G. Frye, C.J. Brinker, T. Bein, C.S. Ashley

and C.S. Martinez, "Controlled Microstructure

Oxide Coatings for Chemical Sensors," IEEE SS

Sensor and Actuator Workshop, Hilton Head,

SC, 2-7 June 1990, p. 64.

[15] H.J. Beie, A. Gnoerich and E. Ivers-Tiffee, "Gas

Sensor and Its Fabrication Process," Pat. No. DE

4027905A 1, submitted by Siemens AG, Patent Review Opening: 28 March 91.

[16] C. Kulp, B. Krafthefer, M. Rhodes and M.

Listvan, "Silicon IR Sensors for Thermal

Comfort and Control," ASHRAE J., 35, 38

(Apr. 1993).

[17] N. Pearman et al., "Low-Cost Gas Btu Meter

Using Physical Property Measurements," Phase

m Final Rept. to GRI, GRI-85/0248, Honeywell

Technology Center, Minneapolis, MN, Dec.

1984.

38
NIST Programs and Facilities in Gas Sensing and Related Areas

Steve Semancik and James R. Whetstone

Process Measurements Division

Chemical Science and Technology Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

Development of improved gas sensing devices requires research in a range of disciplines.

Efforts within different organizational units at the National Institute of Standards and

Technology (NIST) address a variety of key sensor-related issues. These include

fundamental studies of sensing materials and concepts, device calibration, direct

measurements in particular environments, and production of standard gas mixtures. This

paper provides a brief summary of existing programs and identifies institutional contact

points for those requiring more detailed information.

Research and development efforts in the area of gas

sensing are being motivated by a wide range of

identified application areas, such as environmental

monitoring, process control, personal safety, and

other areas which are being discussed in the

Breakout Sessions of this Workshop. It is also

generally believed that technological advancements

that lead to the production of reliable, inexpensive,

low-power sensors will create many new

application areas for which current generation sensors are inadequate and analytical

instrumentation is too costly. The discovery of new

sensing materials and concepts and their

incorporation into new devices requires a broadbased effort extending from basic research, to practical fabrication processing, to testing and

performance demonstration in real world settings.

A number of different groups within NIST are involved in activities that support the required

components of gas sensor development and testing

just mentioned:

1. Gas sensing research efforts centered in the

NIST Chemical Science and Technology

Laboratory (CSTL) relate to developing several

areas, including conductometric microsensor arrays

and humidity measurement (and standards). There

are also efforts in optical spectroscopic research

and fiber optic-based sensing. (In addition,

biosensing research occurs within CSTL.)

2. Development of techniques supporting production of well characterized gas mixtures as standard

reference materials (SRMs). Such mixtures have

direct application to gas sensor development and

evaluation. These activities are also conducted in

CSTL.

3 . Issues associated with air quality in buildings

are being investigated in NIST's Building and Fire

Research Laboratory (BFRL). Additionally,

research is underway on detection of gaseous

species generated during the initiation of fires and

the incidence of building fires.

4. Standards and measurement techniques for

radioactive gas concentration are developed in

NIST's Ionizing Radiation Division, Physics

Laboratory (PL).

In this paper we provide summarized information on a number of these efforts. Those interested in

greater detail than could be included here are encouraged to consult the references below or to contact the NIST Division where the studies are done. We begin by describing an overview of the

NIST effort in solid state microsensor arrays.

39
Conductometric Microsensor Arrays

Background

The program aimed at developing gas microsensor

arrays is centered in the Process Measurements

Division of CSTL, but has involved a close

collaboration with the Semiconductor Electronics

Division of the Electronics and Electrical

Engineering Laboratory (EEEL) at NIST. The

objective is to develop the technology needed to integrate multiple active elements into a planar array

configuration which can be used to provide

compositional information on gas mixtures of

varying complexity. The approach we use involves

combining differing surface-active sensing films

with micromachined-Si array structures that contain

multiple elements which can be individually

temperature controlled [1]. The type of platform

produced is meant to be generic and tunable to a wide variety of applications. Many detection

principles can be applied in solid state gas sensing

(see also other papers in this section, and reference

1), and the selected method, in combination with

the chemistry of the gases to be monitored,

determines the types of active materials employed.

Array devices reduce (or eliminate) the requirement

of using highly selective films, and therefore

permit the use of certain materials that are more

robust.

While our group has investigated diode-based and

surface acoustic wave devices, its research has

been focused more heavily on conductometric

microsensors that have active films of

semiconducting oxides which are sometimes

modified with surface-dispersed catalytic metal

additives. These films, as well as the

micromachined arrays, provide relatively durable

devices able to operate in certain environments

where, for example, polymeric materials would be

ill-suited. Development efforts required for these

conductometric microsensors include the study of

improved films and interfaces, transduction

mechanisms, fabrication and compatibility issues,

response evaluation, and pattern recognition. The

interactive combination of these research

components is illustrated schematically in Figure 1.

Technical Approach

In our semiconducting oxide-based conductometric

sensors, gas adorption can induce changes in the

near-surface charge distribution and oxygen

content that alters the conductance. Reducing gases

increase the conductance and oxidizing gases lower

it. The challenge is to instill a degree of selectivity or uniqueness into each of the multiple sensor elements so that the observed changes in

conductance can be used to indicate the presence

and concentration of a gas or gases. Two

MATERIALS

Semiconducting Oxides

Catalytic Metal

Surface Additives

MECHANISTIC

SCIENCE

Adsorption/

Desorption

Surface Conductance

Dissociation/ Diffusion Oxygen Vacancy

Concentration

MICROSENSOR ARRA Y

mum m

CMOS

TEMPERATURE

CONTROL

AND

SIGNAL

PROCESSING

CIRCUITRY

FABRICATION

Patterning

Compatibility of Electronic/ Chemically Active Materials

PATTERN

RECOGNITION

On-Chip Neural Net

I

RESPONSE TEST

SYSTEM

Figure 1 . Schematic representation of the research components within the gas

microsensor program in the CSTL at NIST.

40
selectivity-enhancing schemes, used in

combination in our approach, involve (1) the

variation of film (and surface) composition and

microstructure of the active layers, and (2) the

temperature-control afforded by the micromachined

arrays, for each of the miniature elements in our

devices.

Active films and interfaces can be varied in a number of ways. The use of differing oxide types

such as Sn02. ZnO, Ti02. and WO3 will, by the

namre of their differing chemistries and electrical

properties, cause variations in the gas-solid

interactions and transduction processes. The

microstructure, stoichiometry, and even the

thickness of the oxide films can also be used to affect the response of the individual oxides. The

action of the oxides can also be significantly

modified by surface-dispersing catalytic metal

additives in the monolayer coverage regime.

Discontinuous overlayers of metal islands produce

new adsorption characteristics and can create

micro-Schottky barriers that influence electronic

transport behavior. Discontinuous additive

morphologies allow the interfaces to maintain

semiconducting (rather than metallic) character, so

that they have larger dynamic ranges of

conductance response to adsorbing gases. The use

of metal/oxide interfaces enhances selectivity and

often lowers the operating temperatures of the

conductometric sensors.

Temperature control has long been recognized as an important if not necessary feature of operation

for gas sensors. For example, commercial Taguchi

sensors [2], in existence for many years, use a heater to raise their active materials to elevated

operating temperatures. Recently, the use of

micromachining technology has introduced the

possibility of much more versatile temperature

programming to gas sensing structures. Other

benefits include the greatly reduced power levels

required to produce elevated temperatures for

miniature sensor elements and the ability to fabricate reproducible planar devices costeffectively through batch processing. The

opportunity to incorporate on-board control and

signal handling electronics also presents itself, and

is most easy to achieve when standard methods are used to form the micromachined structure. The

type of basic sensing element we have been

developing for microsensor array technology is illustrated in Figure 2 [3]. Arrays of these

"microhotplates" have been specially designed for

fabrication at a Si foundry using standard CMOS ~

complementary metal oxide semiconductor —

technology, (which facilitates the incorporation of

on-board circuitr\0. The suspended microhotplate

pixels are realized by a post-fabrication, anisotropic

chemical etch of exposed Si. Each pixel is configured to serve as the platform for a planar,

conductometric sensor film (variations can be used

for applying other sensing principles). As indicated

in the schematic, the microhotplate includes an

integrated heater, thermal distributor/thermometry

plate, and 4 top level contact pads. These

electrically conducting structures are vertically

separated by insulating Si02 layers. The

suspended elements have typical lateral dimensions

of 100-200 jj.m and masses of a few tenths of a \ig.

Their low mass and level of thermal isolation allow

them be heated and cooled rapidly (1 ms time

constant for heating to 500°C with a temperature/power coefficient of 8°C/mW).

This fast temperature modulation can be used to great advantage both in fabricating and operating

the sensing elements [4]. For example, static or dynamic temperature control during or after

deposition can affect the stoichiometry and

microstructure of overlayer (oxide and metal) active

Figure 2. Scanning electron micrograph showing a suspended microhotplate structure with 4 topsurface contact pads for conductance measurements

on an active film. Top and cross-sectional end view

schematics (not to scale) are shown in the lower

panel.

41
films. In certain processing, such as chemical

vapor deposition (CVD), the microhotplates can provide an efficient means for selected area, maskless lithography to place multiple sensing

films of differing composition on a set of elements.

The use of temperature programming for sensor

operation is illustrated below.

To demonstrate our conductometric microsensor

technology, Sn02 has been reactively sputter

deposited on microhotplates so that the underlying

contact pads of the elements can be used in

monitoring gas-induced conductance changes. We

have demonstrated that at a fixed temperature of

350°C, the pure Sn02 shows opposite conductance

excursions in response to the presence of oxidizing

and reducing gases [3]. As a follow up to that

study we have also taken advantage of the rapid

temperature control possible with the

microhotplates to examine pulsed mode operation.

Figure 3 shows a simple example in which an Sn02 film is being used to monitor on/off cycles of

0.1% H2 injection in air. The microsensor

temperature is pulsed to 400°C for 10 ms once

every 1 .0 s. Conductance is measured only at times

where the film is not heated (so that only

adsorption-induced changes in electronic transport are recorded rather than effects of thermal carrier

generation). In this power-saving mode the energy

requirement of the heater could be provided by a 9

V alkaline battery for almost 1 year.

28

26

'24

22

0.1% H2 injections

„ 400°C

pulsed T cycle

30°C

lime (sec)

3000 4000 Time (sec)

5000

Figure 3. Conductance response of a Sn02 film on

a microhotplate using temperature pulsing (see

inset) for a reduced-power mode of operation.

Illustrated are 3 on/off cycles of the 0. 1 % H2 in air test gas.

Further studies are underway with more

sophisticated pulsed temperature cycling (both with

and without catalytic additives dispersed on active

oxide films). Initial results indicate that differing

pulsed temperature schedules have considerable

potential as a kinetic selectivity tool for

distinguishing between similar gas and vapor

species. These investigations generate informationrich response data sets as the detected analytes and

temperature cycles are varied. A recently

completed, fully-automated testing facility [5] is used in controlling test devices and monitoring

their outputs. This system is critical for evaluating

device speed and stability and for obtaining the

large databases necessary for developing pattern

recognition algorithms that will be required for gas

mixture analyses.

Materials Studies

The sensing capabilities of oxide and additive metal

films can be enhanced by the selection of special

operating modes (e.g.- Figure 3) made possible

when the active materials are combined in a compatible way with micromachined structures

(e.g.- Figure 1). However the ultimate level of

performance will be determined by the selection of

film materials and their specific properties as fabricated in the sensing device. To explore and

improve the active films that serve as the hearts of

the sensors, our development program includes a

parallel effort into the relationship between material

properties and transduction mechanisms.

Two separate facilities have been constructed to study the fabrication, properties and interfacial

sensing processes [5]. The Film Deposition and

Characterization Facility is an ultrahigh vacuumbased system outfitted for depositing, modifying

and characterizing films (thus far efforts have

focused on semiconducting oxides and several

metals) and exploring methods for producing new,

microstructure-controlled materials. The Surface

Analytical Facility is a multichambered system

equipped for characterizing the chemical,

structural, electronic, and electrical properties of

the outermost 0.5 to 10 nm of sensing materials.

These analytical capabilities are important for

determining the detailed properties of fabricated

materials and performing model studies of

transduction mechanisms [6, 7]. Among the many

factors that can be examined for sensing materials

are sample purity, composition and stoichiometry,

adsorption and desorption characteristics, the

consequences of surface reactions, and the

variation of electronic transport behavior [1].

42
10^

u

Z

<

H

So iqO

10-

200 400 600

TIME (s)

800

Figure 4. Resistance changes measured for O2-

pump-H2-pump test cycles (gas pressures 10"^ Pa) on 3 ultrathin, epitaxial Sn02 films on (0001)

sapphire. The films, whose thicknesses are labeled

(10 A = 1 nm), have been activated with 1 monolayer equivalent of Pd and the responses were measured at 300°C.

A portion of our research program has involved

examining highly ordered forms of oxides as improved sensing materials. Uniformity of factors

such as particle size, crystalline orientation and

atomic-scale structure can reduce the complexity of

molecular adsorption phenomena in addition to producing more coherent and inherently stable base

electrical properties. These benefits can be expected

to occur for uniformity across the continuum of

structure from the single crystal end toward the

amorphous end. As one example of this work, we

have developed procedures for the heteroepitaxial

growth of Sn02 on sapphire. The films grown

have only a single, substrate-dependent orientation,

with x-ray diffraction measuremen_ts showing that

Sn02 (101) forms on sapphire (lT02) and Sn02

(100) forms on sapphire (0001) [8].

Scanning probe measurements and low energy

electron diffraction have indicated that the

heteroepitaxial films are extremely smooth and that

atomic ordering extends to the surface through a process of layer-by-layer growth [9]. The processing we have developed can therefore be used to produce continuous, ultrathin Sn02 samples. The

ability of such ultrathin oxide films to sense when

they are modified by the addition of 1 monolayer

equivalent of Pd is illustrated by the cyclical model

responses shown in Figure 4 [10]. One noteworthy

aspect in these results is that a sensing response is observed for an epitaxial film that is only 5 atomic

layers (1.5 nm) thick. Efforts are being planned for

incorporating epitaxial oxides into redesigned

versions of our microhotplates.

Scanning tunneling microscopy (STM)

characterization can define interfacial

morphological and structural features which are

critical to sensor performance. Figure 5a shows a STM image taken from a pure, 8.0 nm ultrathin

Sn02 (101) film. Islands of Pd that form when 0.5

and 7 monolayer equivalents are dosed onto this

film are presented in Figures 5b and 5c [11]. Gas

adsorption-induced, localized effects occurring

near island structures similar to those shown in

Figure 5b are collectively responsible for

producing macroscopic sensing responses (related

to those in Figure 4). In the years ahead, STM

imaging and spectroscopy will become increasingly

important as tools for understanding existing (and

new) sensing mechanisms and guiding development of atomically engineered materials with

improved sensing characteristics.

Before closing this section, it is important to note

that device structures, such as the microhotplates

discussed above, are playing a key role in materials

research and development. For example, efficient

surveying of relationships between materials

processing, properties and performance can be

achieved by using differing temperature schedules

for the multiple microsubstrates present in a micromachined array. In addition, properly

designed, systematic cycles of dosing and thermal

schedules can be used to produce valuable

information on surface adsorption [12] and reaction

effects. In essence, these experiments seek to "invert" the device to examine the specific

interfacial processes by which the it will operate as a sensor.

The remainder of this paper briefly addresses

several other efforts at NIST.

43
Figure 5. STM images obtained from (a-left) a pure, epitaxial Sn02 (101)

film, and the same film dosed with (b-center) 0.5 and (c-right) 7 monolayer

equivalents (ML eq) of Pd.

Calibration Gas Mixtures for Sensor Development

and Evaluation

Gas standards are developed by the Organic

Analytical Research Division of NIST's Chemical

Science and Technology Laboratory. These are binary and multi-component gases issued as part

of the NIST Standard Reference Material Program.

Approximately 90 gas SRMs are available ranging

in concentration from 5 ppb to 21%. Inorganic,

reactive and non-reactive species are available

including organic halogenated and non-halogenated

compounds. These SRMs may be obtained

through NIST's Standard Reference Materials

Program [13]. In cases where customer needs

differ from available SRMs in species or concentration, research gas mixtures may be

obtained through direct interaction between NIST

staff and interested parties.

NIST is initiating a new facet to the program in gas

standards to produce cylinders of gases known as NIST Traceable Reference Materials (NTRMs).

This program utilizes the expertise and capabilities

of the specialty gas industry to manufacture

mixtures and relies upon NIST's analytical

capabilities to analyze the mixture for species

concentration. In this case the end user interacts

directly with the specialty gas supplier(s) to obtain

gas cylinders containing gases with species

concentration assigned by NIST.

Optical Methods for Gas Compositional

Measurement

Several research efforts within the Analytical

Chemistry Division [14] of CSTL relate to the use

of optical methods for compositional

measurements. One project is aimed at evaluating

the feasibility of doppler-free spectroscopy in the

infrared spectral region as a means of monitoring

for gaseous oxygenated hydrocarbon species.

Development of such a capability could provide a new tool for real time automotive exhaust analysis.

Fiber optic-based interferomery studies are also

underway in the Analytical Chemistry Division.

Thus far, this work has been focused in the area of

immunoassay biosensors, but aspects of the

detection and signal handling technology being

developed could also impact related optical

schemes for monitoring gases.

Gas Species Sensing for Fire Detection

Detection of gaseous species associated with fires

is being pursued in the Fire Science Division [15]

of the BFRL. Sensing requirements are the

following:

Species of Interest:

C02, CO, H2O, CH4, H2, Light Fuels

Oxygenated Hydrocarbons, HF, HCl, NOx,

HCN, O2, & Carbonaceous Particulates

Concentration ranges:

10"^ - 10"! mole fraction of gases

10"^ to 10"^ vol. fraction of particulates

44
Temp. Range: ambient to 1 500K

Sensor Response Time: lO'^-lOsec.

Research activities are directed at investigation of

fire phenomena under well-controlled conditions.

Particular emphasis is placed on building fire

phenomena. This research utilizes a large fire test facility that includes several types of energy-release

measurement equipment based on calorimetric

methods.

Standards and Measurement of Radioactive Gas

Concentration

Development and maintenance of the National

j Primary Standard for Radon Concentration

' Measurement is one of the responsibilities of the

Ionizing Radiation Division [16] of the PL. The

standards and measurement technology developed

are used in support of EPA and DOE

environmental measurement programs, and for the

U.S. Geological Survey. Calibration of working

standards is offered.

Measurements and Standards for Moisture

Concentration in Gases

The development and maintenance of national

standards for moisture in gases is a responsibility

of the Process Measurement Division [17] of the

CSTL. Primary and secondary standards are developed and maintained. Secondary standards

are precision humidity generators used to provide

calibration services for humidity measuring

instruments and sensors Operating ranges and

uncertainty estimates are given in the table below

for the NIST Two-Pressure Humidity Generator

used to dessiminate calibration services.

References

[1] S. Semancik and R. E. Cavicchi, Applied

Surf. Sci. 70/71, 337-346 (1993).

[2] The mention of commercial sensors based on

the Taguchi design is included only for the

purpose of example and is in no way meant as an endorsement of such products.

[3] J. Suehle, R. E. Cavicchi, M. Gaitan and S. Semancik, IEEE Electron Device Lett. 14,

118-120 (1993).

[4] U. S. Patent No. 5,345,213.

[5] Additional brief descriptions of NIST research

facilities can be found within the Poster

Session abstracts in this volume.

[6] T. B. Fryberger and S. Semancik, Sensors

and Actuators B2, 305-309 ( 1 990).

[7] S. Semancik and T. B. Fryberger, Proc. of the

3rd Int. Meeting on Chem. Sensors

(Cleveland, September, 1990) pp. 23-26.

[8] S. Semancik and R. E. Cavicchi, Thin Solid

Films 206, 81-87 (1991).

[9] R. E. Cavicchi, S. Semancik, M. D. Antonik

and R. J. Lad, App. Phys. Lett. 61, 1921-

1923 (1992).

[10] G. E. Poirier, R. E. Cavicchi and S. Semancik, J. of Vac. Sci. and Tech.

Al 1,1392-1395 (1993).

[11] G. E. Poirier, R. E. Cavicchi and S. Semancik, to appear—J. of Vac. Sci. and

Tech..

[12] See, for example, R. E. Cavicchi, G. E.

Poirier, J. S. Suehle, M. Gaitan, S. Semancik and D. R. F. Burgess, to appear,

J. of Vac. Sci. and Tech..

[13] For information, telephone 301-975-6776.

[14] For information, telephone 301-975-3108.

[15] For information, telephone 301-975-6864.

[16] For information, telephone 301-975-6090.

[17] For information, telephone 301-975-2609.

45
NIST Two-Pressure Humidity Generator, Mark 2, Range and Uncertainty

Humidity Parameter Parameter Range Uncertainty

Mixing Ratio

(g water vapor/

kg dry air)

0.0015 0.005 1.5% of value

0.005 0.1 1.0% of value

0.1 0.3 0.5% of value

0.3 515 0.3% of value

Volume Ratio, V

(PPmv)

3 10 1.5% or value

10 170 1.0% of value

170 500 0 .5% of value

500 820,000 0.3% of value

Dew-Point temperature, Tj -70 -35 0.10

-35 +80 0.04

Relative Humidity, RH, at Specified Test Chamber

Temperatures

-55 < T< -40 °C 3 98 1.5% RH

-40 < T< -20 °C 3 98 0.8% RH

-20 < T< -0 oC 3 98 0.4% RH

-0 < T< 40 3 98 0.2% RH

*The expanded uncertainty with a coverage factor of two.

46
Gas Sensor Technology at Sandia National Laboratories: Catalytic Gate, Surface

Acoustic Wave and Fiber Optic Devices

Robert C. Hughes, D. J. Mareno, M. W. Jenkins, and J. L. Rodriguez

Sandia National Laboratories

Albuquerque, NM 87185

Sandia's gas sensor program encompasses three separate electronic platforms: Acoustic Wave

Devices, Fiber Optic Sensors and sensors based on silicon microelectronic devices. In this paper we

review some of Sandia's research for the fiber optic and acoustic wave sensors and give some detailed new results for the new catalytic gate "robust" sensor. Performance of this sensor for reversible

hydrogen detection is given for gas samples both with and without oxygen present and the effect of

relative humidity is also discussed.

Sandia's gas sensor program encompasses three separate

electronic platforms: Acoustic Wave Devices, Fiber Optic

Sensors and sensors based on silicon microelectronic devices. A review of most of these activities was presented

recently in a article in Science under the title "Chemical

Microsensors" [1]. The focus of the program has been on

understanding and developing the chemical sensor coatings

that are necessary for using these electronic platforms as ef- fective chemical sensors.

Fiber Optic Micromirror Sensors

The principles of operation of the fiber optic micromirror

have been given in [1]. A special gas sensitive coating on

the end of the fiber (50 p diameter) changes its optical

reflectivity in the presence of the species to be sensed. Recently an H2 sensor using a Pd film was reported [2] and

films sensitive to volatile organic compounds and nerve

agent simulants are being tested [3]. The very light system

weight for the micromirrors led to its being selected for an

instrument package for the Mars94 lander. An array of micromirror fibers with different coatings will look for oxidants in Martian soil.

Acoustic Wave Sensors

Surface Acoustic Wave (SAW) devices use piezoelectric

quartz as a substrate; they operate in the 100-MHz regime.

SAWs rely on an identical pair of interdigital transducers to launch and detect a wave that travels from one end of the device to the other. Each transducer is comprised of many

pairs of photolithographically defined fingers, each finger

only a few micrometers wide.

The SAW is even more sensitive to tiny mass changes than

the Quartz Crystal Monitor (QCM), detecting 100 pg/cm^:

less than 1% of a monolayer of carbon atoms. But the nature of the SAW's motion leads to extreme damping by

liquids, so applications focus on gas-phase sensing and thin- film materials characterization in the absence of liquid

contact.

The SAW device responds to changes in surface mass and

other thin-film properties with a change in its velocity and,

often, its attenuation. Measuring both these properties si- multaneously helps to determine the nature and cause of the sensor response. Considerable effort has gone into the measurement of volatile organic compounds (VOC's) with the Sandia SAW devices [4]. Recently a new kind of chemically

sensitive film based on a very thin self-assembled monolayer was reported [5]. It gives quite selective response to simulants of nerve agent compounds.

Catalytic Metal-Based Silicon Sensors

There are significant unmet needs for point sensors to detect H2 and other oxidizing and reducing gases. The presence of H2 can indicate corrosion or leaks and explosion and fire hazards exist for H2 mixed with oxidants. There is considerable literature on the use of catalytic metals,

particularly Pd thin films, for fabrication of microsensors for H2 detection [6]. We recently reported a significant

development of the "Robust, Wide Range H2 Sensor"[7] in

47
which some of the new research results on alloys of Pd were

incorporated into a manufacturable sensor module which

have been produced in large numbers in the Sandia

Microelectronics Development Laboratory (MDL). A

baseline radiation-hard CMOS 1.25 micron technology was

used and the main deviation from standard IC processes was

the deposition of the catalytic metal itself. This sensor has

power transistors for chip heating and 9 p/n junctions for measuring temperature at various places on the chip. An

analog feedback circuit keeps the chip at any desired

operating temperature up to about 200°C. It can maintain

the surface temperature even if cold gas flows are directed on the chip [8].

There are two kinds of gas sensors on each chip: a catalytic

metal gated field effect transistor for low H2 concentrations

and a chemiresistor of the same catalytic metal for higher

concentrations. We have found that sputtered films of about

10%(atomic)Ni and 90%Pd are providing outstanding sensor

10"^ 10" 10^ 10* pHg (Torr)

Figure 1. The response to pulses of H-^ of ten different robust sensors from the same wafer lot. The log-log plot

shows the power law nature of the response.

performance. The alloy does not undergo the hydride phase

transition up to 630 Torr of H2 at 25°C (pure Pd goes at about 10 Torr). This allows reversible detection from about

1 ppm to 100% (pure) H2. In this article we would like to show some detailed performance data for the robust sensor

in two real world situations. One involves the issue of

detecting H2 concentrations around the lower explosive

limit(LEL) with and without the presence of O2. The other concerns the effect of humidity on the response of the robust

sensor.

Fig. 1 shows the response of the chemiresistors on ten separate robust sensors from the same wafer to pulses of H2

ranging over two decades, from 0.63 Torr to 63 Torr (1000

ppm to 10%). The sensors were all operated at 50°C and

were plugged into the same DIP socket, using the same read- out and temperature control circuit. The H2 concentrations were provided by computer controlled flow controllers mixing the proper amounts of H2 and N2 to give the selected concentrations. The sensor head was placed in a Lucite

fixture for exposure to the gas flows, which were kept at a constant 1 standard liter per minute (SLM). The error bars

in Fig. 1 show the spread in raw data values among the ten sensors. The excellent die to die uniformity means that a minimum of calibration will have to be done with these batch produced sensors and shows one of the virtues of

tightly controlled microelectronic batch processing.

The data in Fig. 1 are plotted as a log-log plot because of the power law response of the chemiresistors over a wide range

in H2 concentration: from about 100 ppm to 100%. For

these sensors at 50°C, the power law in units of % change in resistance, is:

AR/Rq = 0.43(pH2)0-'^^ (%)

where pH2 is the partial pressure of H2 in Torr.

Fig. 2 shows how Sandia's Robust, Wide Range Sensor performs in both inert atmospheres like H2 in N2 and in the presence of an oxidant like oxygen. An oxidizing atmos- phere is not required to sense variations in the levels of H2

around the lower explosive limit (4%) on a time scale of a few seconds.

The sensor was put in a purged state at the beginning of the run by annealing at HO'^C in air; the chip was held at an

operating temperature of 80°C for the entire run. A pulse of 10% H2 in N2 (63 Torr) was delivered to the sensor in a flow cell at a measured flow rate of 1 (SLM). The fast response of both the FET and chemiresistor are seen. The

gas composition was then changed to a much lower 0.1%

H2 in N2 by introducing flow from another tank. The purge

pressure of N2 was not allowed to fall below 1 SLM to insure that no air backfilled the flow chamber. There are two seconds between data points and it can be seen that the sensor signal confirms a purging gas stream below the 4%

j explosive limit in less than 4 seconds. The actual sensor response is faster than this since it takes some time to purge

the higher concentration out of the tubing and sensor holder

volume. In less than 20 seconds the resistor sensor is reading the correct value for the mixture, 0.1% H2 ( 1000

ppm). The FET only shows a small change, but it also gives

the correct value for the 0.1% mixture. The next pulse to 10% H2 shows the speed and repeatability of the sensor and

is followed by a purge from a tank with 0.01% H2 (100

j ppm). It takes less than 20 seconds for the sensor signal to '

fall below the level for 0.1% and only 50 seconds to reach

the steady state value for 0.01%, which is close to the

48
4% H3_iii_N2

_0.1% in_N2_

0.0

'w' -0.1

O -0.2

> -0.4

-0.6

1 —I I 1 1 1 1

I

o . o ^ o p o ^ o o ^ \

Air

1 100 200 300 400 500 600 700 800

Time (seconds)

Figure 2. Raw data output from one of the Robust Sensors from a series of pHo pulses of various

concentrations. The top trace is for the chemiresistor and the bottom trace is for the FET. The

data from the two sensors is taken simultaneously and the sensor chip temperature is maintained

at 80°C.

o o

CO —

70

6050

4-0 30

20

10

0

1 1 1 2

1 n1 z1

c c

c

C 5

cu c

u z

X

CV X x'^ o01%

H, CM X x"

^? X 4% in - d d

1 1 t 1

O

aoo Time (seconds)

Figure 3. The same data set as Fig. 2 with each point converted to a value the the caUbration curves give

text.

49
baseline for the resistor. A third 10% pulse is followed by a pure N2 purge. It would be difficult to ensure from either sensor whether the H2 has fallen below 0.01% (100 ppm) in the 100 second time scale. The purge for both the FET and

the resistor is faster in air as shown following the 4th pulse

of 10% H2.

Figure 3 shows the same data set as Fig. 2 with every data

point converted to a pH2 value by the calibration formula for each sensor:

1) for the chemiresistor:

pH2 = 9.4 (R)2-08, (a po^er law from ref.[9])

2) for the FET:

pH2 = exp((AVth* 1 .8 13-.78)/0.02 17), (a Temkin

isotherm from ref.[9])

The deviations in the resistor signals for 63 Torr are not

noise, but small changes in the actual pressure caused by

attempts to fine tune the flow rate to 1 SLM by hand.

It may seem surprising that the FET has such a huge

dynamic range, but this effect has been discussed by several authors [6, 9]. It occurs because the occupation of surface

sites on a "dirty" Pd (or Pd/Ni) surface follows a Temkin

isotherm. This probably means that there is a wide variation

in the energy of adsorbed species; the deeper sites are occupied at low pressures and the shallow ones at the highest

pressures. The ability of the FET in the real world to give

accurate readings of the H2 concenU'ation is limited by the

rale at which the deeper sites approach equilibrium with a given value. Thus it can be seen from Figs 2 and 3, (hat for pHt above about 0.6 Torr both sensors give rapid

reversible readings whether O2 is present or not. For the purge of the FET in air (around 500 seconds), the actual value of pHo is /xro, but the steady state value of the sensor

signal for low pH2 (say lO"^'' Torr) mixed with 140 Torr of Ot would not give an accurate reading of pH2. If the p02 is known fairly accurately from a .separate O2 sensor, then we

have found that the pHi can be fairly accurately determined

down to about 0.01 Torr if time is allowed for steady state to be reached.

From the calibration formulas it would seem that all the necessary information about pHt could be obtained from the FET alone. In theory this would be true since the surface

sites giving the FET threshold voltage shift are thought to be

in equilibrium with the bulk sites that give the resistance change. In practice it turns out that drift in the baseline of

the FET and the logarithmic response make it less reliable in determining the accurate value of pHo in the higher ranges.

It should be remembered that both the surface sites and the bulk are in thermodynamic equilibrium with the gas phase

pH2, but they can independently change calibration and/or

signal size because of materials changes in the surface properties or grain boundaries or other as yet unsjjecified

changes in the metallurgical properties of the thin films.

Summarizing Figs. 2 and 3, the Sandia Robust, Wide Range

Sensor has response times of less than 2 seconds for detect- ing H2 leaks and less than 20 seconds for detecting large variations in the concentration around the 4% explosive

limit including purge information down to 0.01% (100

ppm), more than a factor of 100 lower than the LEL. Most

users will not be interested in fast, accurate measurements

between 1 ppm and 100 ppm, but this can be accomplished

by operating the FET sensor at 140 °C.

1 4 r

\ 1 1

1

1 }

1 0 0

8

i

6

*

0

r

purge

4

0 •D

i.

>

*

'£

2

0

ixexna 1 [ \ \ 1

0 1000 2000 3000 4000 5000 600C

Time (sec)

Figure 4. Response of a chemiresistor on the robust sensor

to 2% pH-) pulses followed by air purges. The third pulse has 100%RH at 21°C mixed with the gas stream. Operating

temperature is 50°C.

The data presented in Figs. 1-3 were taken with 0% relative humidity (RH). In real world situations, even when O2 is purged from a large structure by He or N2, water vapor will probably be present. In a pending publication[10] we show

how higher levels of RH slowed the response of a Pd/Ni

chemiresistor operating at room temperature. The response

for the heated robust sensor is much improved, as shown in Fig. 4. This data set has had every data point converted

from the AR/Rq value to the calibrated pH2 value by the

calibration formula shown above. The first two pulses of H2

were "dry" 2% (pH2 =13 Torr). The first pulse was

performed on a fully annealed robust sensor (140°C in air) and is slightly different from subsequent pulses. Each pulse

of pH2 is followed by a dry air purge at the operating

temperature of 50°C. Before the third pulse the gas stream was routed through a water bubbler to bring the stream up to 100% RH (at 2rC). This adds about 19 Torr of water vapor

to the stream. The gas mixture was then again changed to 13 Torr pH2. The data points were taken 5 seconds apart

and it can be seen that the presence of 19 Torr of water vapor slows the response of the sensor. The steady state value is only slightly lower than from dry pH2 pulses. The

50
purge with "wet" air is also somewhat slower. The operating

temperature of 50°C was chosen because less power is consumed than at 80°C and the signal is somewhat larger.

Higher operating temperatures, like the 80°C shown in Figs. 2 and 3 show faster responses and even less perturbation by

water vapor. It should be noted that the partial pressure of

the water vapor is determined by the temperature of the water in the bubbler; the actual RH on the sensor surface at 50°C is by definition lower. The partial pressure of water vapor in some very hot and humid parts of the country could

be even higher than the 19 Torr employed here for the test. ACKNOWLEDGEMENTS

We would like to thank Tony Ricco, Mike Butler and Steve Martin of Sandia National Laboratories for helpful discus- sions concerning gas sensor research. This work was per- formed at Sandia National Laboratories and was supported

by the U.S. Department of Energy under Contract No. DEAC04-76DP00789.

References

1. R. C. Hughes, A. J. Ricco. M. A. Butler and S. J. Martin,

"Chemical Microsensors", Science. Vol. 254 pp.74-79, 1991.

2. M. A. Butler, "Fiber Optic Sensor for Hydrogen Concentrations Near the Explosive Limit", J. Electrochem.Soc . Vol. 138,pp.L46-47, 1991.

3. R. C. Hughes, A. J. Ricco, M. A. Butler and K. B.

Pfeifer, "The Detection of Organophosponates by Polymer

Films on a Surface Acoustic Wave Device and a Micromirror Fiberoptic Sensor", Appl Biochem. and

Biotech. , vol. 41, 77-85, 1993.

4. G. C. Frye, S. J. Martin, R. C. Cemosek and K. B.

Pfeifer, "Portable Acoustic Wave Sensor Systems for OnLine Monitoring of Volatile Organics", Int. J. of Environmentally Con. Man. , vol. 1, pp. 37-45, 1992.

5. Larry Kepley, Richard M. Crooks and Antonio J. Ricco,

"Selective Surface Acoustic Wave-Based Organophosphonate Chemical Sensor Employing a Self-Assembled

Composite Monolayer: A New Paradigm for Sensor Design."

Anal Chem . 64, 3191 (1992).

6. I. Lundstrom, " Hydrogen Sensitive MOS-Structures Part

1: Principles and Applications", Sensors and Actuators , vol.

1, pp. 403-426, 1981; I. Lundstrom, C. Svensson, A. Spetz, H. Sungren and F. Winquist, "From Hydrogen Sensors to Olfactory Images-twenty years with catalytic field-effect devices". Sensors and Act, vol. B13, pp. 16-26, 1993.

7. J. L. Rodriguez, R. C. Hughes, W. T. Corbett, and P. J. McWhorter, "Robust, Wide Range Hydrogen Sensor", in

lEDM Tech Digest. IEEE cat. # 92CH3211-0, San

Francisco, CA, Dec. 13-16, 1992, pp. 521-524.

8. R. C. Hughes, R. L Buss, S. W. Reynolds, M. W.

Jenkins, and J. L. Rodriguez, "Wide Range H2 Sensor Using

Catalytic Alloys", in "Proceedings of the Symposium on Chemical Sensors 11" Electrochemical Society Proceedings

vol. 93-7, M. Butler, A. J. Ricco and N. Yamazoe, Eds.

(Pennington NJ) pp. 556.

9. R. C. Hughes and W. K. Schubert, "Thin Films of Pd/Ni

alloys for detection of high hydrogen concentrafions", L

Appl. Phvs. . vol. 71, pp. 542-544, 1992.

10. R. C. Hughes, W. K. Schubert, and R. J. Buss, "Solid

State Hydrogen Sensors using Pd/Ni Alloys: Effect of alloy

composition on Sensor response", submitted to Sensors and

Actuators . 1993.

51

Microchemical Sensing Based on Temperature-Programmed Methods

Kensall D. Wise, J.L. Glanct, and J. W. Schwank**

Department of Electrical Engineering and Computer Science

*Department of Chemistry

**Department of Chemical Engineering

The University of Michigan

Ann Arbor, MI 48109-2122

This paper describes a silicon batch-fabricated gas detector formed by an ultra-thin metal sensing film

supported on a selectively-micromachined dielectric window. A 5fim-thick boron-diffused bulk-siUcon heater under the window permits the film temperature to be varied from ambient to over 1200°C with heating

efficiencies in air and vacuum of 6°C/mW and 20°C/mW, respectively. The window area is Imm^ with an

active sensing area of 0.12nun2. The heater has been optimized to produce a simulated temperature uniformity over the film area of better than ±0.5% while interleaved temperature-sensing resistors permit the average

temperature to be measured to better than 1°C. The detectors are realized using a simple six-mask process in a

die size of 2.8mm x 2.8mm. All process steps are foundry compatible. A custom VLSI control chip contains

all the required interface circuitry for the simultaneous operation of four such detectors. Window temperature is set digitally with eight-bit accuracy. Film conductivity (magnitude and phase) is measured from dc to 2MHz for

full-scale film resistances from 5 ohms to 1.3Mohms. The interface chip utilizes an eight-Une bus interface,

allowing the implementation of a multi-chip analyzer as a smart peripheral. The control chip is implemented in an eleven-mask 2|iin CMOS process in a die size of 4.4mm x 6.6mm. This sensor structure can be operated in a number of modes depending on the requirements for selectivity, sensitivity, and time response. Examples

illustrating monolayer sensitivity for oxygen, reversible adsorption of oxygen, and detection of oxygen in the presence of CF4 are presented.

INTRODUCTION

Solid-state gas sensors have been the focus of

considerable research during the past decade and are in high

demand for automotive, medical, environmental monitoring,

and process control apphcations [1-4]; however, substantial performance problems remain in such devices, including slow

response, low sensitivity, poor selectivity, long-term drift, and high input power. In contrast to detection methods based on spectroscopic techniques or gas chromatography,

conductivity-based gas detectors rely on chemical interactions between tiie gas molecules and a surface film to produce a

detectable output signal. Such devices are promising

candidates for many applications because of their low

potential cost and suitability for batch fabrication; however,

the significant amount of research that has been invested in improving these sensors has met with limited success due to the unforgiving nature of the films involved and the complexity of die associated surface chemistries [5,6].

Recent research on gas sensors at the University of

Michigan has focused on silicon-based conductivity-type gas

detectors based on ultra-Uiin (<4-6nm) metal films supported on selectively-heated micromachined dielectric windows [3- 4,7-8]. Since the fihn conductance depends significandy on

gas adsorption as well as on the window temperature,

conductance changes at a known temperature can be used as an indicator of die type and quantity of gas present. Because

in this case the film is very thin, surface effects are much

more significant in determining the fihn conductivity than in thicker films, where bulk reactions and diffusion effects dominate [8]. Gases that chemisorb on the fihn surface will substantially affect the film conductance by changing the number of charge carriers or die mobiUty of charge carriers. On the other hand, inert gases such as helium or CF4 do not chemisorb under typical operating conditions. Therefore,

they do not change the resistance of the sensing fihns. The

resulting devices are relatively fast (<ls), and initial measurements showed them to be stable over repeated

temperature and gas cycling. For example, when operated at 150°C using 35A/65A Pt/TiOx sensing fihns, such detectors responded chemically to oxygen from lO'^Torr to 10+^Torr

with negligible drift and hysteresis, and die detection of sub- ppm oxygen levels in CF4 was demonsti"ated [4,8].

This paper describes a second-generation detector [3] intended as a vehicle for further device characterization and as a prototype in-line sensor for gas purity in semiconductor

manufacturing applications. The new detector offers substantially-improved temperature uniformity over the sensing area, more accurate sensing of the window

temperature, and improved thermal efficiency. It is also compatible with use in a multi-element monolithic gas

analyzer [4,9], allowing the detection of gaseous mixtures by

using several windows, each programmed with a different sensing fihn.

53
The ability to precisely control film temperature is being exploited in various ways. Pretreating the film by

heating it to temperatures in excess of those expected during

subsequent operation has been found to play an important

role in determining gas sensitivity. The use of temperatureprogranmied desorption (TPD) in these detectors should also provide increased selectivity and specificity in analyzing

gaseous mixtures. By tracking the conductivity shifts as the window temperature is ramped through characteristic

desorption thresholds (where the gas molecules have

sufficient energy to escape from the surface), the type and

amount of gas present can, in principle, be determined. At

higher temperatures, TPD can also be used to "reset" the film by desorbing all gases, allowing a time analysis of the film

reactions and disposing of gases that interfere with detection.

DETECTOR STRUCTURE

A cross-section and top view of the new gas detector are shown in Fig. 1. A stress-relieved dielectric window [7], composed of a sandwich of thermally-grown silicon dioxide

(SOOnm), low-pressure chemical-vapor-deposited (LPCVD)

silicon nitride (250nm), and LPCVD silicon dioxide

(700nm), is used to support the sensing film as well as a set of four electrodes for measuring the film conductivity. The

window stress is determined by the ratio of these layer

thicknesses and has been adjusted to provide a stress-relieved window over the normal operating temperature range of 200-

500°C. A boron-doped silicon heater is located under the window, allowing the upper surface of the chip to be highly

planar. This is particularly important due to the very thin nature of the sensing film and the associated continuity

problems over any surface steps. Contacts to the film and

the heater are made with Ir/Ti metallization (200imi/25nm),

which is stable at high temperatures on the windows [8]. The heater contacts are positioned away from the heated area of the detector so that they do not see the full window

temperature. Two boron-doped silicon temperature-sensing

resistors (shown black in Fig. 1) are used to monitor the chip

temperature within its active area and are interleaved with the heater to provide high thermal coupling and temperature

uniformity. The thin sensing film (e.g., Pt/TiOx) is deposited at wafer level and is defined photolithographically

using a lift-off process. For films that are not compatible

with the final silicon etch used for window formation and die

separation, a sihcon micromachined shadow mask technology

has been demonstrated at wafer level to allow the use of

virtually any material that can be vacuum deposited.

DETECTOR FABRICATION

Figure 2 summarizes the process flow for gas

detector fabrication. Processing is performed on <100>-

oriented double-side-polished sihcon wafers. First, a 1.4|imthick silicon dioxide layer is thermally grown and patterned to act as a mask on both the front and back sides of the wafers

during the following deep boron diffusion. Backside

aligrmient is performed using an infrared aligner, with an aluminum pattern added to the front side as an alignment aid. The Al pattern is self-ahgned with the front oxide and does

not require an additional mask. After oxide patterning and

removal of the aluminum, a S^im-deep boron diffusion is performed at 1175°C for 2.5 hours in order to create the supporting rim, heater resistor, and temperature sensing

resistors. In order to form the dielectric windows, the wafers

are now thermally oxidized to about 200nm, and layers of

silicon dioxide (lOOimi), silicon nitride (250nm), and silicon dioxide (700nm) are deposited using LPCVD.

Fig. 1: Basic structure of the thin-film gas detector

Next, the heater and temperature sensor contacts are patterned and opened through the dielectric window using a

combination of wet etching and RIE. After stripping this

resist layer, the wafers are patterned again, and 5imi of Ti and

3nm of Pt are evaporated and lifted off to define a typical

sensing film. The sensing electrodes and connections to the heater and temperature sensors are next formed by sputtering

25nm of Ti and 200nm of Ir onto the wafer using a second

lift-off process. Finally, the silicon wafers are etched in ethylenediamine-pyrocatechol-pyrazine (EDP) in order to form

the windows, heaters, temperature sensors, and separation

lanes between the individual detectors on each wafer. The

EDP anisotropically etches the lightly-doped sihcon but does

not significantly attack the areas that have been heavily doped

with boron. Figure 3 shows a perspective view of the

dielectric window, heater, and contacts after the completion of

the fabrication sequence. All of the individual process steps

are standard in the microelectronics industry and, in fact,

54
similar process flows are now being run commercially. For

individual detectors not containing electronics, the doublesided process could be eliminated and a deep boron-diffused

rim could be formed from the front as in recent thermal

detectors [10]. This would eliminate one masking step along

with the infrared ahgnment and most of die slow EDP etch at the end of the process. OXIDE

R n n

SILICON WAFER

(A)

Heater Co

Ir/Ti Electrode PVTiO Sensing Film

y////A?~f^. . ////,

SWlcon Heater

Resistor Temp Sensing

Resistor

DEEP BORON DIFFUSION

Heater Thin Metal Dielectric Contact Film Window

(D) Hg. 2: Overall process flow for the monolithic gas detector.

Fig. 3: Cross-section of the completed window area of a micromachined gas detector.

ELECTRICAL DETECTOR

CHARACTERIZATION

Figure 4 shows a photograph of a typical detector

chip. Both circular and rectangular heater and sensor

geometries have been explored. The heaters have nominal

resistances of 750 and 1000 ohms, while die temperature

sensing resistors have a resistance of 350 ohms and

temperature coefficients (TCRs) of 1800ppm/°C. The thin sensing films in the case of Pt/TiOx are deposited during the batch wafer processing and are defined using photohUiography

(hft-off)- As noted above, they can also be defined using

shadow masking.

Fig. 4: Top view of a typical detector chip. The circular window has a diameter of 1mm.

Figure 5 shows the simulated window temperature

distributions for both the first- and second-generation detector designs through die middle of the window. The new design

provides a much more uniform temperature and the generated

heat is restricted to the area under the thin film, resulting in a more efficient heater. The fihn temperature uniformity has

55
been improved by more than an order of magnitude and is better than ±0.5% over the active area of OMmnfi (350|im x

350^mi). The total window size here is 1mm x 1mm.

X (nm)

Fig. 5: Simulated window temperature distribution along a

line from the center of the window to the window edge (x- direction). The input heater current is 10mA at room

ambient pressure (maximum convection).

Figure 6 shows the response of the dielectric window to input power in both in room air and in vacuum. The slopes correspond to efficiencies of 6°C/mW and

20°C/mW, respectively. In vacuum, temperatures well

above 1200°C can be achieved. At the anticipated operating

temperatures for gases of interest (200-500°C), a long

operating life is expected for the devices so long as the gases

are not reactive with silicon. In the case where the gas of

interest would react with silicon dioxide, a silicon nitride outer coating on the window could be used.

INTERFACE CIRCUIT DESIGN

In order to form a full gas analyzer, an array of these detectors is needed along with control circuitry for setting the window temperatures and sensing the fihn impedances.

While in this research, the readout/control chip has been

added as a hybrid to form a full analyzer, the basic gas

detector process is compatible with the use of on-chip

CMOS circuitry [11]. The only significant change

introduced into the CMOS process when merging it with the detector process is to perform the etch-stop diffusion as part

of the p-well drive-in procedure. For the present, however,

the detector and its control circuitry have been kept separate

in order to simplify fabrication of the many detectors needed

during on-going characterization studies.

Figure 7 shows a block diagram of the control chip

[31 and its connections to a corresponding detector. The chip

consists of three principal blocks: the heater controller, the conductivity sensing circuitry, and the control/interface unit. The chip communicates over an eight-line interface [12] to either an embedded VLSI microcontroller (forming a smart

sensing node) or to a remote processor. The desired set point

for the heater is entered serially and latched in an eight-bit

digital-to-analog converter (DAC). This DAC generates a

reference voltage for an MOS comparator which drives the

heater. Temperature feedback is derived from the sensing

resistor on the window and is used to limit the comparator

drive at the appropriate level. This window temperature can

also be read out.

The film conductivity can be measured at ac or dc

using the circuitry in the sensing block. Two eight-bit

DACs can be set using serial input data to select the

appropriate current level and frequency of the measurement

Magnitude and phase information is sensed and fed off-chip,

again using the eight-line interface. The chip has been

designed to operate with fihns having resistances (full scale)

from 5 ohms to 1.3Mobms, allowing it to be used with a wide variety of different film types. This control chip

employs over 4000 transistors and was fabricated at MOSIS using a 2fim p-well double-poly double-metal CMOS

process in a die size of 4.4mm x 6.6mm.

The control chip has been tested and found fully

functional with performance at or near the design targets. The heater drive voltage is separate from the logic supply to allow higher temperatures to be reached for special situations. (The temperature saturates at the higher DAC input codes if the heater back voltage exceeds the supply.) At 5V, the windows reach an operating temperature of about 150°C in air and about 350°C in vacuum, increasing in the latter case to 540°C at 7.5V and 100°C at lOV. The fihn conducUvity

measurement uses a film interrogation current that is set over an eight-bit range in amplitude and can be used from dc to 2MHz. The I/O interface logic also functions as required. —•— Temperature (°C), Vacuum —O— Temperature (°C), Air

Power (mW)

Fig. 6: Measured response of the dielectric window to input

power delivered to the heater in vacuum and in air.

SENSOR OPERATING MODES

Several operational modes are available using this thermally-compensated multi-element sensor structure which

emphasize various aspects of the chemical and physical

sensitivity and selectivity of these devices.

56
» COOEIN • DAr* YAueo o»r» out

Fig. 7: Block diagram of one of the four circuit blocks of the gas analyzer control chip.

Thermally-uncompensated mode: When the film is not thermally compensated, the sensor resistance changes are dominated by heat transfer to the gas phase, making the device a pressure and temperature sensor.

Thermally-compensated isothermal adsorption/desorption

jj mode: Accurate thermal compensation makes it possible to operate the sensor in an isothermal or temperatureprogrammed mode. In this mode of operation the sensor response is dominated by changes in resistance caused by

chemisorbed gases. The ability to operate the sensor over a wide temperature range allows us to optimize the sensitivity

I and selectivity of the active film to specific gases by

I selecting a temperature where high surface coverages are

j observed. A reversible response can be achieved by operating

I in a temperature regime where reversible adsorption/

[ desorption occurs.

Thermally-compensated isothermal reaction mode: One of

the major problems in the field of chemical sensing is the need to reset the sensor surface after irreversible adsorption.

This problem can be overcome by using chemical reactions with gases such as oxygen or hydrogen stored in adjacent,

thermally-activated chemical reservoirs. For a specific

j film/adsorbate system, the adsorbed species will show a

characteristic reactivity at a specific reaction temperature.

Thermally-compensated temperature-programmed desorption

mode: For situations where rapid desorption is not feasible,

adsorbed species can be removed by ramping up the temperature and monitoring the desorption of surface species.

The temperatures where adsorbed species can be removed

depends on their strength and nature of bonding to the surface.

There is a characteristic temperature where the chemical bonds

between film and adsorbed species break, releasing the adsorbate into the gas phase. By monitoring this change we

can often differentiate between various types of molecules.

Thermally-compensated temperature-programmed reaction

mode: Chemical reactions can also be used to remove

adsorbed species. The reactivity of adsorbed species on

particular catalytic surfaces depends on the structure of the adsorbed species and the chemistry of the active film. Therefore, for a specific film/adsorbate system, the adsorbed

species will show a characteristic reaction temperature with

typical "cleaning gases" such as hydrogen or oxygen. By

monitoring the response, we can often classify the nature of

the adsorbed species.

Multi-window sensing structures for enhanced selectivity:

Enhanced selectivity or reactivity modes can be accomplished

by combining several sensor windows into an array, where

each window is independently temperature-controlled. The

multiple windows can be equipped with different films to optimize selectivity for classes of molecules or for

storage/release of reactive species. In these configurations, more than one of the above modes of operation can be easily

accommodated on a single chip.

CONDITIONING OF SENSORS PRIOR TO USE

Stabilization of the active films is accomplished by

repeatedly exposing them to chemical and thermal

environments which are more severe than those expected

under normal operating conditions. We have found

experimentally that treating Pt/TiOx films in vacuum vs. oxygen at temperatures in the range of 500-700°C results in films with unique but stable chemical sensitivity.

Films pretreated at 700°C in vacuum show

resistances which are substantially smaller than those of

analogous films exposed to oxygen at the same temperature.

The temperature coefficient of resistance for vacuum-treated

films is positive, a property characteristic for metallic films. The behavior of oxidized films is much more complex and

often indicative of semiconducting behavior. Once stabilized, the sensing films show reproducible behavior for operation at temperatures below 500°C, independent of the chemical

environment the films are exposed to in RIE applications.

SENSITIVITY AND SELECTIVITY OF Pt/TiOx

GAS SENSORS

Response to low-pressure oxygen and hydrogen dosing using

the thermally-compensated temperature-programmed desorption mode:

We have demonstrated monolayer sensitivity by

observing significant and surface-coverage-dependent

resistance changes for both hydrogen and oxygen in a pressure regime of 10"^ Torr. These experiments have been performed

in UHV on both hydrogen and oxygen pretreated films.

57
1.006

1.004 -

1.002 -

1.000 -

0.998 -

0.996 -

0.994 0 200 400 600 800

Temperature (°C)

Fig. 8: Resistance change of a Pt/TiOx sensing film during

TPD following adsorption of lOL of O2 or 5L H2,

respectively. (1 Langmuir, L, corresponds to exposure to 10"^ torr gas for Is).

On adsorption of 5L of H2, the film resistance R

decreases compared to that of the clean film, R(clean film).

When the temperature is raised into the regime where

hydrogen is known to desorb from Pt surfaces, the resistance returns to that of the clean film. Exposure to lOL of O2

initially increases the resistance compared to the clean film,

and during temperature-programmed desorption the resistance slowly returns to the starting point of the clean film (Fig. 8).

Reversible response to oxygen using the thermallycompensated isothermal adsorption/desorption mode:

Figure 9 shows the response of a vacuum-activated

Pt/TiOx film exposed to 4.5x10-4 Torr of oxygen at 400°C.

When oxygen is removed from the reactor chamber, the resistance of the film returns to its initial value in less than two minutes, demonstrating the reversibihty of the response.

Response to oxygen and perfluoromethane mixtures at 10'^

Torr:

Films operated isothermally do not respond to pure CF4, while small additions of O2 in the ppm range lead to resistance changes characteristic for oxygen. Figure 10

shows a rapid increase in resistance when 6|aTorr of oxygen

is added to a How of 10|iTorr of CF4 at 300°C. When the oxygen flow is stopped, the resistance of the film gradually

decreases, indicating that the desorption of oxygen into the CF4 stream is slow. Addition of IfiTorr of hydrogen rapidly removes the remaining oxygen, and the film resistance drops

to the low value characteristic for a hydrogen-exposed film.

AR (mn)

140-1

120-

100-

80-

60

40-

20-

0-

O2 off

Torr O2

50 150

T

100 200

time(s)

Fig. 9: Response of a Pt/TiOx sensor operating at 400°C to changes in oxygen partial pressure. Oxygen was bled into

the system during the first 89 seconds, followed by pumping

down of the system.

CONCLUSIONS

This paper has reported a second-generation

conductivity-type gas detector. The structure is suitable for use with both conventional sensing films (e.g., tin oxide) and

with ultra-thin metal films. The upper surface of the detector

structure is highly planar to eliminate the step coverage

problems associated with polysilicon heaters. Single-crystal

boron-doped silicon sensing and heating resistors are formed

underneath the dielectric window from the wafer bulk. The

heater design results in a temperature uniformity over the sensing area of within ±0.5 percent and allows measurement

of the operating film temperature to within VC. A

monolithic CMOS interface chip allows four such detectors

to be operated simultaneously using digital input commands

received over an eight-line bus. Window temperature can be

set with eight-bit accuracy over the range from ambient to over llOO'C, while film conductance is measured over a broad range in both magnitude and frequency. This sensing

structure can be operated in a number of modes depending on

requirements for selectivity, sensitivity, and time response.

58
Monolayer sensitivity for oxygen and hydrogen has been

recently demonstrated for a Pt/TiOx sensing film operating at room temperature in the temperature programmed desorption

mode. Reversible response to oxygen has been demonstrated

for this same film operating at 400°C. The thermallycompensated isothermal reaction mode has been illustrated using oxygen in the presence of CF4 and removing the oxygen by reaction with hydrogen. Detailed chemical

characterization of these devices is underway in a variety of gaseous environments.

Resistance (Q)

975

965 -

955 --

945 -

935 -

925 --

02 Off

Ix 10-6 TH2

^ I. . . "I

915

6 X 10-6 T 02

H2 off

0 200 400 600

Time (s)

f Fig. 10: Response of an integrated gas detector in 10|iTorr

of CF4 to the addition of 6|iTorr of O2, followed by removal

of oxygen and exposure to H2.

Acknowledgments

The authors gratefully acknowledge the support of

die Semiconductor Research Corporation in sponsoring this research. Dr. Christy L. Johnson was responsible for the

early phases of detector development, while the bulk of the

detector results reported here are the work of Dr. Nader Najafi.

Ms. Robin Merchant and Ms. Hongjun Liu have played an

important role in the chemical characterization of the present

detectors, and Mr. Emmanouil Mavrikakis has added

significantly to the theoretical understanding of their surface chemistry. The authors also thank Mr. Paul L. Bergstrom

for his work in fabricating recent detectors and in developing

the latest generation of their instrumentation.

REFERENCES

1. A. Ikegami and M. Kaneyasu, "Olfactory detection using

integrated sensor," Digest IEEE Int. Conf. on Solid-State Sensors and Actuators, pp. 136-139, June 1985.

2. N. Yamazoe and T. Seiyama, "Sensing mechanism of

oxide semiconductor gas sensors," Digest IEEE Int. Conf. on

Solid-State Sensors and Actuators, pp. 376-379, June 1985.

3. N. Najafi, K. D. Wise, R. Merchant, and J. W. Schwank

"An Integrated Multi-Element Ultra-Thin-Film Gas

Analyzer," Digest, IEEE Solid-State Sensors and Actuators Workshop, Hilton Head, South Carolina, June 21-25, 1992.

4. C. L. Johnson, N. Najafi, K. D. Wise, and J. W.

Schwank, "Detection of Semiconductor Process Gas

Impurities using an Integrated Ultra-Thin-Film Detector,"

Digest of Technical Papers, SRC TECHCON'90, San Jose, pp. 417-420, October 1990.

5. P. Romppainen, V. Lantto and S. Leppavuori, "Effect of

Water Vapor on the CO Response Behavior of Tin Dioxide

Sensors in Constant Temperature and Temperature-Pulsed

Modes of Operation," Digest Intl. Conf. on Solid-State Sensors and Actuators, Montreux, June 1989, pp. 73-76.

6. G. Sberveglieri, S. Groppelli, P. Nelli, V. Lantto, H.

Torvela, P. Romppainen and S. Leppavuori, "Response to Nitric Oxide of Thin and Thick Sn02 Films Containing

Trivalent Additives," Digest Intl. Conf. on Solid-State Sensors and Actuators, Montreux, June 1989, pp. 79-82.

7. C. L. Johnson, K. D. Wise, and J. W. Schwank, "A thin- film gas detector for semiconductor process gases," IEEE

lEDM Digest of Technical Papers, pp. 662-665, December

1988.

8. C. L. Johnson, Ultra-Thin-Film Monolithicallv-Integrated

Silicon-Based Gas Detectors . Ph.D. Dissertation, The

University of Michigan, 1990.

9. N. Najafi, A Generic Smart Sensing System Utilizing A

Multi-Element Gas Analvzer. Ph.D. Dissertation, The

University of Michigan, 1992.

10. W. G. Baer, K. Najafi, K. D. Wise, and R. S. Toth, "A

32-Element Micromachined Thermal Imager with On-Chip

Multiplexing," Sensors and Actuators, to be published.

11. J. Ji and K. D. Wise, "An Implantable CMOS Circuit

Interface for Multiplexed Microelectrode Recording Arrays,"

IEEE J. Solid-State Circuits, 27, pp. 433-443, March 1992.

12. N. Najafi and K. D. Wise, "An Organization and

Interface for Sensor-Driven Semiconductor Process Control

Systems," IEEE Journal of Semiconductor Manufacturing,

pp. 230-238, November 1990.

59

Amperometric Electrochemical Gas Sensors: Description and Applications

Joseph R. Stetter

Transducer Research, Inc. 999 Chicago Avenue

Naperville, IL 60540

The amperometric gas sensor can and does provide industry with a sensitive and often

selective measurement for toxic gases. These devices are relatively simple and low

cost, consume only mW of power and need no consumable supplies to operate.

Gases measured include 0^, CO, HjS, NO, NOj, SO2, O3, HON, HCI, NH3, H2CO, and

many others at the ppm and ppb level. Applications include environmental, health,

safety, industrial hygiene, medical, military, analytical instruments, field research [e.g.

volcanology], and process control applications. Future devices will be improved and

address new industrial markets like stack gases and space station controls.

AMPEROMETRIC GAS SENSORS

This manuscript presents a brief description of

the amperometric gas sensor and is based upon

several recent reviews [1,2]. The focus of this

discussion is sensors of the type with which the

author has been most extensively involved.

There is not attempt to slight other

electrochemical sensors be they excellent

examples of amperometric, potentiometric, or conductimetric sensors. This review is limited for

practical reasons. This work would not have

been possible without the tireless support of my

many collaborators and colleagues [whom are indicated in the citations and references therein].

The low power, small size, and other logistical

characteristics of electrochemical detectors make

them an attractive technology and commercial

amperometric gas sensors are very successful

[1,2]. The sensitivity of these electroanalytical

methods is often impressive. For example, an NO2 sensor, even in a flowing gas stream, can

easily detect about 4 x

10"^^ G/sec and this

corresponds to a detectable concentration of less

than 2 ppb in the 200 cc/min gas sample flowing

through the sensor cell. The typical limit of

detection in these systems is not the detection of

the reaction since the reaction produces

significant electric currents even at extremely low

concentration. Rather, detection using

electrochemical gas sensors is limited by the

ambient background currents, interferences, drift,

and amplifier noise all of which degrade the S/N

(signal to noise ratio) of the amperometric sensor

in a particular application. Therefore, we expect

improvements in the sensitivity of amperometric

gas sensors to come not from increasing the

magnitude of the analyte signal but rather from

the reduction or elimination of the background

61
currents and by employing sensor electronics and

pneumatics that can distinguish the signal over the background, noise, and drift. Investigation of

novel solid electrolytes, new eiectrocatalysts, and

microsensor structures with unique geometries

have produced gas sensor systems with

exceptionally fast response and improved signal

to noise ratios. But these new gas sensor systems appear to contaminate easily.

The electrochemical gas sensor has been used to

measure many industrial compounds including

CO, HjS, NO, NO2, H2CO, N2H4, H2, SO2, HCN,

mercaptans, NH3, HCI, and others. In principle,

any compound that is electrochemically active

[i.e., can be electro-oxidized or electro-reduced] can be measured with this approach. In practice, sensors are most useful for compounds with

significant vapor pressures and functional groups

that are easily reacted to form gaseous products.

Problems occur if the analyte forms residues or contaminants that are deposited in the sensor or dissolved in the electrolyte.

Classical electroanalytical chemistry offers the

tools to characterize gas sensor reactions.

However, there have not been many scientific

investigations of the electrochemical reaction

mechanisms that occur in these gas sensors. There is however, a relationship between the

structure of the sensor and the observed

electroanalytical performance [advantages and

limitations]. One of the most well characterized

gas sensors is the classical Clark-type oxygen

sensor and I suggest a review of this work for

anyone interested in a basic understanding of the

parameters involved in the construction and

application of amperometric gas sensors [1,2].

STRUCTURE

The amperometric gas sensor is a device that

allows a gaseous analyte to reach the surface of an electrode that is also in contact with an

electrolyte. At this triple point of solid electrode,

gaseous analyte, and liquid electrolyte, an electrochemical reaction [i.e., one involving the

transfer of charge] can occur. If the electrolyte is a solid, the triple point is solid-solid-gas. The

structure of this triple point is typically fabricated

using a porous body that allows gas penetration

from one side and electrolyte contact from the

other. However, many variations of this porous

body are possible and are only limited by the

imagination and ingenuity of the sensor scientist.

A schematic of the amperometric gas sensor is presented in Figure 1

.

and Interierences o

Rgure 1 . Schematic view of an amperometric gas sensor lllustratif contact among analyte, electrode, and electrolyte.

Amperometric gas sensors have three major

constituents: a gas permeable layer to allow gas

to get into the electrochemical cell, electrodes at which to perform the electron transfer, and

electrolyte to provide Ionic contact among the

electrodes. The geometry of the structure to

house the electrochemical cell can have a profound influence on the rate of the

electrocatalytic event and on the ultimate

performance specifications of the sensor. An

electrolyte is a material capable of ionic

conduction. Typical examples are illustrated in TABLE 1. In a gas sensor, the electrolyte must

solubilize the analyte in an appropriate form for

reaction, be stable in the potential region [and T,

P, RH] being used for the analyte reaction, and be j inert to the electrode and other cell components i so as not to cause corrosion [or stray currents] to f occur. For the electrolyte system, it is important

to consider the conductivity, liquid range, vapor 1 pressure, dielectric constant, viscosity, stability j [chemical and electrochemical], purity, ability to 1 solubilize analytes and products, effect on ) referenceelectrodes,and spectroscopic properties 1

(if a spectro-electrochemical experiment is

' planned). The best choice of electrolyte will 1 depend upon the application of the sensor. ?
TABLE 1. COMMON ELECTROLYTES

AQUEOUS ELECTROLYTES

NON-AQUEOUS

SOUDS. POLYMERS, and MIXTURES

Acid: Sulfuric. Perchloric, Phosphoric

Base: NaOH, CsOH, uOH, KOH

Neutral: KQ. UCI, UBr, NaHCO^

Solvents: Propylene carbonate,

DMSO, DMF, Acetonitrile, Ethylene

glycol. Oichloromethane, (with

salts e.g., UO or LiCIO« for the

electrolyte)

Nafion/water, PEO'UX, PVA/HjPO,,

PVA/CsOH, AgRb.lj, Agl

The sensor also contains a sensing

(working), counter, and reference electrode.

These are typically chosen from the noble metals

such as Au, Pt, and composites like Pt/TFE. The

electrode material must be compatible with the

electrolyte. Silver and Nickel electrodes have

been used in basic (and non-aqueous) electrolyte

systems and (glassy) carbon electrodes are popular in acidic and basic media. The electrode

material and the potential of operation are chosen

to engineer sensitivity, stability, and selectivity

into the gas sensor.

The gas permeable membrane can be a Teflonbonded diffusion electrode (TBDE) of the kind

used in fuel cells or a simple thin film material. A

thin 0.5 mil solid film of Teflon will allow

permeation of oxygen and is used in the Clark sensor as a barrier to keep out unwanted

interferences in the sample. The TBDE is, typically, a thin 5-10 mil Teflon film, that is porous [1-10 micron pores], to which an admixture of Teflon particles and electrocatalyst

particles [e.g. Pt black] have been bonded by heat

and/or pressure methods. This unique structure

is very rugged, convenient to make and use, and

extremely efficient at maintaining a very high

surface area triple point. Gas access is fast and

the electrode-electrolyte interface is of very high

stability and surface area. Gas sensors with high

sensitivity are made with this approach.

APPLICATION NOTES

The essential components of a sensor (Figure 1)

are always the same but the electrochemistry,

geometry, and size differ greatly. There is an

integral and an important relationship among the

materials of construction, the specific cell geometry, and the analytical performance of the sensor for a particular application. This can be

appreciated by consideration of sensor response

to specific analytes and the wide variety of sensor systems that are available commercially

and that have been reported in the past. A thin

polymer film planar microsensor can have a response time measured in mSec while a large

TBDE sensor for CO may take seconds to

respond. The use of planar structures for both

the sensor and the electronics offers significant

possibilities for future sensor design. It may be

possible to design and construct low cost sensors

with the increased precision and reliability of

silicon fabrication technology and also improved

analytical performance.

Chemical differences also have a profound effect on the sensor performance specifications.

Sensors with aqueous acid electrolyte (battery

acid freezes at about -40°C) can be used at low

temperatures but the solid polymer Nafion uses

liquid water and freezes at 0°C losing much of its conductivity and preventing low temperature use

of the sensor. Basic electrolytes produce well

behaved signals for analytes like NH3 or hydrazines while acid electrolytes produce drifting

irreproducible responses. This is because the

hydrazines are protonated in acid solution but

remain in molecular form in basic solution. The

electrochemistry of these two species

(protonated or molecular) is very different. When

the sensing electrode is made of high surface

area Pt, it will provide a good response to CO,

but when it is made of Au powder, it will not

respond well to CO. Yet a gold electrode will

respond to HjS very well. Therefore, Au is the

electrocatalyst of choice to make an HjS sensor

that can be used even in the presence of CO [i.e., a selective HjS sensor].

Choice of electrochemical conditions is also

important to sensor performance. If a gold

catalyzed electrode is operated at a potential of

about 0.8 V vs. SHE (the standard hydrogen

electrode), then NO2 can be electro-reduced but

NO cannot be reacted (oxidized or reduced).

Therefore, the selective detection of NO2 in the

63
presence of NO is possible with an amperometric

sensor operated with potential control at 0.8V vs SHE [using a potentiostat circuit].

The above discussion provides only a few brief

examples of choices that one can make for

structure, materials, geometry, and method in a sensor. The point is that these are the

parameters that profoundly effect sensor

sensitivity, response time, selectivity, and

stability. The overall performance of a sensor is a direct consequence of these choices.

CONCLUDING REMARKS

The amperometric sensor is a complex and

interactive system of metallic and non-metallic

components. The entire device must be chosen

as a system in order to obtain good analytical

performance for a specific application. The

structure and geometry of the system is important as is the selection of appropriate

materials. Our understanding of the electrochemistry within these geometries and their

relationship to sensor performance currently limits

applications engineering.

This brief essay has been intended to highlight

some of the attributes of the amperometric gas

sensor. There are many more systems that must

be discussed to appreciate the intricate and

fascinating variety of sensors that have been

constructed. The reader is directed to the

references for a more complete review of what

has been accomplished to date by the many

scientists and engineers who contribute to this

field. Be assured that the future will bring even more creative devices that will find their way into

the mainstream of our lives in the next ten years.

REFERENCES

[1] B.C. Chang, J.R. Stetter, and C.S. Cha,

Amperometric Gas Sensors , Talanta, Vol.

40, pp. 461-477, 1993.

[2] Z. Cao, W.J. Buttner, and J.R. Stetter,

The Properties and Applications of

Amperometric Gas Sensors . Electroanalysis, 4, pp. 253-266, 1992.

[3] Opportunities for Innovation: Chemical and

Biological Sensors . N. Madou and J. P. Joseph, eds., NIST GGR 91-93-1,

USDOC, NIST, Gaithersberg, MD, 1991.

[4] Janata, J.. Principles of Chemical Sensors.

Plenum Press, NY 1989, ISBN-0-306-

43183-1.

[5] Sensors and Sensory Systems for an

Electronic Nose . J.W. Gardner and P.N.

Barlett, eds., Kluwer Academic Pub.,

London, 1992, ISBN-0-7923-1 693-2.

64
Gas Phase Sensing in the Chemical Industry: Today's Practiced Technology

Kevin Hool

The Dow Chemical Company

Central Research and Development, 1712 Building

Midland, MI 48674

Robert Bredeweg, Del Lefevor, Mark LaPack, and Larry Wright

The Dow Chemical Company

Analytical Sciences Laboratory, 1897 Building

Midland, MI 48674

The application of analytical techniques for on-line measurements termed

process analytical chemistry is a rapidly growing area of technology

attracting a growing commercial interest. Within the chemical industry, the

majority of process analyzers utilize more conventional analytical methods

than die technologically recent 'sensor' systems. Some reasons are given for

this trend. A number of example process analysis approaches including

sampHng methodology are examined. The potential for gas sensor arrays in

process analytical is discussed.

The evolution of chemical analysis in the

chemical processing industry continues to move

away from traditional off-line analysis, in which

samples are removed from the process

environment and taken to a laboratory, towards

on-line analysis with sophisticated integrated

sampUng and analytical instrumentation

systems. This integration of analytical

techniques to on-line analysis is now recognized

as a sub-discipline of analytical chemistry

known as process analytical chemistry

(PAC)[1]. Within the field of PAC, gas phase

analysis is an area that perhaps can attest to being the most rapidly developed for on-hne

use.

The example applications cited in this paper are intended to give a representative accounting of

how gas analysis is performed in the process

environment within Dow and perhaps the

chemical industry in general. This paper will

highlight aspects of several applications

successfully implemented for on-line or in-situ

gas analysis at Dow. These applications were

selected to emphasize how the major techniques can be implemented. These cases, in turn, can

typify the types of challenges that gas 'sensors' must meet if they are to be utilized for on-line use in the process environment.

It is interesting to note that despite the

tremendous advances made in micro-electronics

and materials processing technology that has

prompted the development of a myriad of gas

'sensors', these devices are in general, not

widely used for on-line gas phase analysis.

Rather, most of the advances in on-hne gas

analysis have resulted from the integration of

the relatively mature analytical techniques such

as gas chromatography, mass spectrometry, and

optical spectroscopy.

There are several significant factors that

contribute to the lack of gas 'sensors' being

widely used for process measurements. First,

the process environment requires an

instrumentation package that provides higher

rehability with lower maintenance than

laboratory counterparts. As mentioned above,

the relatively mature and proven laboratory

analytical techniques for gas analysis have been

easier to re-engineer to meet process analytical

instrumentation specifications. Second, because

the processes requiring gas analysis vary

greatly, instrument vendors have found it difficult to generate multi-purpose or generic

platforms on which to base the process

instrument package. Third, by their very nature,

gas 'sensors' generally respond only to a small

range of compounds, while the detection

65
schemes used in gas chromatography, optical

spectroscopy, and mass spectrometry are far

more versatile for examining the large variety of

gases and vapors in the chemical processing

environment. Because of this, many of the

advances made in process gas analyzers were

generated by industrial scientists with years of

experience applying these techniques in many

on-line applications.

While lagging behind in being utilized for online process applications, by no means are the use of gas 'sensors' absent from use in the

chemical industry. As in many industries, sensors are utilized heavily for ambient air

monitoring. In this arena, O2 and CO comprise

the most numerous applications with metal

oxide and electrochemical based sensors performing the majority of the work. Within the

field of industrial hygiene, in addition to the use of traditional off-line analysis, a number of gas

sensors in the form of dosimeter badges are used

for area and personal monitoring for toxic or noxious gases.

Gas 'sensors' are also used routinely for fugitive

emissions measurements. Here, the portability

of these sensor-based instruments are often the

enabling feature. Some instruments used for

this purpose within Dow are based on photoionization and thermal conductivity.

Gas Sampling

Critical to most process analytical methods is the means of obtaining and introducing a sample

from the process to the instrument. An obvious

way of improving sensitivity towards an analyte

is to provide some means of preconcentrating it prior to analysis [2]. An excellent means of

performing this task is with a membrane based

technique. Figure 1 illustrates a typical hollow

fiber membrane extractor. In this device, a pressure differential across the membrane acts as a driving force to push vapors across the

membrane, while the membrane material

properties determine the relative rates of

diffusion for the various gases. Different

diffusion rates (which are temperature

dependent) leads to enrichment of one species over another. Table 1 gives a listing of

enrichment factors for a variety of organics that can be obtained with a silicone membrane.

Sample In

I

Sample Out

Figure 1. Diagram of a hollow fiber membrane

extractor.

COMPOUND Relative to N 2

26° C 45° C

Relative to H 2°

26° C 45° C

Chloromethane 40 27

Dichloromethane 48 33 1900 1100

Chloroform 91 58 2100 1100

Carbon Tetrachloride 1 10 74 1800 1100

Chloroethene 37 26

1,1 Dichloroethene 57 35 3300 1800

Trichloroetherie 140 81 970 530

Tetrachloroethene 310 180 600 360

Dibromomethane 84 50 190 100

Bromoform 320 170 570 330

Benzene 170 1 10 2600 1400

Toluene 380 230 2300 1300

Ethylbenzene 450 280 2200 1200

Chlorobenzene 550 330 1300 730

1 ,3-Dichlorobenzene 520 350 470 300

1 ,2,4-Trichlorobenzene 780 400 450 390

Table 1. Enrichment factors for various organic

species over nitrogen and liquid water.

As can be seen from Table 1 , several orders of

magnitude of preconcentration can be obtained.

When used to extract organic vapors from

aqueous streams, membranes also eliminate

solids and dissolved ionic species from being

sampled. This can reduce the problems of these

66
compounds fouling or plugging sampling lines

[1].

Liquid Sample

Inlet

Another commonly used technique to sample

dissolved organics from aqueous streams is to sparge with a non-interfering gas. Figure 2

illustrates a typical arrangement.

To Analyzer

Hot Water

Jacket

Helium Sparge

Gas Inlet

N

Sample In

Figure 2. Sparge technique used to purge

dissolved gases from liquid samples.

However, systems which utilize a sparging

arrangement can be plagued by foaming when a small amount of surface active agent is present

in the sample stream [1]. A better technique in

these instances has been developed by

Kozlowski et. al. [3], termed 'thin layer head

space'. Figure 3 shows a thin layer head space

apparatus for purging volatiles from liquid

samples. In this device, the liquid sample is introduced into a coiled glass tube which has a

sparging gas flowing counter current. Surface

tension of the aqueous stream forces a thin film

of liquid to flow via gravity down the inner

surface of the coiled tube. The volatiles are purged from the liquid sample stream provided

enough surface area to the sparging gas is available.

Liquid Sample

Outlet

Figure 3. Schematic of Thin Layer Head Space

sampling apparatus.

SELECTED CASE STUDIES

A. Multi-Point Sampling/Mass Spectrometry

When faced with a task of monitoring a large

volume, area, or a large number of sampling

points, two basic strategies are used. In one

case, a process mass spectrometer is used to check for process leak detection. The

requirements included low ppb sensitivity to the

compound of interest and a relatively fast

analysis time so that greater than 50 points

could be sampled with a reasonable time. In

this case, a specially built 64-way sampling

valve was used to direct sample(s) from the

various sampling positions to the process mass

spectrometer. The process analyzer was used to alarm a process computer when the analyte

exceeded 20 ppb. Expected mean time between

failure(s) is greater than 1 year.

In another application, a small portable mass

spectrometer was used to evaluate the

concentration uniformity of an agricultural

product in an exposure salon. Figure 4 gives a diagram of the case studied.

67
CONCENTRATION (ppm) UNIFORMITY TEST

IN EXPOSURE SALON

X.X - 6-7 ft. above floor

^-3-4 ft. aoove floor

MSD

Restroom

1.3 Door

1.3 1.4

1.3

1.3

Sampling

Prob©

1.3 Door

Figure 4. Sampling ambient air from multiple

locations in an exposure salon.

In this study, participants were exposed in a

controlled test to an agricultural product to determine product uptake in the body. For

safety, the exposure level was monitored in the

salon with a mass selective detector. In this case, a single sampling point physically moved

to various sampling points proved an adequate

solution.

In yet another case, a sampling station in the

form of a tethered island was used to sample the

evolved gases from a waste water treatment

plant. The long tether contained a sampling

probe which retrieved the sample to a process mass spectrometer. This sampling scenario

provided a means to sample locations

immediately above the water's surface without

requiring a human to collect and retrieve

samples.

B. Process Gas Chromatography

Perhaps the most widely utilized technique for

process analytical is gas chromatography [1,4].

Strengths include versatility and low detection

limits. Process GC also maintains perhaps the

best product support, with a number of process

GC's now commercially available in addition to the laboratory GC's which share many parts.

sampling can be employed (as mentioned

earlier). However, if short cycle times are required, a conventional GC may be too slow.

A relatively new development is the micro-GC.

Complete chromatograms can be obtained in

under 1 minute with this technology. A microGC from MicroTechnologies Inc. has been

incorporated into a process analyzer package

employing two different columns with thermal

conductivity detection. This instrument was

utilized for vent stack analysis as required for

the EPA. Figure 5 gives an example

chromatogram illustrating the rapid multicomponent analysis capability of this

instrument.

Currently, the micro-GC is limited to the

analysis of gas samples only, since they lack a vaporization chamber. Additionally, care must

be taken with this technique to avoid

condensation of vapors inside the sampling

lines.

C. On-Line FT-IR

A substantial amount of work incorporating FTIR (also, NIR and Raman) into process

analytical applications has been performed as evidenced by a recent extensive review of the

subject [1]. Strengths of the technique include,

low detection limits (with the use of long-path

cells), improved flexibility with the use of

optical fibers, the simultaneous determination of

multiple species, and excellent reliability.

These instruments for on-line use often exceed a mean time between failures of greater than 1 yr.

In an example application, an FT-IR has been in

used in closed-loop process control for 8 years. In this application, a hot (170°C) process stream

is interrogated via IR using a specially designed

sample cell as shown in Figure 6.

The method of sampling a process continues to be where a significant amount of development

time is spent. In applications requiring a large

number of points to be sampled, multi-point

68
A Module = 4m X 0.1mm ID, DB-5 0.25pL

4-vtrytcyclohexa ne

1 rtyrefw

19 23 27 31 35 39 43 47 51

Time (sec.)

B Module = 6m X 0.1mm ID, OV-1701,

air Ln-propan. QC B

/ n-buUnc

^ cit-2-tA.'Vtrit

VT^ vjjyfldj^ ^^^^

ii^ ll li. 11,1, |l

1

1

1

10 20 30 40 50 60 70

Time (sec.)

Figure 5. Example chromatograms taken on a micro-GC used in vent-stack analysis.

Silicone O-Ring(s)

Figure 6. Special FT-IR cell with heated

sapphire windows to prevent condensation from

a hot sample stream.

An analysis is performed every 50 seconds and

feedback given to a process control computer.

In applications involving closed looped process

control, reliability is essential.

In another application, a custom designed long

path (22 meter) FT-IR process analyzer is being

used to determine organic vapor break-through

from a carbon filter bed. In this application,

instrument resolution was sufficient to simultaneously determine 8 organic vapor

species. Cost of the hardware components was

on the order of S60K.

DEVELOPING GAS SENSOR ARRAYS

FOR VOC'S

In an entirely new way of performing gas

analysis (particularly in the process

environment), the use of arrays of gas sensors has emerged as a 'hot' area of research. The

approach, often termed "electronic olfaction"

relies on a pattern recognition approach for gas

analysis [5]. While not in current use for

process measurements, research is underv-'ay at Dow (and many other institutions) to examine

the utility of arrays of gas sensors for volatile

organic compound (VOC's) determinations.

69
Currently, commercially available metal oxide

gas sensors have been utilized in a flow

injection arrangement for the identification and

quantitation of 10 organic vapors. Provided that

the sensor array can provide a pattern that can

be mathematically distinct from other responses,

complex mixtures can be identified as easily as single compounds.

The use of sensor arrays offers a means of

providing 'state of condition' information within

the process. This can be very useful in

functioning as process alarms. Also,

independent operating sensors placed

throughout the process may prove useful in

correlating sources of process upsets via

chemometric analysis (i.e.. building an intuitive

model of the process via sensor array feedback).

CONCLUDING COMMENTS

It has been reported that providing an adequate

sampling systems consumes 90% of the effort in

making a process analyzer functional [4].

Because the approach taken to determine the

best method to implement is driven by the

process requirements, a large number of

methodologies will have to be supported. In the near future, process analytical methods will

continue to be largely implemented with the

traditional analytical methodology. The trend of

having many of the advances in process

technology being generated in-house is likely to continue until instrument companies better align

themselves to these opportunities [1].

Improvements are also being generated by

alliances between industry and academic and

government laboratories. A large part of the

research effort to improve process analytical

technology will certainly be focused on

integrating the advances in computers,

electronics, materials, sensors, and

chemometrics into process analyzers. In

particular, as parallel processing technology

improves, the use of pattern recognition

techniques should heighten the interest in arrays

of sensors used for process analysis.

REFERENCES:

[1] K.R. Beebe, W.W. Blazer, R.A.

Bredeweg, et.al. "Process Analytical

Chemistry," Anal. Chem., Vol. 65, No. 12, pp.

199R-216R, 1993.

[2] G.O. Nelson "Gas Mixtures: Preparation

and Control," Lewis Publishers, Ann Arbor,

1992.

[3] E. Kozlowski, T. Gorecki, E.F.

Sienkowska-Zyskowska, J. Anal. Chem. 342,

401.

[4] M.T. Riebe and D.J. Eustace, "Process

Analytical Chemistry: An Industrial

Perspective", Anal. Chem., 62 (2) pp. 65A71A,1990.

[5] J.W. Gardner and P.N. Bartlett, "Sensors

and Sensory Systems for an Electronic Nose",

NATO Series E , Applied Sciences- vol. 212,

1992.

70
Development of Differential Mode and Solid Electrolyte Gas Sensors

Qinghai Wu, Wei Peng, Henrique do Santos, and Chung-Chiun Liu

Electronics Design Center and Edison Sensor Technology Center

112 Bingham Building

Case Western Reserve University

10900 Euclid Avenue

Cleveland, OH 44106-7200

Chemical and gas sensing can be accomplished using tin oxide based, Schottky diode, calorimetric and

electrochemical sensors. In recent years, the application of microfabrication and micromachining techniques

has led to the development of these sensors into low mass, low energy consimiption devices. Furthermore, an

array of identical sensors can be fabricated permitting the sensors to be operated in the differential mode. In

the differential mode of measurement, a pair of identical sensors are used, with one consisting of an

electrocatalyst for the chemical or gas of interest, and the other serving as a reference. This operation enhances

the selectivity and sensitivity of the sensor. For electrochemical sensors, solid oxide and solid polymer

membranes have been used as the electrolytes, particularly for oxygen sensors. A comparison of the performance, limitations and applications of these two types of oxygen sensors will be given. We believe that microfabricated and micromachined sensors will contribute significantly to the development of chemical and

gas sensors.

Over the years, it has been demonstrated that gas and chemical sensing can be accomplished using tin oxide based,

Schottk>' diode, calorimetric and electrochemical sensors. For practical applications, solid state electrolytes are often incorporated into these sensing devices. In recent years, the

desire to produce low mass, low energy consumption sensors has led to the application of microfabrication techniques in the research and development of chemical and gas sensors. The advancement of micromachining technology provides a new venue for fabricating these sensors to meet the needs. However, the selectivity and sensitivity of these microfabricated sensors need not be compromised.

Conventional chemical and gas sensors are operated using a

single device for absolute measurement. This mode of

measurement is considered practical, for the commonly used

sensor is large in size and relatively costly. However, there

are circumstances in which interference by other chemical

species, the signal-to-noise ratio and/or the selectivity and

sensitivity of a single sensor are less than desirable. It is feasible to employ a differential mode of sensor operation to overcome these weaknesses. In the differential mode of sensor operation, two identical sensors are used, with one sensor

as the active device, and the other serving as a reference. The active device may incorporate an electrocatalyst or gas

reaction promoter, whereas the reference sensor does not. While these two sensors are exposed to the same sensing

environment, the active sensor will be more sensitive and

selective to the gas or chemical of interest, due to the effect of the electrocatalyst. On the other hand, the reference sensor may detect only the background gases and chemicals in

the testing environment. Consequently, the difference be- tween the two sensor outputs can be used to quantify the detecting species. The reference sensor, in this case, nullifies the background contribution, enhancing the overall sensor selectivity and sensitivity. This approach is very similar

to the well-accepted differential thermal analysis concept. A

similar concept for electrochemical analysis has also been

proposed, such as differential pulse voltammetry for enhancing detection sensitivity.

It is obvious that a sensor operating in the differential mode,

if properly designed, can provide improved performance.

However, over the years, the application of the differential mode of measurement in practical sensor development has

remained elusive, and the potential for this mode of sensor

operation has not been fully realized. This is due to the

difficulties in fabricating highly reproducible, geometrically

well-defined, modest cost sensor pairs on a relatively small

structural substrate. The advancement of microfabrication

and micromachining technology provides a new venue in the development of the differential measurement mode of chemical and gas sensors. Our laboratory has been engaging in

this type of research, and examples will be used to illustrate the merits of this approach.

As mentioned, solid state electrolyte has been employed in electrochemical sensors for gas and chemical sensing.

Among these solid state electrolytes, both solid oxide and

solid polymeric membranes have been used, particularly for oxygen sensing. In oiu" laboratories, a voltammetric sensor

for oxygen detection is developed; one version of the sensor 71
uses a yttria stabilized zirconium dioxide as the electrolyte,

and the other employs a solid polymeric electrolyte (Nafion).

The applications and characteristics of the oxygen sensors using these two different solid state electrolytes will be compared and discussed in this research.

Examples of Chemical Sensors Operated in the

Differential Mode

Calohmetric Sensors for Combustible Gases

Detection of combustible gases is highly important in gas

sensing. A common sensor for gas detection is the catalytic

combustible gas sensor. Oxidation of the combustible gas in the presence of a properly chosen catalyst results in the pro- duction of heat (heat of oxidation). If a temperature sensing

element such as a resistance thermometer is used to measxu-e

the temperature rise due to the heat generated in calories,

this rise in temperature can be used to quantify the combustible gas present. This type of calorimetric gas sensor is often described as a pellistor [1,2].

In our laboratory, silicon-based microfabrication and micromachining techniques are used in the development of a combustible gas sensor operating in the differential mode. Fig- ure 1 shows the schematic structure of a two-sensor array combustible gas detector.

Sensors 1 and 2 in Figure 1 are two identical platinum resis- tant temperature sensing elements. They can also be used as

resistant heating elements. Chemical anisotropic etching is used to selectively remove the silicon substrate upon which

the sensors are formed. This results in a cantilever structure of the platinum resistant film, minimizing any mass heat

loss due to the silicon substrate. Experimental results show

that the power requirement for heating both sensors is very

minute. Figure 2 shows that both sensors can be heated up

to 400° C at approximately 80 milliwatts. With this "generic" sensor structure, various electrocatalysts can be

incorporated forming different combustible gas sensors. The

advantages of producing a sensor of low mass, low power

consumption and differential mode of operation can be real- ized by these micromachined sensors.

A pellistor can be a platinum coil which acts both as a heat- ing and temperature sensing element and is coated with an

electrocatalyst such as platinum black or palladium or

others. This catalyst-coated pellistor is the active sensing

element, and a non-coated pellistor serves as the reference. When this pair of pellistors is heated to a desirable operating

temperature, e.g., 350° C, the oxidation of the combustible gas at the catalytic sensor surface will produce heat, result- ing in a temperature increase. This temperature increase

may be only in the order of degrees or tenth order of degree,

but this increase is measurable and can be used to quantify

the combustible gas present. The differential mode of meas- urement between the outputs of the two pellistors is well

suited to this detection.

600

20 40 60 80 HEATING POWER , mW

100

Figure 2: Heating power and temperature relationship

of a two-sensor array combustible gas sensor.

•SENSOR I

SENSOR 2

Figure 1 : Schematic of a two-sensor array.

Tin Oxide Based Gas Sensor

Another group of chemical and gas sensors used extensively I

is the tin-oxide based sensor, pioneered by Taguchi [3] and

Seiyama et al. [4]. Tin oxide sensors were constructed using

sintered tin oxide beads or bars. In recent years, silicon based microfabrication technology has been employed to produce tin oxide sensors. The selectivity of tin oxide sensors for gas sensing can be enhanced using various catalysts.

Furthermore, in many cases the sensor needs to be operated

at an elevated temperature. Hence, the incorporation of a \ heating and a temperature sensing element to the tin oxide

sensor is desirable. In our laboratory, a tin oxide sensor inte- grated with an on-chip heater and temperature sensor has

been fabricated using microfabrication and micromachining

72
techniques. A doped silicon resistance heater, p-n junction

I diode for temperature sensing and platinum resistance heater

I and temperature sensor have been used in this development

depending on the temperature and heating range required.

1 Figure 3 shows the basic structure of the micromachined tin oxide sensor. The details of this sensor and its fabrication processes have been given elsewhere [5]. In order to minii mize any mass heat loss and to provide stable operating temi perature control, the back side of the silicon substrate is se-

, lectively removed by anisotropic etching. Consequently,

' this leads to a low mass, low power consiunption device.

I Similar to other chemical sensors, tin oxide sensors cannot

j be totally free of interference by other species. The use of

j catalysts enhances the selectivity and sensitivity of the tin

I oxide based gas sensors, and Yamazeo and his associates [6] have reported the results of this improvement. We believe

that further enhancement can be accomplished by using a

j pair of tin oxide sensors, with one having the chosen catalyst

I for the detecting gas, and the other does not. This pair of

1 sensors operates in the differential mode, and the difference

I in sensor output between the two sensors is then used to

' quantify the detecting gas. Figure 4 shows the experimental

, results of a tin-oxide based H2S gas sensor operating in the

f differential mode. One of the tin oxide sensors is doped with

CuO which is known to catalyze the oxidation of the H2S

reaction, whereas, the other tin oxide sensor does not contain

any CuO. The results showing that the sensor operates in

^! the differential mode are very desirable.

2100

1800 ^ 1500

> 1200

> 900

'5S BOO

: T-200°C

: 10% 0,

*

-''^^^

^'^'^ dlllarantlal mode

/*

'

slnglo mode

0 10 20 30 40 50

H,S Concantratlon (ppm)

Figure 4: Characteristics of a CuO-doped tin oxide sensor operated in differential mode.

Catalyst Doped

Sn02

Figure 3 : Basic structure of a single micromachined tin oxide gas sensor.

OXYGEN SENSORS USING DIFFERENT SOLID STATE

ELECTROLYTES

Electrochemical sensors, both potentiometric and amperometric modes, have been used for oxygen detection. Either mode of operation has its merits and limitations, but

the amperometric type of electrochemical sensor, in general,

provides better sensitivity and detectable ranges than the potentiometric one. A solid state electrolyte is used in these oxygen sensors. For high temperature gas sensing, calcia- and yttria- stabilized zirconium dioxide have been used for the monitoring of O2, CO, H2 and others. At ambient temperature, solid polymeric electrolytes (SPE) have been used

for gas sensing. Among the SPE, Nafion is commonly used. In our laboratory, oxygen sensors using yttria stabilized zir- coniimi dioxide and Nafion are fabricated, and each of these sensors has its own merits which will be discussed as fol- lows.

73
TEMPERATURE

, DETECTOR v

I

HEATER ELECTRODES HEATER

Figure 5: Schematic structure of a solid oxide oxygen

sensor.

Figure 5 shows a schematic structure of the solid oxide electrolyte oxygen sensor. This device is fabricated using microfabrication and micromachining techniques. The amperometric mode of operation is used, and both working and

reference electrodes are platinum films.

Figure 6 shows the schematic of the solid polymer electrolyte

(SPE) oxygen sensor. Nafion is used as the SPE and the

substrate on which the electrode elements are deposited.

This oxygen sensor operates in the voltammetric mode. All working, coimter and reference electrodes are platinum film,

and the reference electrode is, in fact, a pt/air reference. The

deposition of these platinum films is accomplished by electroless chemical deposition. A thin gold layer ~ 2500 A

thick is deposited by ion-beam coating technology defining a

diffusion barrier layer for the oxygen. This sensor demonstrates long-term stability when operated in an ambient envi- romnent. However, the sensor carmot be operated in an ex- tremely dry environment, and can be affected by the humidity of the testing medium. This sensor has a relatively fast response time. A 90% response time is 5 seconds, and

shows good long-term stability.

In summary, microfabrication and micromachining tech- niques are well suited to develop practical gas and chemical

sensors for various applications.

Acknowledgment

Support of this research by the Edison Sensor Technology

Center, Department of Development, State of Ohio, and by

the NCRR, NIH Grant No. RR02024 are gratefully

appreciated.

References

A heating and a temperature sensing element, both platinum

film, are incorporated into the device. The backside of the sensor is selectively removed by chemical anisotropic

etching. This also results in low mass-heat loss. Initial testing shows that the sensor can be heated up to 700° C at

less than 2 watts. Further reduction in energy consumption

is feasible by changing the sensor structures to a cantilever form.

Solid polymer electrolyte ( Nafion 117 )

Counter electrode

[1] A. R. Baker, British Patent #892,530 (1962).

[2] J. G. Firth, A. Jones and T. A. Jones "The Principles of

the Detection of Flammable Atmospheres by Catalytic

Devices." Combustion and Flame 21 (1973) 303-311.

[3] N. Taguchi, Japan Patent No. 45-38200 (1962).

[4] T. Seiyama, A. Kato, K. Fuji and M. Nagatani "A New

Detector for Gaseous Components Using

Semiconductive Thin Film." Anal . Chem. 34 (1962)

1502-1503.

[5] Q.H. Wu, K. M. Lee and C. C. Liu "Development of

Chemical Sensors Using Microfabrication and

Micromachining Techniques." Sensors and Actuators B

13-14 (1993) 1-6.

Figure 6: Schematic structure of a solid polymer

electrolyte oxygen sensor.

74
II. Poster Summary

Abstracts

75

SURFACE ACOUSTIC WAVE SENSOR (SAW) SYSTEM TECHNOLOGY

R. Andrew McGill' and David L. Venezky

Chemistry Division, Naval Research Laboratory

Washington, D.C. 20375-5342

During the 1980 's small chemical sensors based on

microelectronic devices emerged as the leading technology for a

variety of chemical detection problems. A number of these sensor

technologies have been developed and investigated at the Naval

Research Laboratory, including optical waveguide chemical sensors,

chemiresistors, and surface acoustic wave (SAW) vapor sensors.

Both the SAW and chemiresistor chemical microsensors are capable of

detecting organic vapors with high sensitivity. Selectivity is

substantial but can be improved dramatically through the use of

arrays of sensors whose responses are analyzed using pattern

recognition algorithms. SAW sensors are readily adapted to such

sensor array systems because of the great flexibility in tailoring

the chemical selectivity of the individual sensors, and our in

depth understanding of their reversible response mechanisms. As a

result, SAW vapor sensors have become a leading microsensor

technology for chemical vapor detection. Smart sensor systems

based on arrays of SAW sensors and pattern recognition are being

investigated for chemical agent detection and as intelligent fire

detectors. The SAW devices, the analyte and its influence on

selecting chemically selective coating materials, pattern

recognition, and sensor system design and integration into a field

system are current topics of investigation. The key features of

our current system are an array of four SAW vapor sensors,

temperature control of the vapor sensors, the use of pattern

recognition to analyze the sensor data, and an automated sampling

system including thermally desorbed preconcentrator tubes.

Organophosphorus analytes were detected at concentrations as low as

0. 01 mg/m^ in 2 minutes, and an organosulfur analyte was detected

at 0.5 mg/m^ in 2 minutes. Pattern recognition algorithms correctly

classified these analytes at these concentrations and discriminated

them for a variety of other organic vapors^.

1. Geo-Centers, Inc., 10903 Indian Head Highway, Fort Washington,

MD 20744

2. "Smart Sensor System for Trace Organophosphorus and

Organosulfur Vapor Detection Employing a Temperature-controlled

Array of Surface Acoustic Wave Sensors, Automated Sample

Preconcentration, and Pattern Recognition", Jay W. Grate, Susan L.

Rose-Pehrsson, and David L. Venezky, Analytical Chemistry, 1993,

65, 1868-1881.

77
Surface Acoustic Wave Gas Sensor Technology at Sandia National Laboratories

Dr. James Wiczer

Microsensors Research and Development Department

Sandia National Laboratories - Albuquerque New Mexico 871 85

Sandia National Laboratories, an 8500+ person, multiprogram research and

development facility operated for the U.S. Department of Energy, has over 400

research, development and applications scientists and engineers working on sensor

technologies. We describe here some of Sandia National Laboratories research and

development activities using surface acoustic wave sensor devices coated with

chemically sensitive films to sense gases and vapors. The coated SAW device, typically a SAW delay line structure, is configured in a resonant circuit so that the frequency

and amplitude of oscillation of the circuit change when the film on the SAW device

changes. When these SAW sensors are exposed to a gas of interest, the film changes

mass and/or elastic properties through a chemical sorption process or other chemicalfilm interaction. These changes can be monitored and calibrated for each surface film

and each chemical species anticipated.

We have developed SAW sensors to detect vapors from volatile organic compounds

(VOCs), small inorganic molecules, humidity, organophosphonates, styrene, and a

variety of other compounds. We have applied these sensors to such diverse

applications as the monitoring of cleaning chemical concentrations in industrial

process effluent streams and the monitoring of contaminant concentration levels in ultrapure process gases. For one application, a SAW sensor using a thin film of

chemically absorbing polylsobutylene, demonstrated 400 ppb ( part per billion)

sensitivity to trichloroethylene (TCE). The application required the continuous real-time

monitoring of TCE and d-llmonene emitted Into a fume hood exhaust duct at a printed

circuit board cleaning station. The SAW-based real-time monitor tracked the emissions

of volatile organic compounds from this industrial process. By implementing a solvent

substitution from TCE to d-llmonene and providing the cleaning station operator direct

feedback on the solvent vapor emissions during the cleaning process, VOC emissions

were reduced by over a factor of 40. Part of the reduction was directly attributable to

the operator adjusting the air-solvent mixture going into the nozzle and the nozzle

aim based on the SAW sensor output.

New research projects have been Initiated to address SAW sensor specificity issues

which are determined in part by the chemical characteristics of the transducer film.

Since most films respond to several chemical vapors of interest, we and others are developing arrays of SAW transducers In which each SAW device is coated with a

different film. Although no single film will have absolute selectivity, analysis of the

array output using pattern recognition techniques will enable these systems to resolve

different species In a gas mixture.

This work was performed at Sandia National Laboratories and supported by the U.S.

Department of Energy under contract No. DE-AC04-76P00789.

78
Selection of Polymer Coatings for SAW Chemical Microsensors

R. Andrew McGilV, Michael H. Abraham^, Jenik Andovian-Haftvan^, Chau My Du\ Valerie

Diart^, Gary S. Whiting^, and Jay W. Grate^

'Geo-Centers

10903 Indian Head Highway

Fort Washington, MD 20744

^University College London

20 Gordon Street London WCIH OAJ, UK

^Chemistry Division

Naval Research Laboratory

Washington, DC 20375-5324

The choice of polymeric coatings for use with surface acoustic wave (SAW) chemical sensors is an

important factor in the development of a successful operating sensor system. We have based the selection of

coatings, for different vapors, on the use of a new solvation equation.

Gas-liquid partition coefficients, K, have been obtained by inverse gas-liquid chromatography for 20 to 70 solute analytes on 14 polymers at 25 °C. The polymer can then be characterized through a solvation

equation, where Log K relates to a series of solutes on the same polymer:

Log K = c + r.R, + s.TT^ + a.a^ + b./S^ + I.Log L'*

The explanatory variables are solute parameters, indicates the polarizability contribution from n and tt electrons, tt^ the dipolarity /polarizability, and /S^ the hydrogen-bond acidity and basicity, and Log L'* where

L'* is the K-value on hexadecane. The regression coefficients then characterize a polymer, the most important

being "s" the polymer dipolarity /polarizability, "a" the polymer basicity, "b" the polymer acidity, and "I" which

reflects the ability to discriminate between a homologous series of solute vapors. The coefficient "r" reflects the

polarizability properties of the polymer and "c" is the constant resulting from the regression. The size and

relative magnitude of the coefficients are used to identify polymers with high selectivity and sensitivity as coatings for chemical sensor applications. A term-by-term investigation of Log K values shows the solubility interactions that lead to sorption of a solute by a polymer.

The selection of polymer coatings for SAW chemical microsensors can be made based upon the relative magnitude of "r," "s," "a," "b," and "I" and the solubility properties of the vapor of interest. To illustrate this process a specific example is described for detection of a vapor with hydrogen-bond basic solubility properties

in the presence of gasoline vapor. Dimethylacetamide (DMAC) is strongly dipolar and hydrogen-bond basic, octane is non-polar and has no hydrogen-bonding properties. In order to match the solubility properties of the polymer and DMAC the sorbent coating will be dipolar and exhibit maximum hydrogen-bond acidity with

minimum hydrogen-bond basicity. Out of the 14 polymers studied, SXFA (fluoroalcoholpolysiloxane) best matches these solubility properties. The solvation equation at 25 °C for SXFA is:

Log K = - 0.08 - 0.42. R2 + 0.60.7ry + O.VO.a^ + 4.25./3^ + 0.72. Log

Solute Parameters R2 <A ^5 Log V

DMAC 0.36 1.33 0.00 0.73 3.72

n-octane 0.00 0.00 0.00 0.00 3.68

The calculated Log K values are 6.35 (+ 0.12) for DMAC and 2.57 (+ 0.12) for octane. This means that for equivalent vapor concentrations DMAC will partition into the SXFA polymer coating much more strongly than

octane. In fact for every one molecule of octane collected in the polymer coating, approximately 6,000

molecules of DMAC will be reversibly absorbed.

The selection of polymeric materials used for coating SAW devices can be rationalized and quantified by

using the solvation equation as described, and arrays designed for SAW sensor systems.

McGill, R. A., et al.. Choosing Polymer Coatings for Chemical Sensors, CHEMTECH 1994, 24(9), 27-37.

Abraham, M. H., et al.. Hydrogen-bonding. XXIX. The characterisation offourteen sorbent coatings for

chemical microsensors using a new solvation equation, submitted to J. Chem. Soc. Perkin Trans. 2.

79
Real-Time Neural Network Analysis of Chemical Sensor Arrays:

One Step Closer to Artificial Olfaction

Paul K. Clifford and Michael G. Dorman

Mosaic Industries, Inc., 5437 Central Avenue Suite 1, Newaik, CA 94560

Phone: 510-790-8222 • Fax: 510-790-0925 '

Neural network implementations of nonlinear pattern recognition algorithms have been combined with arrays of

sensors to identify and selectively measure gases. These networks are shown to provide good generalization, they

are able to estimate errors on computed concentrations, and they are parsimonious in their calibration requirements.

Many promising chemical sensors are limited by their unselectivity and nonlinear responses. These drawbacks may

be remedied by coupling sensor airays to chemometric analysis tor selective quantitation. Neural networks provide a useful implementation; they partition the analysis into a computation-intensive training phase and a faster run- time computation. Consequently, microprocessors can calculate the nin-time solution in real time at the sensor site.

UnfoHunately, although neural networks perform well for pattern classification they often fail when used for the continuous, high-resolution mappings needed in chemometrics. Additionally, they usually require long training

times, their solutions aie often trapped in suboptimal minima, and they aie so demanding in their requirements for calibration data as to prevent their practical implementation.

We have developed optimized network (opologies and training methods that overcome many of these problems,

resulting in artificial neural systems well suited to chemometric analysis. These innovations include:

• Biasing the network's solution toward preconceived internal representations well matched to the nature of the

chemical sensor responses. This is done by choosing the internal nonlinear functions on the basis of the sensors' expected functional behavior. In contrast to general purpose transformations, these exhibit nonsaturating

monotonic behavior which prevents oversensitivity to noise and amplification of back-propagation training

errors.

:

" t. n:.

• Designing the network topology and training method to constrain the number of independent data pathways in the network. These constraints ensure that the network forms an internal representation of the sensor-to-gas

mapping that uses a minimal number of nonlinear principal components. The hidden units are chosen to model

physically significant features including gas concentrations, temperature, humidity, and historical behavior.

• Using signal-to-noise criteria and cross validation to sequentially build optimal data flow paths through the network. This avoids the chronic overtraining that is characteristic of back-propagation networks and assures

the predictive ability of the learned transformations.

These techniques have significantly reduced training times compared to the standard back-propagation algorithm,

while dramatically improving the network's predictive ability. Using optimized network topologies and training

strategies, we have trained feed-forward networks that efficiently convert sensor responses into analyte identities and measurements. These techniques ai e demonstrated using anays of MOS sensors; two examples are provided:

• A multi-layer autoassociative perceptron is used in conjunction with a five sen.sor array to resolve mixtures of

three gases with widely varying compositions. The network computes analyte concentrations and their expected

eiTors, and, in conjunction with a Bayesian classifier, identifies dominant gases and detects outliers or phantom

analytes. It has also achieved robust identification of a library of gases using small MOS sensor arrays.

• A feed-forward functional link network uses a minimal number of MOS sensors for interference-free measure- ment of CO and methane.

This research is part of a broader program at Mosaic Industries aimed at the development of low cost implementations of artificial olfaction. Efforts are now focused on more efficient training algorithms so that all calibration functions can be incorporated in a small microcontroller tightly coupled to the sensors.

80
Application of Olfactory Neural Networks

to Processing Sensor Information

T. McAvoy* and D. Pan

Department of Chemical Engineering

and

Institute for Systems Research

University of Maryland

College Park, MD 20742

ABSTRACT

The nose has a truly remarkable ability to detect and

then accurately classify an odor based upon being exposed to

minute amounts of a chemical. If such an ability could be

duplicated artificially, then there would be numerous,

significant practical applications. There is also the

possibility of discovering completely new engineering

algorithms for handling sensor information and for

classification. This paper presents preliminary results on

using olfactory neural nets to process sensor information,

and discusses potential applications of such networks.

We have been studying the use of olfactory neural net

models coupled with various sensors to detect fires. The

problem of detecting fires is one of pattern recognition. A

recent paper by Okayama illustrates the ability of two tin

oxide detectors to discriminate between smoke from smoldering

fires and ordinary odors from organic compounds, when the

sensors were coupled with a neural network. Okayama used a

standard backpropagation type neural network. In our work

alternative neural network architectures , based upon modeling

the olfactory system, are being studied for their ability to

enhance fire detection. In addition to detecting fires there

are other potential process applications of our approach.

One application involves hazardous emissions from manufacturing plants. Tighter and tighter emission standards are being

set for industry, and it is unclear how these standards will

be met. If an olfactory chip could be developed to combine

thin film sensors and signal processing (an artificial nose),

then it could be placed at strategic locations around a plant

to warn of emissions. Olfactory computation may also be

useful for fault detection using standard plant sensors. In

this way one would artificially "smell" a process fault. An

approach that couples 12 thin film sensors and a neural net

has also been reported for following the progress of a

brewing process. The purpose of this paper is to give an

overview of olfactory neural networks and how these networks

might be applied to solve process problems.

* to whom correspondence should be sent

81
Second Order Devices: The Coming Revolution in Sensors

Barry M. Wise

Molecular Science Research Center

Pacific Northwest Laboratory

Richland, WA 99352

Abstract

Analytical instruments can be classed by the dimensionality or "order" of the data they produce.

For instance, a pH probe, which produces one datum per sample, is zero order. A spectrometer,

which produces a vector (first order tensor) of data for each sample, is first order. Many modem

analytical instruments, such as the hyphenated techniques like GC-MS, produce a matrix (second

order tensor) of data for each sample and are, therefore, second order instruments. There are inherent advantages to higher order devices. In a zero order device, the presence of an interferent

species cannot be detected. Correct quantitation is lost and no indication of a problem is given. In a

first order device, the presence of interferents can be detected, but quantitation is still mathematically impossible. In second order systems, however, it is possible to achieve correct

quantitation in the presence of interferents that were not included in the original calibration matrix.

We refer to this quality as "the second order advantage."

Recentiy, researchers have begun to devise single sensors that produce second order data. These

sensors are potentially much more robust to interferent species. TTiis will be an especially important

advantage in environmental sensing where the background matrix is often unknown.

Simulated liquid chromatography/near infrared spectroscopy (LC-NIR) data is used as an example

of how second order calibration works. In LC-NIR an absorbance is measured as a function of

retention time (the first order) and wavelength (the second order) producing a response such as the one shown in the figure. Given the response to a pure analyte and an unknown mixture possibly

containing the analyte, the Generalized Rank Annihilation Method (GRAM) can be used to determine the amount of analyte in the unknown mixture, even without information about the

interfering species. This capability is a revolutionary advance in calibration and analysis.

There are several possible strategies for developing second order sensors. A sensor array, e.g. a SAW device with different chemically selective coatings, can be coupled with a separation step

such as LC or even a chemically selective membrane. It is also possible to develop a second order sensor "on a chip" by controlling the time-temperature profile of array elements. This approach is being actively pursued at PNL for detection of hydrogen in the presence of VOCs.

Response to Analyte #1

82
SENSOR TECHNOLOGY FOR ADVANCED COMBUSTION

CONTROL AND MONITORING INSTRUMENTATION

M.A. Richard, O.W. Bynum, D.R. Sheridan, P.H. Mark, G.C. Morrison, and L.T. Brewer

Sonoxco, Inc, 430 Ferguson Drive Bid # 3, Mountain View, CA 94043

ABSTRACT: With increasingly stringent environmental legislation, there is a growing need for low cost instrumentation for combustion control and emissions monitoring. While low cost is necessary, advanced

instrumentation also must be simple to operate and calibrate, require minimum maintenance, and give stable, reliable

data. Combustion of fossil fuels leads to formation of CO, NOx, SOj, and other pollutants depending on the fuel and the combustion conditions. We will describe catalytic heat flux sensor technology and instrumentation based on these sensors for the quantitative measurement of CO, NOx, ^nd SOj. Various strategies for control of emissions

and for maximum fuel efficiency based on these measurements will be presented.

The 1990 Amendments to the Clean Air Act require tighter control of the emissions released during the combustion

of fossil fuels. The new legislation is now targeting small industrial and commercial size combustion processes such as heaters, boilers, and stationary IC engines. Continuous Emissions Monitoring (CEM) systems capable of

monitoring the major fossil fuel combustion emissions, NOx, SO,, and CO, have been used for over ten years on

utility size boilers and large gas turbines. However, the prohibitively high cost of these systems, as much as $150,000, is too high for smaller combustion processes. Sonoxco has developed a line of sensors to measure the stack gas levels of NOx, SO,, and CO on coal-, oil-, and gas-fired processes. The sensors are low cost and easily

configurable into monitoring and control instrumentation.

The Sonoxco CO, NOx, SO, sensors are catalytic heat flux devices. Each sensor is comprised of two

temperature sensitive elements, one active and the second a reference. The active element is coated with a highly

selective catalyst that promotes an exothermic reaction of the component to be measured. The temperature

difference between the active and reference elements is directly proportional to the gas concentration. As an example, the CO sensor operates by catalyzing the reaction of CO with oxygen as follows:

CO + Vi O2 CO, AH^K = -67.6 kcal/mol

Resistance temperature detectors (RTD) are used for the temperature measuring elements for the three sensors. Because the RTD resistance is proportional to temperature, the corresponding difference in resistance between the

active and reference elements is linear with gas concentration. A bridge circuit can be used to produce a 0-5 Vdc

signal that is directly proportional to the gas concentration as shown in Figure 1 for the CO sensor. The designs

of the NOx, CO, and SO2 sensors are identical with the exception of the proprietary active catalyst coatings.

CO Concentration, ppm

Figure 1. Signal linearity of the Sonoxco CO sensor.

83
NEW SEMICONDUCTING MIXED OXIDE-BASED SOLID-STATE GAS

SENSORS FOR CARBON MONOXIDE AND HYDROGEN

A.M. Azad, L.B. Younkman and S.A. Akbar

Department of Materials Science and Engineering

The Ohio State University, Columbus, OH 43210-1179.

Solid-state gas sensors based on semiconducting metal oxides have been widely used for

the selective detection and metering of reducing gases (such as carbon monoxide, hydrogen,

hydrocarbons, etc.) in the flue gas streams of combustion furnaces and in the automobile exhaust

systems. High-temperature application oriented new carbon monoxide gas sensors based on M0O3

and the anatase phase of Ti02 have been developed and their sensing characteristics such as

selectivity, sensitivity, threshold detectable gas concentration and response time were investigated.

It was found that M0O3 thick films could be used as an ON/OFF type detector, whereas those

based on the two-phase mixture of M0O3 and Zr02 could be employed for measuring the

concentration of CO in the flue gas stream. Significant enhancement in the sensitivity of these sensors in terms of the magnitude of the signal as well as the response time, was achieved by the

addition of small amounts of palladium catalyst. In the Ti02-based sensors, experiments showed

that pure titania is a very good but nonselective sensor (responds to both CO and H2 gases).

Remarkable change in the sensing characteristics of the anatase modification of Ti02 was observed

when admixed with an insulating second phase, such as a-alumina or yttria. In the case of titaniaalumina sensor, the response was found to be exclusively dependent on the hydrogen

concentration alone; the presence of CO and/or CO2 did not affect the sensitivity. On the other

hand, the sensor based on titania-yttria showed increased sensitivity to CO and decreased

sensitivity to H2; the sensitivity was immune to the presence of NO and/or NO2. Addition of

elemental iron, in small concentrations, to the two-phase mixture of titania and yttria seemed to further improve the sensitivity to CO gas. X-ray and XPS (ESCA) studies, together with the

experimental dc measurements and the reversibility characteristics, were used to elucidate the

possible sensing mechanisms operative in these sensors. The danger of rather easy oxidation of the

elemental iron present in small amount in the titania-based devices was circumvented by replacing

iron with high activity noble metal. This chemistry variation resulted in higher stability and longer

shelf-life of the latter, without affecting the sensitivity.

In order to understand the sequential contributions of grain boundaries, grains and twophase mixtures, ac electrical data in the frequency range 5 Hz </< 13 MHz were acquired at the

ambient as well as elevated temperatures (400 °C < T < 900 °C). These were used to establish the

role of microstructures on the resulting electrical behavior in these polycrystalline materials. The ac

data, when analyzed utilizing the lumped parameter/complex plane analysis (LP/CPA), reveals

several contributions from simultaneously operating mechanisms to the terminal admittance of the

grain boundary. While the room temperature impedance spectra offers the lumped response alone,

at high temperatures two semicircular relaxations observed in the impedance plane, are attributed to the low-frequency related grain boundary and high frequency related grain response. The grain

boundary response, however, is still difficult to quantify even at elevated temperatures via LP/CPA

and dc measurements. The electrical path homogeneity is examined via the presence of the

depression angle which remained nearly invariant in the range of measurement temperatures.

The nature of electrically conducting paths is suggested via an equivalent circuit

representation incorporating the underlying mechanisms in a systematic manner. The

transformation of the room temperature equivalent circuit into that at high temperatures is shown in the Hght of experimental observations.

84
Research and Technology for Tin Oxide Gas Microsensor Arrays

R. E. Cavicchi, S. Semancik, G. E. Poirier

Chemical Science and Technology Laboratory, NIST

J. S. Suehle and M. Gaitan

Electronics and Electrical Engineering Laboratory, NIST

Gas microsensor arrays offer many potential advantages over discrete sensor devices. A

fundamental feamre of arrays is the improved selectivity obtained by taking advantage of

pattern recognition algorithms to deconvolute signals from overlapping responses from

different sensors in the array. By using batch fabrication methods to produce the arrays, lower cost and improved reliability can be expected. Miniaturization also permits operation

at lower power, and therefore greater portabiUty of instruments that use microsensors. To

achieve these goals, improvements in fabrication technology and sensor materials, as well

as improved understanding of how these devices operate, are required. Results are presented here in two areas: microhotplate technology and growth of epitaxial tin oxide.

A microhotplate is a micromachined structure with the ability to produce a wide temperature

range We have fabricated microhotplates using a CMOS-compatible method which is described elsewhere 1. The design used for a tin oxide gas sensor consists of a four element

array, where each element contains a polysilicon heater, an aluminum hotplate/temperature

measuring layer, and aluminum electrical contacts. The devices have a thermal efficiency of

8°C/mW, a temperature range of 0-550°C (limited by the aluminum layer), and a thermal

time constant of 0.6mS. Tin oxide was deposited on top of the electrical contacts while the

heaters maintained elevated deposition temperatures. Sensing action at 350°C to hydrogen

and oxygen was demonstrated. Microhotplates were also used as a substrate array for

materials processing. An array of 36 elements, with a temperature range 0-1000°C (no

aluminum layer) was used to examine the microstructure of tin oxide as a function of

deposition temperature. Subsequent scanning electron micrographs of the array elements

showed an increase in grain size with deposition temperature. Such temperature processing

by arrays can be an efficient way to optimize a materials process, as well as provide thermal

conditioning for gas sensor elements.

A limiting factor in the performance of thin film sensors is the instability of the interfaces

between grains in the film. Bulk sensors are usually sintered, creating "necks" between the

grains, which are relatively stable. We have developed a method for producing epitaxial tin oxide films^, which have properties closely related to single crystal tin oxide and may

provide improved stability for thin film sensors. Films were deposited on sapphire

substrates which are produced commercially for silicon-on-sapphire technology. The

deposition method was reactive sputter deposition using a pure tin target, argon and oxygen

sputtering gas, and a substrate temperature of 5(X)°C. X-ray diffraction showed single

orientation films which were (101) on sapphire (lT02) substrates and (100) on sapphire

(0001) substrates. Atomic force microscopy showed 400 A films to be atomically flat with

steps from the underlying substrate still visible as steps in the top tin oxide layer. This form

of tin oxide is capable of producing a sensor response at thicknesses of only 15A.

[1] J. S. Suehle, R. E. Cavicchi, M. Gaitan, and S. Semancik, IEEE Electron. Device

Lett., vol. 14, no. 3, p.l 18 (1993) and references therein.

[2] R. E. Cavicchi, S. Semancik, M. D. Antonik, and R. J. Lad, Appl. Phys. Lett. vol. 61 no. 16, p. 1921 (1992).

85
Micro-Hotplate by CMOS Technology With Application for Gas Sensors

Michael Gaitan, John S. Suehle, Richard E. Cavicchi*, and Steve Semancik*

Electronics and Electrical Engineering Laboratory

^Chemical Science and Technology Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899

We have developed the design and fabrication methodology for a silicon

micromachined micro-hotplate that is manufactured using commercial CMOS

foundries with additional post-fabrication processing. The device can be considered

"generic" in that we foresee a host of new applications that can be implemented with

this structure as a basic element. The methodology for the fabrication of this device

is based on prior work on commercial CMOS-compatible micromachining. The novel

aspects of this device are in the design, choice and layout of the materials layers, and

applications for the device.

Figure 1 shows a SEM micrograph of the suspended micro-hotplate structure after

the deposition of a Sn02 film. The composition and placement of the various material

layers are shown in the inset. The thermal charcateristics of the device are shown in

Figure 2 which plots the temperature of the micro-hotplate versus input power. The

thermal efficiency of the device was determined to be 8 °C/mw.

This device has the advantage over other similar devices by its manufacturability in

a standard CMOS process which leads to low cost and easy integration of VLSI

circuits for drive, communication, and control. Also, this device can be easily

incorporated into arrays of micro-hotplates, each with individualized circuits for

control and sensing for independent operation.

Fig. 1. SEM micrograph of suspended micro-hotplate structure with SnO, film coating. The inset shows a schematic illustrating the various

layers comprising the structure.

86
Properties of Ultrathin SnOj Gas Sensors

G.E. Poirier, R.E. Cavicchi, and S. Semancik

Chemical Science and Technology Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899

Many commercially available, conductance-based gas sensors use compressed powder tin oxide (Sn02)

active elements. In developmental sensor research, however, there is a move toward sensors using thin

film active elements. ^ This move is motivated by the enhanced compatibility of thin films with

microelectronic fabrication technology. Microelectronic-based integrated sensors^ have the advantages of

lower power consumption, higher manufacturing throughput, and greater miniaturizabihty. Moreover,

integrated sensors can be fabricated in arrays to provide chemical selectivity and can be fabricated with on- board control and signal processing electronics. Sn02 sensors operate by ambient gas-induced variations

of the surface chemistry that lead to changes in the sheet resistance. For example, reducing gases can

create surface oxygen vacancies. These vacancies act as donors and increase the sheet conductance. One

source of error in the sensor response is the variation in surface stoichiometry due to migration of bulk

oxygen atoms to the surface. This migration occurs at around 700 K and leads to an undesirable slow drift in the baseline conductance. Our group theorized that this source of error may be suppressed or eliminated

by minimization of the bulk material. To this end, tin oxide films, 1.5, 4.0 and 8.0 nm thick, were grown

on elevated-temperature sapphire (lT02) and (0001) substrates by reactive sputter deposition. The

structural, chemical, and electrical properties were investigated by scanning tunneling microscopy (STM),

low energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and 4-point

conductance measurements. LEED data suggested that the Sn02 films grown on sapphire (1 102) were

crystalline with the [101] axis parallel to the growth direction. In contrast, for films up to 80 A thickness

grown on sapphire (0001), no long range order was

evident in LEED images. STM images of the Sn02 films

grown on sapphire (lT02) showed atomically flat terraces separated by regularly spaced single atom steps. XPS

measurements indicated that the only Sn02 film impurity

was carbon. This was probably deposited on the film

surface from the laboratory air while transporting the

samples from the deposition chamber to the analysis

chamber and was subsequently removed by exposure to an oxygen plasma. Gas sensing measurements were

carried out on films activated with 1 monolayer of vapordeposited palladium. STM measurements indicated that

the Pd forms 3-dimensional particles, roughly 100 A in

diameter, which do not completely cover the surface.

The STM image on the right shows 2 monolayer

equivalents of Pd deposited on a thin film of (101)

oriented Sn02. The extremely low surface roughness is evident in line scan below the image. Sensing response

measurements were carried out in UHV by exposing the

films to cycles of H2 and O2 gas at 1x10-3 while

measuring the film conductance with an m-situ, collinear, 4-point probe. A sensing response was

achieved for all the film thickness studied. The initial experiments suggest that the 1.5 nm thick film

shows less hysteresis and less drift than the thicker films. This indicates that elimination of the bulk

material does, indeed, result in improved sensor response characteristics. Experiments are underway to determine the sensing response of these films at more realistic gas pressures. IM.J. Madou and S.R. Morrison, Chemical Sensing with Solid State Devices, Academic, San Diego, (1989).

2v. Demarne and A. Grisel, Sensors and Actuators, 13 301 (1988).

100Q

x(A)

87
Solid State Sensors Based on Semiconducting Metal Oxides

With Surface-Dispersed Metal Additives:

Modeling of the Mechanism of Response Formation

Valeriy Sukharev, Richard Cavicchi, and Steve Semancik

Process Measurements Division

National Institute of Standards and Technology

Gaithersburg, MD 20899

Solid state sensors based on metal oxide semiconductors with surface dispersed metal

particles are characterized by strong sensitivity to definite gases which in some cases do not cause the conductivity response of pure metal oxide adsorbents. To understand the

mechanism of such sensor response we investigated the adsorbent conductivity behavior

under metal deposition and surface metal cluster formation. We considered Pd dispersions on

nearly stoichiometric thermally oxidized and oxygen-rich plasma-oxidized SnOj (110) for

coverages ranging from 0 to 10 monolayers-equivalent. The results were interpreted using a model that includes oxidation of metal species, formation and slow-filling of surface states,

and the effects of overlapping depletion regions that result from the Schottky barriers formed

around each particle. It has been shown that in all cases the measured G(t) kinetics was the

adsorbent electroconductivity relaxation caused by a disturbance in the adsorbate-adsorbent

electronic equilibrium. A comparison of experimental data for the conductivity relaxation

kinetics of the thermally oxidized SnOj and theoretical dependencies is shown in the figure.

D-GltJ = 12.5 -O.BB ln{l + 16e 2.83

• ^W = 14 -5.3 cxp{ - 7.3(1 -c"^^ *])

• • . .

.

103 3 10- t sec

The possible mechanism of adsorption-induced response formation due to the breakdown of

the overlapping of the space charge regions of adjacent surface metal clusters has been

described. The existence of definite deposited metal concentration and adsorbent thickness

ranges characterized by the biggest value of adsorbent conductivity response has been

predicted.

88
Gas Sensor Research Facilities in the NIST Process Measurements Division

S. Semancik, R. E. Cavicchi and G. E. Poirier

Process Measurements Division

Chemical Science and Technology Laboratory

- National Institute of Standards and Technology

Special research capabilities are required for the detailed study of sensing materials and transduction

mechanisms as well as for the fabrication and performance evaluation of prototype sensing devices. Three

custom research facilities have been constructed in the Process Measurements Division of the Chemical

Science and Technology Laboratory at NIST in order to support development of optimized materials and

concepts for next-generation sensors. These facilities are the (a) Film Deposition and Characterization

Facility, (b) Surface Analytical Facility, and (c) Sensor Response Test Facility. Specific objectives for

research using this equipment include:

• Determining the basic properties of active materials

• Developing practical methods for fabricating microstructure-controlled, planar gas sensor

structures

• Understanding the molecular scale gas-solid interactions that lead to macroscopic responses

• Modeling the performance characteristics of prototype sensors to efficiently optimize devices

• Developing databases for use in constructing pattern recognition schemes for gas sensor arrays

A brief description of each facility follows.

FILM DEPOSITION AND CHARACTERIZATION FACILITY. This facility is a dual chamber, ultrahigh vacuum (UHV)-based system used to develop procedures for fabricating oxide and metal films of

controlled microstructure. Oxide films (1-1000 nm thick) are deposited by reactive sputter deposition and

ultrathin metal overlayers (monolayer regime island structures) are deposited by evaporation. The films can be characterized, in situ, using 4-point conductance measurements and their structures can be studied

by low energy electron diffraction (LEED) and reflection high energy electron diffraction (P.HEED).

SURFACE ANALYTICAL FACILITY. This multi-chamber UHV-based system is equipped with a complement of analytical hardware for characterizing the outermost regions of samples (0.5-10 nm). In order to perform thorough examinations of sensor material properties, instrumentation is included for

performing chemical, structural, electronic and electrical analyses by x-ray photoemission spectroscopy

(XPS), Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), secondary ion mass

spectroscopy (SIMS), energy loss spectroscopy (ELS), ion scattering spectroscopy (ISS), low energy

electron diffraction (LEED), electron stimulated desorption (ESD), scanning tunneling microscopy

(STM), ultraviolet photoemission spectroscopy (UPS), measurement of work function change and fourpoint conductance measurements. A variety of sample preparation and surface modification hardware (ion

guns, evaporators, gas sources, quartz crystal monitors, etc.) critical to tailoring sensor materials is also

mounted on the three chambers of this system.

SENSOR RESPONSE TEST FACILITY. This fully-automated facility operates under computer control

to mix gases in desired ratios and flow them, at specified rates and pressure, to up to eight samples

mounted within the test chamber. Electrical characteristics from the test devices are computer recorded

with an update rate of up to 100 Hz. Efficient studies of adsorption/desorption kinetics and response

functions of customized films can be performed in order to optimize active sensor interfaces. Prototype

array devices can also be examined to acquire databases for development of pattern recognition/neural net algorithms.

89
Calibration Mixtures for Gas Sensor

Development and Evaluation

Gerald D. Mitchell and William D. Dorko, NIST

The NIST produces many gas standards which are used for the calibration of analytical

instruments and procedures employed to perform measurements for regulatory purposes.

These same calibration mixtures can be used to determine the performance of gas

sensors during their development and subsequent evaluation. Most of the standards are

binary gas mixtures contained in cylinders and are Standard Reference Materials (SRMs).

These gas SRMs are stock items which can be purchased from the NIST Standard

Reference Material Program (SRMP) at any time. There are approximately 90 gas SRMs

and the analytes or gases of interest include CO, NO, CO2, Propane, Methane, O^, SO2,

NOj, with the balance or matrix gas being either nitrogen or air. There are some

multicomponent SRMs, one contains 18 volatile organic compounds some halogenated

and some not, while another contains 15 non-methane organic compounds non of which

are halogenated. The concentrations of the analytes in the gas SRMs range from 5ppb

to 21%. The NIST analyses each analyte in each SRM cylinder which is sold

accompanied by a certificate describing the certification process and uncertainty in the

concentration value. Most of the gas SRMs are certified to 1% relative, some to 5%

relative, and two series of carbon dioxide SRMs are certified to 0.1% relative.

Another type of standard is the Research Gas Mixture (RGM). These are mixtures

containing components or concentrations outside the range of the SRM program. RGMs

can be requested by the private sector or government organizations. NIST determines

the feasibility and then performs research to develop an analytical procedure or primary

standards to analyze the requested mixture(s). The work is reimbursed by the requesting

organization which is supplied with the mixtures along with a certificate of analysis when

the work is completed. This program will enable NIST to be responsive to standards

needs. Whereas it may take two years or more to develop an SRM, it is feasible that an

RGM can be concluded in three to five months.

The third type standard is the NIST Traceable Reference Material (NTRM). NTRMs are mixtures similar to SRMs but are produced and distributed by the specialty gas industry.

A company produces a "lot" of ten to twenty identical cylinder mixtures and analyzes each

mixture against several gas SRMs after which the data are sent to NIST. NIST selects

two or three cylinders to be sent to its facility and these are analyzed for concentration

value assignment. NIST then combines its data and the producers data to assign a

concentration to each cylinder in the lot. A certificate for each cylinder is supplied to the

producer by NIST. This program allows the specialty gas industry to determine end user needs and respond to them but still maintaining NIST traceability.

90
NIST Humidity Standards and Calibration Facility

Gregory Scace, James Whetstone, and Peter Huang

Chemical Science and Technology Laboratory, Process Measurements Division

National Institute of Standards and Technology

NIST strives toward more accurate, uniform measurement of humidity by providing

humidity calibration services and supporting these services through development and

maintenance of humidity standards.

Hygrometers calibrated by NIST are subjected to moist air produced by the NIST Two

Pressure Humidity Generator. Within the generator, a continuous stream of CO, free air at constant temperature and pressure is saturated with water vapor over a plane surface of pure

water or ice. The moist air is then expanded isothermally into a test chamber maintained at atmospheric pressure. Moisture content of the test gas is determined based on the measured

temperatures and pressures within the saturator and test chamber. The NIST Two Pressure

Humidity Generator produces test air with moisture content ranging from 3 to 80100 PPMy

at flow rates from 28 to 280 standard liters per minute.

Humidity standards under development at NIST include a new primary standard hygrometer

and a low frost point humidity generator that will extend NIST calibration capability to part

per billion concentration levels.

The new primary standard hygrometer separates test gasses produced by a humidity

generator into water and dry gas. Desiccant filled collection tubes extract the water from

the gas. Weighing the tubes before and after a test yields the mass of water contained in the

test gas. The carrier gas is collected in one of two glass prover tubes. Its volume is obtained by measuring the displacement of lightweight, mercury sealed pistons within the

prover tubes, using laser interferometry. Once a prover tube is filled, pressure and

temperature within the tube are measured, allowing calculation of the mass of the collected

gas. The prover tubes are alternately filled and emptied until sufficient water,

approximately 0.6 grams, is extracted from the test air.

The low frost point humidity generator under construction at NIST features a new saturator design that eliminates the large temperature controlled baths and cryogenic cooling

previously required for saturation of air under constant temperature and pressure conditions.

The saturator, a cascaded series of massive copper plates with internal spiral passageways,

will be maintained in a vacuum, thermally isolated from the laboratory environment.

Thermo-electric coolers will maintain the saturator at operating temperatures between -40

and -100 degrees Celsius by pumping heat to isothermal heat removal plates. Liquid

refrigerant supplied by a remote refrigeration system, expanding within the isothermal

plates, will remove the heat from the vacuum environment. The new generator will

generate humidities as low as 14 PPBy using air, argon, oxygen, hydrogen, or helium as the

carrier gas. It is expected to be operational by late 1994.

91

III. Breakout Group

Reports

93
I

i

!

I

I

r

i

I
Gas Sensors for Process Control in Manufacturing

John Steichen

E. I. DuPont de Nemours & Company (Inc.)

P.O. Box 80357

Wilmington, DE 19880-0357

Gary W. Kramer

Chemical Science and Technology Laboratory

National Instimte of Standards and Technology

Gaithersburg, MD 20899-0001

This paper summarizes the breakout session on using Gas Sensors for Process Control in

Manufacturing that was held during the NIST Workshop on Gas Sensors. This study group

examined the barriers that limit the application of new gas sensor technologies in the process

control industry such as the lack of clearly defined performance requirements in a multifaceted market. Other barriers include a reluctance to apply new, non-plant-proven

sensors, the high cost of sensor installation, and the lack of proven reliability for new

technologies. The session participants then suggested several mechanisms that NIST might

develop to assist in promoting new sensor devices for process control including having NIST

become more active in sensor development, in addition to its current role in sensor research,

by incorporating commercialization plans into internal funding proposals for research and

development. NIST might also carry its involvement further down the commercialization

path and broker technologies to the marketplace, identify common industry application needs

including lists of analytes and specifications, provide forums for industry groups to collaborate on special sensing needs, and arrange for collaborative demonstrations of new

technologies in manufacturing plants.

A breakout session on Gas Sensors for Process

Control in Manufacturing was held during the

NIST Workshop on Gas Sensors: Strategies for

Future Technologies. A group of about 25

individuals representing the chemical, nuclear, and

1 electronic processing industries, national

laboratories, and universities attended this session.

Most of the members of this group were familiar

I with sensor developments over the last 20 years.

\ The primary question addressed was, "Why have

' recent, major efforts in sensor development not

produced any measurable impact on industrial

process control?" The group identified many

barriers to the practical application of gas sensors

] in process control and proposed ways in which

NIST could facilitate the process control

ji application of the new and developing sensor

' technologies.

Barriers To Using New Sensor Technologies in

Process Control

There are a number of barriers that limit the

application of new sensor technologies in the

process control industry. Primary among these is a

lack of clearly defined performance requirements.

Because the process control market is so diverse,

there is no single view of sensor needs. Although

the sensor requirements of the markets listed in

Table 1 vary substantially, manufacturers in these

areas share a reluctance to accept new, unproven

technologies. When added to the other perceived

barriers listed in Table 2, it is not surprising that

the new sensor technologies have found limited

industrial control acceptance.

Table 1 Process Control Industry Segments

1. Chemicals and Petrochemicals

2. Polymers and Fibers

3. Semiconductors and Electronics

4. Food and Drug

5. Combustion and Waste Incineration

95
Table 2

Barriers to the Application of New Sensor

Technologies

1. Market diversity and the lack of a clear set of

sensing requirements.

2. Reluctance to apply new sensors which have not

been proven in plant applications.

3. Few vendors offer the new technologies.

4. Analytes often evaluated by researchers in

developing new technologies are of little interest to most plants.

5. High cost of applying sensors and analyzers,

regardless of the sensor cost.

6. Reliability and predictable maintenance

requirements of new sensors not demonstrated.

7. Safety requirements for hazardous areas.

8. Secrecy surrounding industrial process

information.

An additional barrier to the deployment of new

technology in process control markets is the

misunderstanding in the sensor development

community that sensor cost is a major impediment

to acceptance. In fact, there is a minimum expense

in installing any sensor which will be part of a control system. Since control points are selected

for their impact on overall process yield and

quality, the sensor must be carefully installed.

Issues of safety, maintenance, and good

engineering practice must be considered. Typical

sensor installation costs are listed in Table 3 which

shows a minimum expense, excluding the cost of

the sensor, of about $60,000 for an installation on a gas or liquid stream in an existing Class I, Division

2 area. Clearly, in most sensor/process control

programs, the reduction of sensor cost is a secondary issue, since the total installed cost is very high.

On the other hand, because the installed cost of

adding a measurement and control point is so high,

the justification often used in the present economy

is a payback of much less than one year. When

such returns are expected, the risk associated with

the installation must be low. If a plant

administration is willing to install a new

technology sensor to improve their operating costs,

then the risk associated with that installation

should not be technical, but rather market related.

It was the perception of the breakout session

attendees that the reliability of many new sensor

technologies has yet to be demonstrated.

Device packaging requirements necessary to meet

the physical, reliability, and safety constraints of

the plant environment seem to be poorly

understood by sensor development researchers.

The gulf between a developed sensor technology

and plant-ready devices seems to be very wide.

Because of the expense and real risks involved in

experimenting with on new technology for plant

control, few manufacturers are willing to turn their

operating lines into "testbeds for new technology."

On the other hand, sensor development researchers

often do not have access to "real life" applications

for testing their devices. There seems to be no

formal mechanism for establishing a "track record"

for new sensor technologies.

Opportunities for NIST to Facilitate the

Application of New Sensor Technologies to

Process Control

Because of new Federal and/or state environmental

regulations, plants are now frequently required to monitor their emissions more carefully. Again,

reliability of the measurement is of paramount

importance. Because these regulations permit the

monitoring system to be out of operation for only

brief periods, often less than one percent of the

total operating time, the failure of a sensor can be

extremely costly. Therefore, most plants will rely on traditional, often more expensive technologies,

since the risk associated with the new approaches

is too high.

It was the opinion of the session participants that

the efforts in new technologies should be focused

into areas where traditional technologies have not

performed reliably, are not available, or where

lower cost sensors are needed. Table 4 lists several

such applications. Although not necessary for

control, many plants now elect to measure fugitive

emissions rather than calculate them from process

variables, since the regulated limits for calculated

emissions are much lower than those for measured

emissions. The sensing of fugitive emissions

represents an opportunity for new, low-cost gas sensor technologies. If reliability were

demonstrated for at-line measurement of these

emissions, then plants would become more secure

in applying the same measurement to in-line

control of a process. Several fugitive emission

analytes of interest identified during the session are

listed in Table 4.

96
Table 3

Typical Process Control Analyzer Installation Costs*

Engineering, Installation, and Training Costs

Installation Assessment and Engineering Estimates 5,000

Piping 10,000

Electrical, DC Loops 5,000

Procedures, ISO 9000 Review - 10,000

Control Algorithm 10,000

Training 20,000

Subtotal [Not Including the Sensor/Analyzer, Sampling System, or Certification] 60,000

Analyzer/Sensor Costs

Photometer 20,000

NIR/FTIR 60,000 to 100,000

Oxygen 10,000

Emission Certification 20,000

Sampling System 5,000 to 30,000

Total Sensor/Analyzer Installed Cost 75,000 to 210,000

Assumptions: Class I, Division 2 area classification; Process measurement is a process

control point within an existing facility.

Table 4

High Value Applications for New Gas Sensor

Technologies

Traditional analytical techniques have not worked

well for water measurement in the low part-permillion region and below. On the other hand, the

need for measuring such low water levels has

expanded particularly in semiconductor, electronic,

refining, and chemical industries. The need for

real-time low-level water determinations is great

enough that many plants would be interested in any

new technology which offers the promise of

making such moisture measurements, even if a performance track record had not been established.

In several areas, such as combustion and

incinerator control and monitoring, current sensing

technologies are hard pressed to provide the

desired information. New methods are needed, but

such devices would have to be very rugged to survive and operate reliably under very demanding

conditions.

NIST has played an important role in the

development of sensor technologies in the past and

should continue to do so in the future according to the breakout session participants. It was the view

of the group that the NIST involvement should be

aimed toward better defining the industry needs

and then aiding in bringing the new technologies

into actual use. Some members of the group

voiced their displeasure with several of the process

analytical consortia which, although they provide

1. Fugitive Emissions

• Driving force is tightening of environmental

regulations.

• Example Analytes:

Methyl isocyanate

Phosgene

Vinyl chloride

Styrene

HE

2. Semiconductor and Chemical Manufacture

Contaminants

• Lx)w-level water is the critical analyte.

3. Combustion and Stack Scrubber Control

• Analytes are related to various combustion

optimization and pollution abatement schemes.

4. Incinerator and Stack Scrubber Monitoring

• Analytes are related to the incineration of

hazardous wastes.

97

/
good research, have failed to transfer any

technology into plants.

A substantial effort should be mounted to bridge

the gap between sensor research and sensor deployment. The attendees felt that in many cases sensor research has become an end in itself and,

while the results new technology research can be

valuable, the real payback is not realized until

devices are commercially available. More effort

should be expended to make newly developed

transducers into sensors, new sensors into

measuring systems, and new measuring systems

into industrially hardened prototypes.

NIST should become more involved with this

development process and carry its current research

efforts much further toward commercialization.

NIST could act as the needed forum and catalyst in

getting researchers, developers, system integrators,

and industrial users together. Furthermore, NIST's

Advanced Technology Program (ATP) is particularly well suited to provide funding for the

missing link in the new sensor development cycle.

NIST should continue to encourage those involved

in sensor development to apply for such funding.

In certain areas, special sensing needs are pushing

the envelope of existing technology. One example

is the semiconductor industry need to measure

extremely minute concentrations of contaminants.

Through one-on-one industrial Cooperative

Research and Development Agreements

(CRADAs), NIST-sponsored or NlST-organized

industrial consortia and other joint ventures, NIST

can help the industry spread out the costs and risks

of developing new technology to meet these needs.

Again, ATP funding could be appropriate for some

types of these joint ventures.

Since there appears to be no formal mechanism for

establishing "track records" for sensing

technologies, and since the lack of such credentials

is often cited as a reason for not using newly

developed sensors, it was suggested that NIST

establish some means for matching industrial users with researchers, developers, and system

integrators to demonstrate new technologies in real

plant environments.

Many attendees felt that much of modern sensor

research did not address their sensing needs and

that analytes being studied were of little interest in

process monitoring applications. It was suggested

that NIST help identify the real gas sensing needs

of the industrial control community namely what

analytes are important, what concentration ranges

must be sensed, what operating conditions must be

met, and what reliability concerns must be

addressed to make sensors for the plant

environment that is, after all, very different from

the laboratory.

Many members of this breakout session felt that

NIST had taken the first step in improving the gas sensor technology development process by

sponsoring this workshop and most expressed their

desire to reconvene in the future to assist in

defining specific process measurement and control

need's, to review new technology proposals, and

reports, and to plan in-plant evaluations.

98
Indoor Air Quality and Personal Safety

Jarrell Wenger P. E.

Johnson Controls, Inc. P.O. Box 423, M-36

Milwaukee, WI 53201-0423

Andy Persily

Building and Fire Research Laboratory

National Institute of Standards and Technology

Bldg. 226, M/S A313

Gaithersburg, MD 20899-0001

This report is a summary of the discussions of the Indoor Air Quality and Personal Safety

breakout session of the NIST Workshop on Gas Sensors. The application areas discussed in this session were indoor air quality, industrial hygiene and general health and safety. Specific

discussion topics included contaminants to be sensed, required sensor capabilities, sensor market

potential, promising emerging technologies and commercialization issues. The lack of proper

technology development was identified as the major impediment to wide scale commercialization

of gas sensors for these applications. Required features for commercialization that require

development efforts include very high sensitivity for lAQ applications, robust compound-specific

sensors for IH and H&S applications, and long term reliability with minimal required calibration

for all applications. Unit costs must be driven down to low levels to allow deep penetration into

commercial and residential lAQ markets.

Introduction

This report summarizes the discussions of the Indoor

Air Quality and Personal Safety breakout session of

the NIST Workshop on Gas Sensors. To stimulate

discussion, the session started with short presentations on contaminants of concern for indoor air quality

(lAQ), industrial hygiene (IH) and general health and

safety (HcfeS) applications. These themes were

carried throughout the session, with distinctions made

for the characteristics of the separate applications as necessary. An additional short presentation discussed

application of an array of non specific gas sensors to lAQ sensing. To further stimulate discussion,

specific questions were posed to participants including

contaminants to be sensed, required sensor

capabilities, sensor market potential, promising

emerging technologies and commercialization issues.

Introductory Presentations

Andy Persily of NIST discussed contaminants of

interest for lAQ. ASHRAE Standard 62 was noted as

a reference for contaminants and relevant

concentrations, including the National Ambient Air

Quality Standards for S02, particulates, CO, and 03

as contaminants of outdoor air used for ventilation.

The standard also lists maximum allowable indoor

concentrations for C02, radon, chlordane and 03.

Maximum allowable concentrations for additional

contaminants, mainly organic chemicals, are listed in appendices to the standard, taken from Canadian and

the World Health Organization exposure guidelines.

Other lAQ sensing needs identified were: tracer gases

such as SF6, selected refrigerants, odors, contaminant

mixtures such as environmental tobacco smoke,

temperature and relative humidity.

Alan Schnieder of MSA discussed Contaminants of

Interest for Industrial Hygiene and General Health

and Safety, building on his plenary talk on a similar

topic. Primary IH sensing requirements for 02, CO

and H2S were outlined and ammonia and freons were

identified as other general needs. Specific

99
applications such as the plating industry have typical

needs. Hospital H&S needs include the sensing of

halothanes, NO, anesthesia gases, ethylene oxide (at half of the action level), formaldehyde, and Sidex (a

liquid sterilizing agent). Contaminants that are not

well covered by the existing sensor market are anesthesia gases and general IH contaminants; the

entire ACGIH book of threshold limit values (TLVs)

for example.

Jarrell Wenger of Johnson Controls presented a strategy for sensing lAQ contaminants using an array of gas sensors. A distinction was made between lAQ

and IH contaminants in that lAQ contaminants consist

of hundreds of compounds that appear to start causing

problems at 2 to 3 orders of magnitude lower

concentrations than the limited number of compounds

that are typically found in an industrial workplace.

In the short term, lAQ exposure to individual

contaminants does not generally pose a health risk,

suggesting that individual compounds need not be

monitored. Using advanced pattern recognition

techniques, signals from an array of sensitive but non

specific gas monitors have been correlated with a measure of human response. Reasonably good

predictions of the odor perception of a trained panel

of humans were obtained.

Discussion Topics

The following summaries are paraphrased from the

discussion that followed the posing of specific

questions.

1. What substances should be sensed? Building on

the short introductory comments, it was suggested

that lAQ contaminants be split into 2 categories:

contaminants that impact people, and contaminants

that impact equipment and building materials. The

latter category would include particulates, VOCs and

strong oxidants such as ozone. While many of the same contaminants would be included in each

category, allowable concentrations may differ. Another type of environment is a submarine, where

sophisticated analysis can be used to characterize the

contaminants from the ship, the crew and the crew's

belongings. Real-time sensing systems could then be

devised. If the air cleaning systems on the ship can

not remove these contaminants, the sources must be

removed. The environments in battleships and

carriers are more similar to buildings since

contaminants can be exhausted and ventilation can be

provided with outdoor air.

Air cleaning systems can potentially generate

contaminants that are "worse" than the inputs.

Breakthrough sensors for such devices are an emerging need. This concept can be taken to the

point of installing sensors inside of respirators to monitor real-time performance.

Required levels of detection were also discussed. CO

monitoring for a fire detection application requires a detection threshold of about 30 ppm, but high

accuracy and resolution are required above that. For

IH, sensors must be able to detect compounds at the

TLV (or somewhat below, to allow control decisions

to be made). Since suggested total VOC

concentrations for lAQ are typically sub-ppm,

detection levels for groups of compounds or

individual compounds must be tens of ppb or better.

2. What sensing capabilities are currently available?

Other than carbon dioxide, virtually no sensors that are currently available are adequate for the lAQ

application.

Relatively good CO sensors based on several

technologies (electrochemical, infrared, tin oxide) are

available for other applications. Sensors cost as little as $100, have a life of more than 1 year, and require

little calibration (although it is performed every

month in some applications such as mining). A $50

CO sensor that meets UL 2034 guidelines is scheduled to be released for the home market soon. Absence of calibration requirement (or use of

automatic calibration) is seen as essential for

residential (and to a lesser extent, commercial)

applications. For environmental monitoring to protect

electronic equipment, reliability is more important

than an ultra-low detection limit and a low first cost. For some other applications, even the $20K ion

mobility spectrometer can be a cost effective sensor because of its high performance.

3. What sensing capabilities are needed; what are the current gaps (substances and performance

parameters)? For lAQ, the key need is for devices

with lower limits of detection (tens of ppb) for VOCs

and some inorganics. For electronic equipment

environments, even sub-ppm total VOC would be

100
useful. A radon gas sensor would be useful in the

residential market, where real-time instruments are very expensive; such a sensor could be used to operate radon control systems on an as-needed basis.

Multi-sensor strategies have applications for lAQ and

IH, because of flexibility for general monitoring

purposes; such systems can potentially be tailored for

the classes of contaminants found in specific

applications.

A good, inexpensive ammonia sensor is a current need for IH applications. Some VOCs such as vinyl

chloride are toxic in very low concentrations and a sensor with an appropriate detection limit and

sensitivity would be useful. Sensors and electronics

that are immune to RF interference are also needed.

Sensors and systems that are self-monitoring, self- healing and self-calibrating are highly desirable for all applications. Maintenance costs can be much higher

than first costs, or as in residential applications,

maintenance simply will not be performed. For high

precision or high risk applications, periodic

calibration with test gases may be necessary, but it can be simplified with calibration cocktails or automated calibration systems. Sensing mechanisms

can be exploited to perform calibration; infrared CO

sensors can potentially be calibrated with the much

more benign C02. Reference channels can be built

into instruments for calibration checks. Barriers to such innovative calibration strategies may be more

regulatory than technical.

4. What is the market potential for lAQ, IH and

general health and safety sensors? Market potential

will obviously depend on cost. At high prices,

market penetration into lAQ and residential

applications will be limited, but as costs drop,

markets will expand. The lAQ market for example,

is potentially huge if sensors are inexpensive enough

to be applied in each thermostat zone. A large

potential market exists for inexpensive (integrated) sensors for total VOC, C02, temperature and relative

humidity. Calculations performed by an HVAC

control company indicate that integrated sensors for demand controlled ventilation must sell for less than

$300 per building zone to achieve an adequate

payback for customers through energy savings.

Another control company estimates that selling price

must be closer to $30 to achieve wide scale

application. If residential sensors can be developed

to have a 20 year maintenance free lifetime, $5 to $20 sensors would penetrate most of the market.

Wiring can be very expensive and cost-effective

telemetry may be an additional required feature. Standard interfaces are another feature that would

help convince customers to apply environmental

sensors; the ability to easily plug in alternative sensors from different manufacturers would be

attractive.

Systems engineering, modeling and control strategy

development can not be ignored; complex strategies are required to balance control of thermal comfort,

acceptable lAQ and energy costs in a wide variety of

systems. Yet, inexpensive, high performance,

properly applied devices still may not be sufficient. Experience with smoke detectors suggests that regulation and insurance incentives were the final steps necessary to achieve deep market penetration.

5. What are promising emerging technologies (in the

research pipeline)? The Naval Research Lab is looking at SAW (surface acoustic wave) devices for

environmental applications. These sensors exhibit

good sensitivity and low detection levels, but stability over their lifetime is unknown. Current tin oxide

detection levels are inadequate. Atomic force

microscopy and scanning tunneling microscopy are possible sensor transducers that can be micro

machined; these technologies have been used for

studying antibody-antigen interactions.

With more sensitive detectors, NDIR sensors have the

potential for detection levels in ppb range. Higher

detection level for C02 have potential to drop to $30

per device in large quantities. Ion mobility

spectrometers exhibit very good performance, but it is unlikely that sensors could drop below $1000 each.

6. What are commercialization

potential/pitfalls/resources required? The question was raised of why some of the promising emerging

technologies of 5 years ago, such as SAW devices,

remain promising emerging technologies rather than

commercial products. One potential manufacturer

spent substantial sums of money testing several new

technologies including SAW and micro machined

sensors, and could not get them to work.

101
Commercial devices must be reliable; false alarms are

as undesirable as outright failures.

Some of the commercialization pitfalls are the hard to meetuser wish® lists of price and performance without

regulations creating a firm market. As a counter

argument, it is difficult to put regulations into place

before the required technology is available, and once

in place, compliance withregulations can still be slow.

One alternative is to provide choices in regulations,

such as the ASHRAE Standard 62 lAQ procedure,

which can not be met now, but keepsoptions open for

creative applications as technology becomes available.

One barrier to commercialization of new sensors is a lack of communication between researchers, potential

manufacturers and potential users. Presentations from more users would have been a useful addition to the

research results presented at this workshop. Many

researchers do not appear to be targeting their work

for the real world; micro devices are very popular in research, yet macro devices are more appropriate for many customers in IH (more robust). Perhaps more

research should focus on monitoring electronics;

production SAW sensors will be of negligible cost, but signal monitoring electronics can be prohibitively

expensive.

User groups could potentially interface with

researchers if the prohibitive proprietary issues and

intellectual property concerns could be addressed.

Users could develop testing standards to guide

research testing under realistic conditions. The gap

between researchers and users appears to be in the

development area, reflecting general trends in US

business. Hitachi spent $20 million to develop an

electronic nose without success, but is ready to invest

again with a suitable US partner. Government

CRADAs can help small companies through

development, but some past agreements have had

intellectual property problems. The NIST ATP

appears to be better suited to large consortia rather

than small businesses, and for research rather than

development.

7. Open discussion

Market potential and possible pitfalls are illustrated by the telecommunications industry; 34,000 buildings

have sensing needs, but any sensing system must be

entirely fail safe because false alarms can not be

tolerated. Totally automated HVAC systems are the wave of the future, and automated diagnostics for

controlled systems and control systems are needed.

Conclusions

The most significant impediment to wide scale

commercial application of gas sensors for lAQ, IH

and H&S is the lack of proper technology

development. Promising technologies in the research

pipeline are not emerging into the commercial arena,

yet rapid commercialization of current research

technologies is probably not the answer. Unless the

investment is made in proper development of these

technologies, critical user requirements will not be

met. These requirements include very high

sensitivity for lAQ applications, robust compoundspecific sensors for IH and H&S applications, and

long term reliability with minimal required calibration

for all applications. Development efforts and high

volume manufacturing will be required to drive unit costs down to the levels that allow deep penetration

into commercial and residential lAQ markets. Most

of the required technology improvements are not mutually exclusive between these applications, or

versus process control, outdoor environmental

monitoring and automotive applications. Substantial

sharing of development efforts between applications

should be possible.

102
Gas Sensors in Outdoor Environmental Monitoring and Site Remediation

Barry M. Wise* and Franklin R. Guenther*

*Molecular Science Research Center K2-12

Pacific Northwest Laboratory^

P.O. Box 999

Richland, WA 99352

'*Computer Science and Technology Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899

A special session on sensors in outdoor environmental monitoring and site remediation was held as part of the NIST Workshop on Gas Sensors. This

manuscript summarizes the main points of the workshop. Application

areas, issues of concern, and potentially fruitful areas for further research

and development were discussed. The main conclusion of the group was

that the problems and potential solutions to problems in environmental

monitoring were common to other application areas of sensing as well. Of

particular concern to the group were the many barriers to final development

and commercialization of sensors. Barriers included lack of information on

potential markets, lack of support for development, (as opposed to more

basic research), and difficulties in developing the final packaging for a device. The characterization and development of chemically selective

materials for sensor coatings was viewed by the group as a particularly

important area for future research.

Introduction'

A special "breakout group" session on

gas sensors in environmental monitoring

and site remediation was held as part of

the NIST Workshop on Gas Sensors. The

breakout group had -35 attendees, who

were about equally divided between

academic institutions, industry and

government laboratories. The discussion

was broken into three topics: application

areas, important issues in environmental

sensing, and promising areas of research.

Highlights of the discussion follow. It should be noted that the topics discussed

'Pacific Northwest Laboratory is operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC06-

76RLO 1830.

most likely reflect the particular biases of

the group and that a somewhat different

group may have different concerns.

Applications of Environmental Sensors

The group was polled concerning the areas of application of sensors in environmental

monitoring. Two application areas in

particular stood out as having a great

potential for eventually being a very large

market. The first of these was monitoring

of stack emissions. While large chemical

and power plants can afford fairly

expensive equipment for monitoring

emissions, smaller plants will have to rely on less expensive alternatives. It has also

recently been found that in many urban

areas, such as Los Angeles, the major

contributors to air pollution are non point

103
sources such as dry cleaners and bakeries.

Small businesses such as these cannot

support expensive equipment for

monitoring emissions, yet it is clear that if progress is to be made in improving air

quality, these small sources must be

monitored.

Another area with a potentially large

market is the detection of leaks of volatile

and highly volatile organic compounds

from valves and fittings in chemical

plants. Current regulations require

frequent testing of these systems, but it is entirely possible that continuous

monitoring will eventually be required.

This application will require distributed

monitoring systems where the sensors are located far from power sources and may

have to report to a central location.

Sensors will also face the additional

requirement of explosion safety. Related

areas include the monitoring of chemical

storage tanks for fugitive emissions and

the monitoring of oil rigs.

Environmental monitoring and site

remediation efforts being addressed by the

Department of Energy constitute a wide

variety of applications for gas sensors. A

major area is the monitoring of the vadose zone in soils for volatile organic carbon

compounds. This needs to be done both as a screening procedure in order to determine appropriate remediation

measures and continuously as a worker

safety measure during remediation

activities.

Gas monitoring is also an important concern in nuclear waste storage and

processing for remediation. The vapor

head space in some nuclear waste storage

tanks must be monitored for hydrogen

and other gases. Gas formation in process

pipelines is also an issue.

Another application is the monitoring of

test wells for groundwater contaminants.

These contaminants can often be detected

in the vapor space above the well water.

As an example, there are several thousand

wells at the Hanford site alone that must

be checked at least yearly, with many of

them requiring testing more often than

that. Sensing technology that would

eliminate sampling of the wells and

transport of the samples to testing

laboratories would greatly improve the

efficiency of the monitoring effort. There

are many other specific needs within the

DOE complex.

National security needs for gas sensors include monitoring to detect the

production of chemical weapons and the

detection of chemical warfare agents

themselves. In the former case, it is generally the precursors to chemical

weapons that must be detected, and are often present at only the part per billion

level. A particular problem in this area is that many of the precursors are similar to

relatively common pesticides in structure and chemical behavior. Thus, specificity is of concern, since it is very important in

this area to not have any false alarms.

Detection of warfare agents has been of concern to the military for some years.

Here the cost of false alarms is less severe and quantitation is not required. However,

ruggedness and portability become very

important issues in these applications.

Issues in Environmental Monitoring

In the paragraphs that follow, the issues of concern to the group are discussed. These

follow in no particular order, though the

issues thought to be of greatest concern

are noted.

A representative from the Environmental

Protection Agency pointed out the

104
differences between characterization and

monitoring. Typically, sensors will be

more suitable for the monitoring problem,

where you already know what you are looking for, while more extensive

analytical procedures are often required for

characterization. Sensors can also be used

in "screening" applications where a yes/no

question about the presence of

contaminants of interest must be

answered, e.g. is analyte y present in the

samples at concentrations greater than x?

Unfortunately, screening techniques,

which in practice can be very reliable for

answering relevant environmental

questions, have suffered a bad reputation

due to the term "screening," which seems

to imply highly uncertain results. It was

noted that the most important requirement

for screening tests is a reliable zero level.

Fouling and corrosion of sensors in

outdoor environments is a concern. This is particularly true in applications where

moismre levels are high and where there is the possibility for biological fouling of

sensor surfaces.

Making measurements in an uncontrolled

environment presents special challenges.

Often, the background matrix is both

unknown and variable. In the face of

varying background matrices, a single sensor system must be totally selective for

the analyte of interest. On the other hand, a sensor array, producing a vector of data

for each measurement, need not have any

sensors that are totally selective; however,

the variable background matrix must be

included in the calibration of the array so

that a combination of sensors not affected

by the background variation can be

determined. Recent developments in

second-order sensors, those that produce a matrix of data for each sample, where

sensor response is a function of two

parameters, hold the promise of

quantitation in the presence of varying

background that were not included

specifically in the cahbration matrix.

It was generally agreed that more work

needs to be done in material science in

order to achieve better understanding of

the way that analytes interact with sensor

coatings, both at the surface and in the

bulk material. An example of this is the

development of polymeric coatings for

surface acoustic wave devices. A thorough

understanding of the way analytes interact

with the polymers is critical to a full understanding of the way that SAW

devices operate. Many new materials are on the horizon, and the ability to grow

surfaces through epitaxial and other

methods will certainly impact the

development of sensors. These techniques

also hold the promise of enhancing the

understand of the interactions of the

materials because of the very well

characterized nature of the materials. This

is in contrast to the way much sensor development has occurred in the past,

when materials were simply tested in

applications and the underlying reasons

for their behavior was not of concern. It has been demonstrated that understanding

of materials is especially critical in the

development of sensor arrays where a

variety of coatings are used. Fundamental

understanding of the materials is essential

in determining how to best combine

sensors to achieve selectivity of the

analytes of interest in the presence of

background matrix variation.

The cost of sensors was of widely varying concern to the group. At one extreme are the national laboratories responsible for

environmental monitoring critical to safety

and the prevention of further

environmental contamination. In these

instances, it is not unusual to spend

hundred of thousands, or even several

million dollars developing a device for an

application that occurs only in a small

105
number of instances. At the other extreme

are the automobile manufacturers, which

may require millions of copies of a single

device but are only willing to pay a very

small sum for each copy.

The lack of information about the

performance, cost, and availability of

systems for environmental monitoring is a hindrance to their integration into the

marketplace. This results in some

confusion in several areas. Often, it is difficult to sort out the claims of vendors

and achieve a reliable estimate of the

performance expected of a device in a particular application. There is a real need

for unbiased, real-world testing. Often, sensor users are not aware of working

technologies for particular applications and

either purchase a suboptimal system or embark on unneeded development of a new device.

Concerns about sensor drift appeared to correlate with the complexity of the device

under consideration. It was pointed out

that many of today's single sensor

systems include automatic zero and span

set features. With more complex arrays,

however, it is more difficult to correct for

changes in the sensitivity and baseline of

the instrument.

Portability of sensor systems is of some

concern in environmental monitoring and

site remediation applications. Often

instruments must be taken "into the field" to remote locations. The physical size and

weight of a system can be a factor in how

widely it is used. Power supply is often an

issue in remote locations.

There appears to be a need for more

streamlined methods for developing cost

effective packaging for environmental

sensors, as well as sensors in other

applications. Several remedies to this

problem were suggested. For instance.

would it be possible to develop some

generic packages for sensors that could be

used to house a variety of devices? Also,

the need for concurrent engineering was

noted. The development of a package

must not lag too far behind development

of the transducer itself. A side issue in environmental monitoring

is the lack of a reliable baseline for

naturally occurring chemicals. Such a baseline would be useful for both

regulatory purposes and in the

development of sensors for specific

applications. Knowledge of the

background matrix is critical in the

development of most sensor systems.

High Potential Areas for Research and

Development

As noted above, materials science was

seen as a critical research area with regard

to the development of environmental

sensors. Advances in the understanding of

materials and improvements in our ability to tailor make materials for specific

applications will have a great impact on

the development of selective

environmental sensors. Chemically

sensitive films is an especially important

area in the general field of materials. There

is a great deal of variety in sensitive films,

including polymers, catalysts,

chemiluminescence, etc.

Many sensors have a nonlinear response

to chemical and physical changes in their

surroundings. Research in chemometrics,

particularly in the area of nonlinear

multivariate calibration, will be an

important aspect of making nonlinear

devices practical. A wide variety of

nonlinear methods exist but more work

needs to be done to make these methods

more accessible to the nonexpert user. Research in second-order calibration

methods may be particularly important.

106
While many second-order analytical

instruments produce well behaved

"bilinear" data, many second order

sensors are expected to produce the more

challenging "nonbilinear" data. Methods

for dealing with these data types are still in

their infancy.

The group agreed that fiber optic based

sensors will be an important area for

further development. The potential

richness of the data produced by such

devices, essentially the same as spectrophotometric methods, allows for

selective sensing in many applications

provided that suitable calibration matrices can be obtained. Furthermore, it is possible to combine fiber optic sensors with other technologies, such as chemically selective membranes, to form

the basis for the second-order devices

discussed above.

Miniaturization of sensors will continue to be an important research area, particularly

to the extent that the transducers and

electronics of these devices can be

integrated for form robust packages.

Arrays of sensors will also be important

as they can be combined to operate as first or second-order devices. Research into the

processes required to build such devices is important. Streamlining the manufacturing

process is an important step in the

commercialization of any sensing device.

The development of biological sensors may be important, particularly for the

detection of biologically active analytes.

Conclusions

Many of the problems involved with

using and developing sensors for

environmental monitoring and site

remediation appear to be common to other areas of sensing. There are a few

exceptions, including an increased

emphasis on the ability to obtain a

quantitative reading in the presence of an unknown and possibly varying

background matrix, and the importance of

a stable zero reading.

Barriers to the commercialization of

environmental sensors was one of the

major concerns of the group. Often the

size of a potential market is not known,

nor are the prices that the market segment

would be willing to pay. While support

for research, particularly in the national

laboratories and other government

laboratories appears to be adequate,

support for the final development is often

lacking. This, in part, may be due to the

fact that individuals prefer to work in the

more glamorous domain of research

rather than the more tedious area of

development. A related issue is the

packaging of sensors. It was noted during

the main workshop program by a

representative from Ford Motor Company

that a complete sensor includes the

package and connectors, not just the

transducer. Often, it is development of the

package that slows down final

development. It was noted that concurrent

development, or holistic design can

alleviate the packaging problem.

The group did not appear to be concerned

over transducers themselves. It appears

that the variety of transduction

mechanisms is adequate for most needs in

environmental monitoring. More attention

needs to be paid to the coatings for

transducers, which is generally the only

chemically active part of the sensor. One

researcher noted that this is "where the

rubber meets the road."

107

Gas Sensors for the Automotive and Other Transportation Industries

Galen B. Fisher

Physical Chemistry Department

General Motors NAO Research and Development Center

Warren, MI 48090-9055

Kenneth G. Kreider

Chemical Science and Technology Laboratory

National Institute of Standards and Technology

Bldg. 221, M/S A303

Gaithersburg, MD 20899

Abstract

The needs for and results of a workshop session on gas sensors in the transportation industries are reviewed. Regulations calling for the on-board diagnosis of vehicle emissions performance

provide the main motivation for sensor development. Because of difficulties with the present

method adopted for monitoring catalyst performance, several more direct sensors of hydrocarbon

conversion efficiency were discussed, including dual-element calorimetry and non-dispersive

infrared measurements.

Introduction

This session was intended to examine the needs and technology for chemical gas sensors

for the automotive and transportation industries. The 27 attendees represented users and

suppliers of gas sensors and independent research and development institutions including

government, academic, and private organizations. They considered both short and long term

needs as well as technology available at present and in the foreseeable future. Because the needs

of the automobile industry were well-defined, well-represented, and of large economic impact,

these needs dominated the discussion of the full session.

The session was initiated by introductions and brief statements of interest by all participants. This was followed by a statement of purpose by the co-chairs which was prompted

by a participant. Dr. Galen Fisher, one co-chair, specifically stated the need for identifying

problems and coming up with solutions for onboard diagnostics for automobiles. Dr. Kenneth

Kreider, the other co-chair, described NlST's role as a facilitator to bring the key participants

together to address the technology of gas sensors and contribute to bringing these technologies

into commercial use.

The workshop session then turned to the definition of the sensor needs of the auto

industry followed by presentations of proposed solutions, a lively discussion of the advantages

and shortcomings of these solutions, and a discussion of some of the broader issues related to the needs, such as research needs and usefulness of standards. The statement of the need for the

109
automotive sensors which will be a result of the 1990 Clean Air Act was made primarily by

Galen Fisher of the General Motors Research and Development Center. Supporting remarks were made by others, including Dr. Jaco Visser of the Ford Scientific Research Laboratories.

Gas Sensors Needed For Transportation Applications

The needs of the transportation industry for gas sensors are manifold, but there are a few

new challenges that are receiving considerable attention. Among the most acute needs are those

caused by recent changes in automotive emissions control regulations, in addition to the more

stringent emission standards which new vehicles must meet in the 1990's (summarized in [1]),

The California Air Resources Board and the Environmental Protection Agency have promulgated

rules which require automakers to incorporate comprehensive on-board diagnostics for emissions

control systems nationwide by 1996. In California vehicles from several manufacturers have

them in 1994 model year vehicles. The intent of these regulations is to ensure that drivers are made aware, when any component of their vehicle which affects emissions is not functioning

properly, by means of a dashboard malfunction indicator light. Among the monitored systems

is the catalytic converter which converts gas phase pollutants consisting of hydrocarbons (HC),

carbon monoxide (CO), and nitrogen oxides (NO,, mainly NO), to the more benign species

carbon dioxide (CO^), water (H^O), and nitrogen (N,).

It is difficult enough to monitor species in the exhaust at all because of the high

temperatures and hydrocarbons and water present, but to do it for the life of the vehicle is even

harder. At the same time the emissions standards are also becoming more stringent. This has

led to the development of new methods to meet hydrocarbon standards. Strategies include having

multiple converters, some closer to the engine so that they warm up faster to become active.

With these new standards, the level of hydrocarbons that must be detected in exhaust will also

fall during the 1990's. All in all it makes for a very difficult problem, to diagnose the HC

conversion efficiency of possibly several converters in cars that are designed to convert almost

all of the hydrocarbons.

The current approach to monitoring catalytic converters is called the dual or multiple

oxygen sensor approach. Its rationale of operation is that there is a relationship between the

oxygen storage of a catalyst, measured by the oxygen sensors, and the HC conversion efficiency

[2,3]. This method has been found wanting from a fundamental point of view, since there is no

clear causal connection between oxygen storage and HC conversion efficiency and the available

data show a very non-linear relationship [1,4]. Particularly for close-coupled converters, it has

been shown [5] that this method detects the loss of oxygen storage that occurs during the aging

of converters, even though the HC conversion efficiency remains very high. This could lead to the unnecessary recall of good converters.

These problems with the present method have aroused considerable interest in other

methods of measuring hydrocarbon or related emissions that are more direct. A method is needed that will detect the malfunction of the first catalyst in a system defined as the point when

its HC conversion efficiency falls below 50%-60%. The regulations are actually expressed in terms of non-methane organic gases (NMOG) emissions. Methods that have been discussed

include non-dispersive infrared, calorimetric methods, resistance measurements, zirconia-based

sensors, and other approaches. Whatever the method, the diagnostic exhaust gas sensors should

110
satisfy certain requirements. The first goal would be for a direct measurement of one or more

of the three regulated constituents; HC, CO, and NO. If the sensor output involves an inferred

relationship with, for example, HC concentration, then the relationship must be robust, wellestablished and documented. Table I sets approximate targets that are necessary for these

measurements as generally agreed upon by the On Board Diagnostics II (OBD II) Catalyst

Monitoring Committee of the USCAR Low Emission Partnership made up of representatives of

General Motors, Ford, and Chrysler.

Table 1. Approximate targets for detection of hydrocarbons, carbon monoxide, and nitric

oxide by a sensor for OBD 11 catalyst monitoring. Only HC measurement is called for by

current regulations.

Constituent Range Minimum Detectable

Resolution

Threshold

HC (NMOG) 0 - 1000 ppm (0.1 %) 25 ppm 25 ppm

CO 0 - 10000 ppm (1 %) 500 ppm 500 ppm

NO 0 - 1000 ppm (0.1 %) 25 ppm 100 ppm

In addition to the above measurement capabilities for HC, CO and NO,, the sensor system

will have to survive and perform for at least the order of 100,000 miles (160,000 km) in a very

hostile environment, automotive exhaust. A minimum service interval would be 50,000 miles

(80,000 km). A sensor in the exhaust, behind an engine, will see temperatures that can vary

from -40 °C to 800 °C with spikes above that possible; the normal ambient temperatures may be

between -40° C and 120°C. The sensor will also be exposed to a range of gases in these

approximate proportions by volume: 10% CO,, 10% H.O, 1 % 0_„ 1 % CO, 0.3% H, and 0.1%

HC, nitric oxides (NO,, mainly NO), and SO,. There are also trace amounts of phosphorus (P)

and silicon (Si). The balance is nitrogen (N,). The flow rates are generally between 10-30 g/s

and can be as high as 150 g/s.

A few other associated requirements occur for automotive applications. The entire device

with its packaging must fit under the body of the vehicle. The devices should be totally

interchangeable, with no calibration required and should be compatible with a 12 V dc system.

The device should have characteristics that make it easy to carry-out self-diagnosis. Response

times should be on the order of tens of seconds in the worst case; it does not need to respond

to individual cylinder events. The test of this diagnostic and the others on the vehicle will all have to occur at least during the time of the Federal Test Procedure (FTP) for emissions

performance.

Gas Sensors Proposed for Automotive Needs

After the discussion of sensor needs, the breakout session went on to cover a number of

gas sensor technologies. Three interesting approaches, mainly for HC gas sensing, were

presented to the workshop to solve the catalyst monitoring problems. They were presented by

111
Mike Richard of Sonoxco, Atiil Shah of Cerametal, and Jacob Wong of Telaire Systems, and by

other participants whose devices were under research and development.

One proposed solution, discussed by Dr. Richard, consists of a dual calorimeter

comparing the signals from catalyzed and non-catalyzed elements, it can have the capability of

measuring CO, HC, NO,, and SO2 depending on the selection of catalysts. Devices typically can be produced with a response time of seconds by conventional manufacturing processes. The

catalytic process requires sufficient oxygen to oxidize CO and HC's; these devices have lacked

sensitivity to CH4. A newly developed microfabricated version of the sensor may have a faster

response time and less dependence on flow rates. The complex technology of preparing these

devices for automotive applications would require partnerships among the sensor producers and

automobile manufacturers. The discussion at the workshop covered the sensor's capability to meet the measurement criteria stated above and its durability.

A second solution, presented by Dr. Wong, uses a non-dispersive infrared sensor for

detection of HC, CO,, CO, NO,, SO,, and/or ozone. The selectivity of the sensor depends on narrow band pass filters limited to an absorption band of the molecule of interest. The design

presented had a simple IR source (a light bulb) powered by a pulsing waveform and a unique

waveguide which, by design, simulates the 10 m pathlength normally needed for adequate

sensitivity in measuring IR signals. The designer claimed that the IR sensor complete with the

pyroelectric detector could cost less than $15 and require only 1 .5 W of power. Questions were

raised concerning the stability and durability of the device when exposed to 160,000 km of

automotive exhaust.

The third approach which was discussed related to various solid state and electrochemical

sensors, including ZrO^, SnO,, ZnO, and SrTiO,. The zirconia sensors used on present vehicles

would be improved and combined with selective membranes to measure oxidizing species. Zinc

oxide sensors would be used for reducing species such as CO and hydrocarbons. There was

considerable hesitancy to disclose information on the mechanisms of operation or even the

transducing materials in these sensors, but it was clear that nimierous organizations were

interested in this billion dollar market.

The international competition was discussed as well as the techniques that would be used

to meet the need for low emissions vehicles. Worldwide there is much interest in lean burn

engines. A lean exhaust technology also is available for diesel engines and the new 2-stroke

engine technology. In addition, a discussion of new, improved catalysts took place, primarily

those for NO,, possibly using zeolites. These technologies all depend heavily on the quality of

the fuel and it was the consensus of the automobile manufacturers that improvements in fuel

quality, especially as it relates to sulfur content, are needed. Since the primary job of the sensors

is and will be to monitor catalytic converter performance, there was extensive discussion about

converter technology. It was also apparent that research on the behavior of catalytic and sensor

materials is still important to the development of this technology, since many questions remain on material behavior and stability. New approaches to these general problems were discussed

including the consortium approach (i.e. Chrysler, CM, Ford Low Emissions Partnership within

USCAR) and government programs, such as the Advanced Technology Program.

112
Summary

Our automotive sensor breakout session featured a lively discussion focussed on the near- term needs of the auto industry to meet requirements of the EPA and California Air Resources

Board (CARB). These needs have been further defined by the USCAR Low Emissions

Partnerships. They include responses to CARB's "Low Emission Vehicles" (LEV's), transitional

LEV'S or TLEV's, and ultra LEV's or ULEV's. They require extensive on-board diagnostic

systems, which means an extensive market for automotive sensors in the near future. The

workshop participants included knowledgeable representatives from automobile manufacturers,

sensor manufacturers, and members of the R&D community. Although interesting solutions

to the sensor rec^uirements were proposed, the extremely stringent requirements for performance

and durability indicate intense activity in improving the technology will be needed. The

interaction at the workshop was an excellent way to further communication between the

principals of this technical activity.

References

L J. R. Theis, W. J. LaBarge, and G. B. Fisher, "The Effects of Catalyst Volume and

Ceria Content on the Emission Performance and Oxygen Storage Capacity of automotive

Catalysts," SAE Paper #932666, 1993.

2. W. B. Clemmens, M. A. Sabourin, and T. Rao, "Detection of Catalyst Performance Loss

Using On-Board Diagnostics," SAE Paper #99062, 1990.

3. J. W. Koupal, M. A. Sabourin, and W. B. Clemmens, "Detection of Catalyst Failure OnVehicle Using the Dual Oxygen Sensor Method," SAE Paper #910561, 1991.

4. J. S. Hepburn and H. S. Gandhi, "The Relationship between Catalyst Hydrocarbon

Conversion Efficiency and Oxygen Storage Capacity," SAE Paper #920631, 1992.

5. G. B. Fisher, J. R. Theis, M. V. Casarella, and S. T. Mahan, "The Role of Ceria in Automotive Exhaust Catalysis and OBD-II Catalyst Monitoring," SAE Paper #931034,

1993.

113

IV. Discussion Sessions

115

THE ROLE OF EMERGING TECHNOLOGIES IN GAS SENSING

Richard E. Cavicchi and Steve Semancik

Chemical Science and Technology Laboratory

NIST, Gaithersburg, MD 20899

Advances in a number of diverse technologies are converging to make possible a new

generation of gas sensors with improved selectivity, sensitivity, portability, and reliability at lower cost. These advances range from improved sensing materials and new transduction

methods to new computational techniques for analyzing multi-sensor data. It is the challenge to the sensor community to rapidly synthesize developments from these diverse areas and produce

marketable sensors and sensing instruments. Each competing new technology brings both a new set of benefits as well as new limitations for application. In this field, competing

technologies for a given sensor application may lie outside the realm of one individual's

expertise. It is, therefore, the purpose of this session to highlight important developments in

varied fields that can be expected to have an impact on gas sensing technology in the next 5-10

years.

Micromachined Devices

Microfabrication of electronic devices is a mature technology with well-defined procedures for

film deposition, materials processing, lithography, and packaging to produce reliable devices.

These methods are now being applied to create micro-machined structures on the length scale of

10 [Lm to 1 mm. The majority of micro-machined devices are based on Si wafer processing,

partly because of the maturity of this technology, and partly because of the suitability of Si for

micro-machining. Sensors based on micromachining may include miniature Taguchi

(semiconducting oxide) sensors, pyroelectric devices, sensors using electro-osmotic pumps for

fluids, and possible tunneling transducers. These devices offer the potential for integration into

arrays of sensors with integrated electronic devices, as well as capabilities for self calibration

and self-regeneration.

Some micromachined devices are created through process equipment which, while similar to commercial electronic device fabrication technology, requires special process steps, such as back-side wafer etching and wafer alignment, which are not part of the standard electronics

manufacturing protocol. Facilities devoted specifically to micromachining technology offer the

greatest flexibility for device design and material selection. Drawbacks to this approach mainly

involve longer commercialization times due to the large capital expenditures for such facilities,

and untested reliability issues. There are also efforts to adapt commercial electronics processing

rules to form micro-machined devices. Dr. Michael Gaitan (NIST) described the use of existing

CMOS (Complementary Metal Oxide Semiconductor) foundry operations to produce microhotplates and other devices. In this methodology, circuit and layer sequence designs are submitted through the MOSIS (Metal Oxide Semiconductor Implementation System) wafersharing service of ARPA (Advanced Research Projects Agency) to commercial foundries for

device fabrication. Returned chips require only simple process steps such as etching or low

resolution lithography to produce the micro-machined structures. Advantages are the

reproducibility and reliability of the commercial process, the ability to integrate electronics onto

the same chip, and low start-up costs. In this approach, however, there are limited materials and

layer sequences available, as the designs must conform to the CMOS device fabrication rules.

Multi-variate Analysis and Neural Networks

The ability to fabricate sensor arrays presents new computational problems for the real-time

analysis of sensor data. If the individual sensors in the array are not perfectly selective, many of

117
the array elements may produce a response for a single gas. For example, the carbon monoxide

sensor in an array may produce a response in the presence of a hydrocarbon. The patterns of

responses generated by the array in the presence of different gases at different concentrations

may, however, be used to correctly produce a gas-specific analysis. Computational methods

that address these problems are found in fields such as character recognition and process

chemometrics. A key requirement for all analytical algorithms, however, is calibration models

and calibration sets that are well chosen.

The methods of multi-variate analysis were discussed by Dr. B. M. Wise (Pacific Northwest

Labs). A key problem in sensor instrumentation is correctly compensating for drift and

interfering signals from species other than the target analyte. It was noted that 0th order (single

sensor) instruments are unable to detect drift or interfering signals ; 1st order (array sensors)

instruments can detect drift and interfering signals , but cannot compensate mathematically; and

with 2nd order instruments multi-variate analysis can correct mathematically for the effects of

drift and interfering signals . Examples where second order instrumentation is used include

combined gas chromatograph-mass spectrometer analytical techniques and combined liquid

chromatography-infrared spectroscopic systems. Mathematical techniques used to deconvolute

these data to detect drift and interfering signals can also be used in sensors. One example is fiber optic sensors with distal tip membranes, where the analyte diffuses into a membrane. Here

the first order is the transport time and second order is response as a function of wavelength. A

second example is microfabricated array sensors in which the first order results from varying

the materials on each sensor and the second order uses temperature programming to give a matrix of data. It was noted that the multi-variate methods are computationally intensive, which

therefore will place demands on instrumentation that uses arrays of gas sensors.

Alternative algorithms for coping with large quantities of data from only partially selective sensors are based on neural networks. Prof. Tom McAvoy (Univ. MD) noted that the nose performs such operations rapidly and can distinguish specific odors from a complex mixture.

He has developed models based on a nonlinear chaotic oscillator that operates in an unstable

state. When a stimulus is detected, the neurons are "kicked" into a new state, i.e. they jump to a new "strange attractor". This built-in instability gives speed and amplification of the detection

process. Computational algorithms that mimic this process are being developed which can use

existing sensors.

The need for computational capability interfaced to sensor array architectures is being met with

instrumentation of decreasing size and increasing computational power. One method, discussed

by Dr. Paul Clifford (Mosaic Industries) incorporates partial least squares data analysis with

neural nets, allowing partitioning of the problem into learning and application. This model is incorporated in a small computer which analyzes responses from several Taguchi sensors.

Packaging and Telemetry

Key aspects of gas sensing technology that is often neglected by researchers are the problems of

packaging the transducer and sending the signals from the transducer to the user. In automotive

applications, the package is usually the most expensive part of the sensor system, due to the

requirements for ruggedness in a harsh environment. Sensors for hazardous environments face

similar issues. For signal transmission to remote or dangerous locations, radio-frequency

transmission methods used in cellular telephone technology are being used, as are fiber optic

systems, which provide immunity to electrical noise and can be combined with optical sensors. Remote sensors, for example, that will be used for space applications will require very low

power operation and will be interfaced to other solar powered instrumentation. For array sensors that would have hundreds of sensing elements, signal communication will also a problem. Circuitry for multiplexing, controlling, and amplifying sensor signals will have to be

integrated in the sensor design.

118
New Device Technologies

A number of approaches for improving gas sensors are being demonstrated. These approaches can be expected to expand the apphcation areas for sensors.

Optical detection methods continue to advance. Fiber optic sensors exploit the interaction of

light which travels down the fiber to interact with the sampled gas at the distal end. Light

traveling away from the distel end carries with it spectroscopic information about the sampled

environment. Advantages of optical fibers are the long transmission distances possible,

enabling the remote sampling of inaccessible or hazardous environments with immunity to electrical interference. Dr. Jacob Wong (Telaire Systems Inc.) discussed an optical sensor which uses nondispersive infrared technique. The gas to be tested is sampled using a sampling

chamber which is positioned between an IR source and a detector. Narrow band interference

filters are used to achieve selectivity. Multiple sensors can be integrated into a single instrument.

The device has been used for smokestack monitoring.

Surface acoustic wave (SAW) devices have long been of interest for use as gas sensing devices.

These devices are incorporated into a resonant circuit and operate by measuring the change in

resonant frequency when a gas is adsorbed on the device. Chemically selective films are used to provide selective detection of gases. A new development in this technology, described by Dr.

James Wiczer (Sandia), takes advantage of the recent advances in creating self-assembled

monolayers (SAM) on metallic and semiconducting surfaces. A SAM consists of an ensemble

of long chain hydrocarbon molecules, in which one end of each molecule is designed to bond

strongly to the substrate and the other end is tailored to produce a desired surface property. For

example, thiol molecules have a sulfur group at one end which bonds strongly to gold. For

sensor applications, the surface end group can be designed to be selective to the species of

interest. The work at Sandia has involved the development of sensors for chemical warfare

agents with a sensitivity of 100 ppb using a carboxy terminated long chain alkyl with a Cu2+

chelating agent. Differential measurements between a chemically selective SAW and a blank

SAW are used to enhance sensitivity and compensate for drift. The sensors can be fabricated

into arrays. For array devices, a method for patterning SAMs is required. Dr. Michael Tarlov

(NIST) described a new patterning method for SAMs. Ultraviolet irradiation is used to photooxidize an exposed thiol region to create thiolate ions which can then be replaced in

solution of another thiol with different chemical selectivity.

SAMs are one example of new materials systems being used for sensors. Other new materials

which may find use in gas sensors include fullerenes, mixed semiconducting oxides, zeolites,

sol gels, conducting polymers, and chemically selective membrane materials. Dr. Steve

Semancik (NIST) described work at NIST to produce epitaxial semiconducting oxide films

which could be used in Taguchi type sensors. Inhomogeneities in microstructure and orientation

in polycrystalline-based sensors may be responsible for drift and slow response times in these

devices. The atomically smooth, single-orientation epitaxial films may result in faster, more

reliable sensors.

The invention of scanning tunneling microscopy has spawned the creation of many transducing

instruments with position-sensitive detection at the sub-angstrom level. Dr. Gregory E. Poirier

(NIST) discussed the possiblities for using this position sensitivity to create a gas partial

pressure-mechanical displacement transducer. Micro-machined physical sensors (such as accelerometers) based on tunneling are being developed by Dr. William J. Kaiser et al. at JPL

(Jet Propulsion Laboratory). There is also work to create micro-machined tunneling instruments

in Prof. Noel MacDonald's group at Cornell University. Technological challenges for this

approach include the development of chemically selective films that will alter the distance

between the film and the tunneling tip, and vibration isolation.

119

Commercialization and Standards Issues

James R. Whetstone

Process Measurements Division

Chemical Science and Technology Laboratory

NIST

and

William C. Lyndon

Office of Technology Commercialization

Technology Services

NIST

Commercialization and standards issues related to sensor technology development involve both

private sector and governmental activities. The private sector is largely responsible for development

and evolution of commercial products. Federal government efforts impact the commercialization

process through standards and regulations , Cooperative Research and Development Agreements,

and licensing of government-owned technology, i.e., patents.

Commercialization - The Government Role

Government supports sensor technology development and commercialization through its research and

development activities, patent licensing, and cooperative research efforts with private industry. The

patent process is the only way government can protect intellectual property developed by government

institutions. Government research efforts support generic sensor technology and attempt to transfer

such technology to the U. S. private sector. As a result of their research activities, governmental

agencies hold patents. These may be licensed by U.S. companies. The conditions of the license are negotiated for each agreement. NIST actively seeks to license technology patented by NIST research

efforts through its Office of Technology Commercialization. Other government agencies pursue

similar programs.

U. S. industry can utilize government research and development expertise in several ways.

Agreements between individual government laboratories and private sector firms are a primary

method used. This is facilitated through cooperative research and development agreements

(CRADAs). CRADAs provide protection of both intellectual property developed during

collaborative efforts and propriety information that may be divulged to the government. On a larger

scale, consortia of private firms may interact with government laboratories in joint efforts that involve

industry-wide issues. NIST and other government agencies encourage CRADAs and consortia for

effective technology transfer methods of government research and development efforts. Additionally,

various mechanisms are in place that provide access to government research capabilities by the

private sector. At NIST these include both formal and informal agreements where NIST staff and

staff of private companies perform collaborative research efforts. Formal agreements include Guest

Researcher agreements, where an employee of a private sector firm would work at NIST in a

collaborative effort with NIST staff. Recently NIST has established a mechanism where NIST staff are encouraged to spend up to a year's time at a private sector company working on a collaborative

121
effort. Informal contacts are an important way in which NIST and other government laboratories

work together on topics of mutual interest.

Commercialization - The Private Sector Role

The private sector brings sensor technology to market engaging in the spectrum of associated

business activities. It protects that technology through use of the patent process where possible.

Identification and determination oftechnologies with good potential for commercialization is a critical phase of the development cycle. In bringing sensor technologies to market a variety of issues must

be addressed to make such efforts successful.

Standardization

Standardization efforts in the U.S. are led by private industry through several organizations, e.g., ANSI (The American National Standards Institute), ASTM (American Society for Testing, and

Materials), ISA (Instrument Society of America), NEMA (National Electrical Manufacturers

Association). ANSI bears the responsibility for coordination of U.S. standardization activities

internationally. Government supports these efforts in the following ways:

• Acts as a neutral third party in technology assessment to evaluate performance claims.

• Provides measurement standards that support uniformity in measurements, both nationally

and internationally.

• Participates in international standards activities by facilitating communication between

participants, particularly where direct govemment-to-government interactions are helpful.

This becomes an important fianction in those cases where standardization activities of

other nations are the province of the national government. Such efforts are generally

undertaken in partnership with ANSI.

An important aspect of participation in standardization activities is addressing non-tariff trade barrier

issues in international commerce. These barriers, at times, take the form of standards compliance as

a requirement for access to markets outside the U. S. The impact of such trade barriers on

measurement-related technology has become more important in recent years. In addition,

standardization activities may provide a forum for information exchange on a variety of related topics.

Discussion Topics

Discussion during the session involved a number of issues confronting both users and developers of

sensor technology products. Several categories of concerns were identified during the discussions.

These are given below and include various comments from workshop participants.

• Internalional Standards: particularly in the European Economic Community (EEC),

impact not only suppliers of measurement and sensor equipment, but also users of that

equipment. Efforts of various U.S. standards bodies were identified as being pertinent.

Concerns were raised that results from on-going activities should be freely available

because their impact could be significant.

122
Performance ofMeasuring Instruments: both short and long term. It was suggested

that performance testing by NIST would be of use to the user community. (NIST staff

noted that NIST, and NBS before it, has avoided this type of testing due to the potential

for implied product endorsement.) Several in the user community noted that some of the

round robin testing sponsored by private testing organizations was much too slow in reporting results.

Regulatory Compliance for Measuring Instruments: Discussion focussed primarily on

regulatory requirements for environmental emission measuring instruments. Issues not

directly related to sensing were the driving force. Participants were especially concerned

with requirements by various government agencies (federal/state/local) for reporting of

results, and the potential for differing interpretations resulting in disputes between

regulatory agencies and private sector users.

Risks in Commercialization: Utility of marketing surveys and identification of sensing

applications categorized by the manufacturing sector was desired. Discussion of this

topic left unresolved the identification of an entity to perform this task.

Installatioti/Use Protocols and Requirements: The requirements for installation in many

user facilities, particularly manufacturing plants of significant size, are not well recognized

by the sensor manufacturing community. This is particularly the case for small in- strumentation companies because they do not usually have ready access to the knowledge.

At one point in the discussion, a representative of a major chemical manufacturer noted

that the cost of installation of a single instrument in a plant approached $60,000. Issues

relating to safety requirements are usually not well understood by smaller instrumentation

developers. It was suggested that a method be developed to address these areas. This

would also be advantageous to the user community because much of the innovation in

sensing/measurement technology is currently found in the small instrumentation

companies.

123

V. Appendices

125

Appendix A —Final Program

NIST Workshop on Gas Sensors: Strategies for Future Technologies

National Institute of Standards and Technology

Gaithersburg, Maryland

September 8-9, 1993

All meetings will be held in the Green Auditorium of Building 101 at NIST, except as noted.

Wednesday, September 8, 1993

8:00am-8:30am On-site check-in/coffee

8:30 am - 12:40 pm Morning Session

Moderator: Dr. Steve Semancik

Process Measurements Division, NIST

Welcoming Remarks

Dr. Hratch Semerjian, Director

Chemical Science and Technology Laboratory, NIST

Invited Presentations

8:50 am - 9:30 am Solid State Gas Sensors: World Markets and New

Approaches for Gas Sensing

Dr. Marc Madou

Microfabrication Applications

9:30 am - 10:00 am Gas Sensing for Industrial Safety and Health

Dr. Alan Schneider

Mine Safety Appliances

10:00 am - 10:30 am Gas Sensing Needs of the Environmental Protection

Agency

Mr. David Friedman

Environmental Protection Agency

10:30 am- 10:50 am Break

10:50 am - 1 1 :20 am Present and Future Gas Sensors for Automobiles

Mr. Joseph Giachino

Ford Motor Company

1 1:20 am - 1 1:50 am Gas Sensor Needs and Technology at the Department

of Energy

Dr. Glenn Bastiaans

Iowa State University

127
1 1:50 am - 12:20 pm Thermal Microsensors for Environmental and

Industrial Control

Dr, Ulrich Bonne

Honeywell

12:20 pm - 12:40 pm , Introduction of Breakout and Discussion Session

Chairpersons

• Breakout Group Sign-up

• Survey Material Distribution

12:40 pm- 1:30 pm Lunch

1 :30 pm - 5:00 pm Afternoon Session

Moderator: Dr. Kenneth Kreider

Process Measurements Division, NIST

1:30 pm - 2:00 pm NIST Advanced Technology Program

Dr. Stanley Abramowitz

ATP Program

2:00 pm - 2:30 pm NIST Facihties and Programs in Gas Sensing

Dr. James Whetstone, Dr. Steve Semancik

Process Measurements Division, NIST

2:30 pm - 4:00 pm Technical Poster Session (with refreshments)

Employees' Lounge

Invited Presentations (continued)

4:00 pm - 4:30 pm Gas Sensor Technologies at Sandia National

Laboratory

Dr. Robert Hughes

Sandia National Laboratory

4:30 pm - 5:00 pm Microchemical Sensing with Temperature Programmed

Methods

Dr. Kensall Wise, Dr. John Gland

University of Michigan

5:15 pm Bus to Gaithersburg Hilton

6:00 pm Product Poster Session (with cash bar)

Gaithersburg Hilton

7:00 pm Dinner at the Gaithersburg Hilton

128
Thursday, September 9, 1993

8:20 am - 12:40 pm Morning Session

Moderator: Dr. Richard Cavicchi

Process Measurements Division, NIST

8:20 am - 8:40 am Instructions for Breakout Groups

Invited Presentations (continued)

8:40 am - 9: 10 am Amperometric Electrochemical Gas Sensors

Dr. Joseph Stetter Transducers Research, Inc.

9: 10 am - 9:40 am Gas Sensors in the Chemical Industry: Today's

Practiced Technology

Dr. Kevin Hool

Dow Chemical Company

9:40 am - 10: 10 am Development of Differential Mode and Solid Electrolyte

Gas Sensors

Dr. Chung-Chiun Liu

Case Western Reserve University

10:10 am- 10:30 am Break

10:30 am - 12:40 pm Breakout Group Meetings

(rooms assigned at 8:20 am)

A. Process Control in Manufacturing

Chair: Dr. John Steichen, Dupont

Co-Chair: Dr. Gary Kramer, NIST

B. Indoor Air Quality and Personal Safety

Chair: Mr. Jarrell Wenger, Johnson Controls

Co-Chair: Dr. Andrew Persily, NIST

C. Outdoor Environmental Monitoring and Site

Remediation

Chair: Dr. Barry Wise, Batelle Pacific Northwest

Laboratories

Co-Chair: Dr. Frank Guenther, NIST

D. Automotive and Other Transportation

Chair: Dr. Galen Fisher, General Motors Research

Laboratories

Co-Chair: Dr. Kenneth Kreider, NIST

12:40 pm - 1:30 pm Lunch

129
1:30 pm -4:20 pm

1:30 pm -2:30 pm

2:30 pm- 3:40 pm

3:40 pm-4:20 pm

4:00 pm-5:00 pm

4:20 pm-5:00 pm

Afternoon Session

Moderator: Dr. Gregory Rosasco, Chief

Process Measurements Division, NIST

Reports on Breakout Groups

Breakout Chairpersons of Groups A, B, C and D

Discussion

• The Role of Emerging Technologies in Gas Sensing

Co-Chairs: Dr. Steve Semancik and Dr. Richard

Cavicchi, Process Measurements Division, NIST

• Commercialization and Standards Issues Co-Chairs: Mr. William Lyndon, Office of

Technology Commercialization, NIST and

Dr. James Whetstone, Process Measurements

Division, NIST

Lab Tours (see sign-up sheets)

Executive Meetings for Breakout and Discussion

Chairpersons

130
Appendix B —Participants List

Workshop on Gas Sensors: Strategies for Future Technologies

September 8-9, 1993

National Institute of Standards and Technology

Gaithersburg, Maryland

Stanley Abramowitz

NIST

BIdg. 222, Rm. A353

Gaithersburg, MD 20899-0001

USA

Anoop Agrawal

Donnelly Corp.

4545 E. Ft. Lowell Tucson, AZ 85712

USA

Bryan Bentz

David Sarnoff Research Ctr. 201 Washington Rd.

Princeton, NJ 08540-6449

USA

Ulrich Bonne

Honeywell

10701 Lyndale Ave S. Bloomington, MN 55420

USA

Richard Cavicchi

NIST

BIdg. 221. Rm. A303

Gaithersburg, MD 20899

USA

Ashok L Cholli BOC Group

100 Mountain Ave. Murray Hill, NJ 07974

USA

Mark Anderson

NRL

Code 6170

Chem. Div. Washington, DC 20375

USA

Gordon Arnold

Sierra Monitor

1991 Tarob Crt. Milprtas, CA 95035

USA

Scott Bradley

Kaman Sciences, Corp.

2560 Huntington Ave.

Ste. 200

Alexandria, VA 22303

USA

Emil Braun NIST

BIdg. 224, Bm. A249

Gaithersburg, MD 20899-0001

USA

Steve Choquette

NIST

BIdg. 222, Rm. B158

Gaithersburg, MD 20899-0001

USA

Paul Clifford Mosaic Industries 5437 Central Ave.

Ste. 1 Neward, NJ 94560

USA

Abdul-Majeed Azad

Ohio State Univ. 2041 College Rd.

Dept. Materials Science

Columbus, OH 43210

USA

Michael Barnes

Emissarins Ltd. 3 Hillcroft Dr. Rome, GA 30161-0500

USA

Glenn Bastiaans Iowa State Univ. 1915Scholl Rd. Rm. ASC2, CATD

Ames, lA 50011

USA

John Brennan

Texas Instruments 34 Forest Street MS 10-13

Attleboro, MA 02703

USA

Laurie Brown

NIST

BIdg. 222, Rm. B158

Gaithersburg, MD 20899-0001

USA

Arthur Buckingham

Westinghouse Savannah River P.O. Box 1521

MS3K28

Baltimore, MD 21203

USA

Greg Collins Geo-Centers, Inc. 10903 Indian Head Hgwy.

Fort Washington, MD 20744

USA

Michael Collison NIST

Gaithersburg, MD 20899-0001

USA

William Danley

156 Hamilton Road

Landenberg, PA 19350

USA

Dan Deery

Texas Instruments 300 N. Main St. 168

Versailles, KY 40383

USA

131
Sarn Dsnny Michael Gaitan Bjarne Hagen

Univ. oi Maryland k 1 1 OT

NIST Univ. of Maryland

Dept. of Fire Prot. Eng. BIdg. 225, Rm. B360 Dept. of Fire Prot. Eng.

College Park, MD 20742 Gaithersburg, MD 20899 College Park, MD 20742

USA USA USA

William Dorko Ronald Garnett John Hastie

1 HOT NIST Texas Instruments NIST

Blag. 222, Rm. B158 300 N Mam St. BIdg. 223, Rm. B106

Gaithersburg, MD 20899-0001 Rm. 6006 Gaithersburg, MD 20899-0001

USA Versailles, KY 40383 USA

USA

Steve Dorris Victor Henrich

Argonne National Lab. Joseph Giachino Yale Univ. 9700 S. Cass Ave. Ford Electronics 212-G233 1 7000 Rotunda Dr. James Hill Argonne, IL 60439-4838 C375 NIST

USA Dearborn, Ml n 1 —J AAA n a a a BIdg. 226, Rm. B306

USA Gaithersburg, MD 20899-0001

Michael Dunbar USA

IC Sensors J. Gland

1701 McCarthy Blvd. Univ. of Michigan Barbara Hoffheins

Milpitas, CA 95035 930 N. University Oak Ridge National Lab. USA Rm. 4549 P.O. Box 2008

Ann Arbor, Ml 48109-1055 3606 MS/6002

Manfred Fink USA Oak Ridge, TN 37831-6002

Univ. of Texas USA

26th Street William Glaunsinger

RLM 10.316 Arizona State Univ. Kevin Hool

Austin, TX 78712 Dept. of Chem. Dow Chemical Co. USA Tempe, AZ 85287-1604 Central Research

USA 1712 BIdg.

Galen Fisher Midland, Ml 48674

General Motors R&D Center Richard Grace USA

30500 Mound Rd. Carnegie Mellon Research

P.O. Box 9055

A J A A ^* f I t_ A 4400 Fifth Ave. Brent Horine ^ -

Warren, Ml 48090-9055 Pittsburgh, PA 15213 Sawtek

USA USA 1818 S. Hwy 441

Apopka, FL 32703

Norm Foss William Grosshandler USA

Honeywell NIST

10701 Lyndale Ave S. BIdg. 224, Rm. B356 Peter Huang

MN09-C100 Gaithersburg, MD 20899-0001 NIST

Minneapolis, MN 55420 USA

n 1 AA ^ nAAA

BIdg. 221, Rm. B306

USA Gaithersburg, MD 20899-0001

Frank Guenther USA

David Friedman NIST

U.S. E.P.A. BIdg. 222, Rm. B158 Robert Hughes

401 M. St., SW 1 I K AAAAA AAAJ

Gaithersburg, MD 20899-0001 Sandia National Lab. RD-680 1 1 A USA P.O. Box 5800

Washington, DC 20460 Dept. 1315

USA Albuquerque, NM 87185

USA

132
Christopher Jahnes

IBM Corp.

P.O. Box 218

02-218

Yorktown Heights, NY 10598

USA

Adishwar Jain Trans Tech Associates

8 Carol Crt. Hicksville, NY 11801

USA

Kenneth Johnson

Gas Tech., Inc. 8407 Central Ave. Newark, CA 94560

USA

Kenneth Jones

Telaire Systems, Inc. 6489 Calle Real

Goleta, CA 93117

USA

Tom Jones

Texas Instruments DSEG

Dallas, TX

USA

Linda Joy

NIST

BIdg. 101, Rm. A903

Gaithersburg, MD 20899-0001

USA

Weng Poo Kang

Vanderbitt Univ. Box 1661 -B

Nasville, TN 37235

USA

Richard F. Kayser

NIST

BIdg. 221, Rm. A105

Gaithersurg, MD 20899

USA

Kevin Kirk W.L Gore & Associates

555 Papermill Rd. Newark, DE 19711

USA

Klara Kiss Akzo Chemicals, Inc.

1 Livingston Ave. Dobbs Ferry, NY 10522-3401

USA

Julie Konrad

Ford Electronics 17000 Rotunda Dr. C490

Dearborn, Ml 48128

USA

Gary Kramer

NIST

BIdg. 222, Rm. A343

Gaithersburg, MD 20899-0001

USA

Ken Kreider

NIST

BIdg. 221, Rm. A303

Gaithersburg, MD 20899

USA

Sol Krongelb

IBM T.J. Watson Research Ctr. P.O. Box 218

Yorktown Heights, NY 10598

USA

Paul Kroninger

Leeds and Northrup

P.O. Box 2000

117

North Wales, PA 19454

USA

Earl Lankheet

AC Rochester Div., GM

1300 N. Dort Hwy.

Dept. 32-24 EB

Flint, Ml 48556

USA

Jeffrey Leavitt Westinghouse Savannah River P.O. Box 1521

MS 3K 28

Baltimore, MD 21203

USA

Chung-Chiun Liu Case Western Resen/e Univ. 10900 Euclid Ave. Bingham BIdg., Rm. 112

Cleveland, OH 44106-7200

USA

Ron Livingston

Westinghouse Savannah River P.O. Box 6809

BIdg. 773-A

Aiken, SC 29808

USA

William Lyndon

NIST

Gaithersburg, MD 20899-0001

USA

Kevin Lyons

NIST

Gaithersburg, MD 20899-0001

USA

William MacCrehan

NIST

BIdg. 222, Rm. B158

Gaithersburg, MD 20899-0001

USA

Marc Madou

Microfabrication Applications

3680 Bryant St. Palo Alto, CA 94306

USA

Trevor Marshall

Seatronics, Inc. 3235 Sunset Ave.

Hatboro, PA 19040

USA

133
Janet Marshall NIST

Btdg. 225, Rm. B360

Gaithersburg, MD 20899-0001

USA

Joaquin V. Martinez de Pinillos Air Products & Chemicals

7201 Hamilton Blvd. R4202

Allentown, PA 18195-1501

USA

Larry Mason

Martin Marietta P.O. Box 179

B0560

Denver, CO 80201

USA

Bruce Mattson NIST

BIdg. 224, Rm. B256

Gaithersburg, MD 20899-0001

USA

Thomas McAvoy

Univ. of Maryland

Dept. of Chem Engr.

College Park, MD

USA

Kevin McDonald

Sentrol Inc. 10831 SW Cascade Blvd. Portland, OR 97223

USA

R. Andrew McGill

Geo Centers, Inc. 10933 Indian Head Hgwy.

Ft. Washington, MD

USA

Gerald Mitchell NIST

Bldg. 222, Rm. B158

Gaithersburg, MD 20899-0001

USA

Janet Morrison

NIST

Gaithersburg, MD 20899-0001

USA

Mayandren Naidoo

American Univ. 4400 Mass. Ave, NW

McKinley Bldg, #102

Washington, DC 20010

USA

S.E. Nave

Westinghouse Savannah River SRTC

773-41 A 1170

Aiken, SC 29804

USA

Glen Neuburger

Bellcore 331 Newman Springs Rd. Red Bank, NJ 07701

USA

Eugene O'Sullivan

IBM Research

P.O. Box 218

01-15

Yorktown Heights, NY 10598

USA

Dongling Pan

Univ. of Maryland

Dept. of Chem. Eng.

College Park, MD 20770

Andrew Persily

NIST

Bldg. 226, Rm. A313

Gaithersburg, MD 20899-0001

USA

Gerald Phillips

Columbia Scientific Industries 11950 Jollyville Rd.

Austin, TX 78759

USA

Gregory Poirier NIST

Bldg. 221, Rm. A303

Gaithersburg, MD 20899

USA

Marc Porlnoff Carnegie Mellon Research

4400 Fifth Ave.

Pittsburgh, PA 15213

USA

Cedric Powell

NIST

Bldg. 222, Rm. B248

Gaithersburg, MD 20899-0001

USA

Wally Raisanen

AZI

P.O. Box 1930

Tempe, AZ 85281

USA

Claudia Randolph

Kaman Sciences, Corp.

2560 Huntington Ave.

Ste. 200

Alexandria, VA 22303

USA

David Rath , IBM Corp.

P.O. Box 218

01-117

Yorktown Heights, NY 10598

USA

Carolyn Ribes

Dow Chemical Co.

P.O. Box 400

Bldg. 2510

Plaquemine, LA 70765

USA

Michael Richard

SONOXCO, Inc. 430 Ferguson Dr. Mountain View, CA 94043

USA

134
Steve Robey AtuI Shah Mark Steimer

NIST Ceramatec W.L. Gore & Associates

BIdg. 222, Rm. B248 2425 South 900 West 555 Papermill Rd.

Gaithersburg, MD 20899-0001 Salt Lake City, UT 84119 Newark, DE 19711

USA USA USA

Gregory Rosasco David Sherve Gregory Steinthal NIST MTI Teiaire Systems, Inc. BIdg. 221, Rm. B306 41762 Christy St. 6489 Calle Real

Gaithersburg, MD 20899-0001 Fremont, CA 94538 Goleta, CA 93117

USA USA USA

Susan Rose-Pehrsson Erika Shoemaker Joseph Stetter Naval Research Lab. Argonne National Lab. Transducer Research, Inc. Chem. Div. 9700 S. Cass Ave. 999 Chicago Ave. Code 6110 BIdg. 362 Naperville, IL 60540

Washington, DC 20375-5342 Argonne, IL 60439 USA

USA USA

John Suehle

Gregory Scace Robert Shull NIST

NIST NIST BIdg. 225, Rm. B360

BIdg. 221, Rm. A303 BIdg. 223, Rm. 8152 Gaithersburg, MD 20899

Gaithersburg, MD 20899-0001 Gaithersburg, MD 20899-0001 USA

USA USA

Valeriy Sukharev

Alan Schneider Spencer Silverthorne NIST

MSA Leeds and Northrup BIdg. 221, Rm. A303

P.O. Box 427 P.O. Box 2000 Gaithersburg, MD 20899

Pittsburg, PA 15230 111 USA

USA North Wales, PA 19454

USA Michael Tarlov Reginald Seiders MIST

Army Research Office Fred Sittler BIdg. 221, Rm. B306

P.O. Box 12211 Rosemount, Inc. Gaithersburg, MD 20899-0001

RTP, NC 27709-2211 12001 Technology Dr. USA

USA AB1-A

Eden Praire, MN 55344 John Tozier Steve Semancik USA Bachbrach, Inc. NIST 625 Alpha Dr. BIdg. 221, Rm. A303 Mark Sobolewski Pittsburgh, PA 15238

Gaithersburg, MD 20899-0001 NIST USA

USA BIdg. 221, Rm. B306

Gaithersburg, MD 20899-0001 Jarda Ulbrecht Hratch Semerjian USA NIST

NIST BIdg. 224, Rm. B356

BIdg. 222, Rm. A317 John Steichen Gaithersburg, MD 20899-0001

Gaithersburg, MD 20899-0001 DuPont Co. USA

USA P.O. Box 80357

Wilmington, DE 19880-0357

USA

135
John Vetelino James R. Whetsone

Univ. of Maine NIST

Sawyer Res. BIdg. BIdg. 221. Rm. A303

Lab. for Surface Sci. Gaithersburg, MD 20899

Orano, ME 04401 USA

USA

Julie Whitney

Jaco Visser Texas Instruments Ford Motor Company 1300 N. Main St., #168

P.O. Box 2053 Versailles, KY 40383

Research Lab. MD3028 USA

Dearborn, Ml 48121

USA James Wiczer

Sandia National Lab. Michael Vogt P.O. Box 5800

Argonne National Lab. Dept. 1315

9700 S. Cass Ave.. 372 B110 Albuquerque, NM 87185

Argonne, IL 60439 USA

USA

Kensall Wise

Jarrell Wenger Univ. of Michigan

Johnson Controls, Inc. 1301 Beal Ave.

P.O. Box 423, M-36 1246 EECS BIdg.

Milwaukee. Wl 53201-0423 Ann Arbor, Ml 48109-2122

USA USA

Barry M. Wise

Pacific Northwest Labs.

Battelle Blvd. P.O. Box 999, K2-12

Richland, WA 99352

USA

Jacob Wong

Telaire Systems, Inc. 6489 Calle Real

Goleta, CA 93117

USA

Wen S. Young

Universal Sensors and Devices

9205 Alabama Ave. Unite

Chatsworth, CA 91311

USA

Mona Zaghloul

NIST

BIdg. 225, Rm. B360

Gaithersburg, MD 20899-0001

USA

John Zeigler

Edwards Co. 195 Farmington Ave. Farmington, CT 06032

USA

136
Appendix C —Laboratory Stops

September 9,1993 4:00-5:10 pm

1 . Sensor Surface Processes

Process Sensing Group, CSTL

Bldg. 221, A-310

2. Ultrathin Film Deposition

Process Sensing Group, CSTL

Bldg. 221, A-314

3. IC Compatible Processing

IC Technology Group, EEEL

Bldg. 225, B-365

Contact:

S. Semancik

R. Cavicchi

J. Suehle

4. Calibration Gas Standards

Gas Metrology Group, CSTL

Bldg. 222, B-332

W. Dorko

5. Humidity Calibration

Process Sensing Group, CSTL

Bldg. 221, B-353

P. Huang

G. Scace

6. Fiber Optic Waveguides

Sensors and Automation Group, CSTL

Bldg. 222, A-332

S. Choquette

L. Brown

7. Field Monitoring of Indoor Air Quality

Indoor Air Quality and Ventilation Group, BFRL

Bldg. 226, A-312 A. Persily

8. Large Scale Fire Test Facility

Large Fire Research Group, BFRL

Bldg 205*

* transportation required

E. Braun

W. Grosshandler

137

Appendix D —Advanced Technology Program

Advanced

Technology

Progtram

U.S. Department

of Commerce

Technology

Administration

National Institute

of Standards and

Technology

Overview

Begun in 1990, the Advanced Technology Program at the National

Institute of Standards and Technology invests directly in the nation's

economic growth by working with industry to develop innovative

technologies with strong commercial potential—technologies which, if successful, would enable novel or greatly improved products and services

for the world market.

The ATP concentrates on promising, but high-risk, enabling technologies

that can form the basis for new and improved products, manufacturing

processes, and services. It accelerates technologies that, because they are

risky, are unlikely to be developed in time to compete in rapidly changing

world markets without such a partnership of industry and government. It does not fund product development.

Essential Features

The unique mission of the ATP—support for civilian technologies in the nation's economic interest—requires some special features, which have

become hallmarks of the ATP and major factors in its success.

The ATP has a broad mission to promote large economic

benefits for the nation.

The legislative mandate of the ATP is to promote "commercializing new

scientific discoveries rapidly" and "refining manufacturing practices."

This offers tremendous scope. The objective of some projects is to develop technologies that enable lower cost, higher quality, or

faster-to-market products. The ultimate objective of others is to develop

the know-how to provide new-to-the-world or radically improved

products and services. The ATP has a high potential impact on U.S.

economic growth because, unlike other federal technology programs, it makes investments explicitly for this reason rather than for some other

national goal.

139
The ATP works as a partner with industry.

While government provides the catalyst, industry conceives, partially

funds, and executes ATP projects. Management of projects is geared to ensure that the work performed is what industry believes should be done

and is what it can do best. The ATP relies on the substantial involvement of industry to define and

implement its R&D programs. ATP research directions are selected based on suggestions from industry and developed in consultation with industry.

Specific R&D projects are selected from proposals developed and

submitted by industry. All awards are made through announced

competitions.

The ATP emphasizes cost sharing—ATP recipients on average pay more

than half the total costs of the R&D. This helps ensure that companies

have a vested interest in the success of projects and in timely

commercialization. At the same time, participation by small companies

and start-ups is not precluded, because the single-applicant requirement

for cost sharing is that the company cover its indirect costs. Since most

start-ups and small companies have low indirect cost rates, this requirement is not prohibitive. i,,^, , ,(. The ATP also takes an active role in helping to ensure the success of the projects it supports. ATP program managers work to build close,

cooperative relationships with their counterparts in industry.

Projects are selected on the basis of both technical and

business merit through a fair and rigorous competition.

Each proposal is reviewed thoroughly by scientists and engineers expert

in the subject area—a common procedure for government technology

programs. But ATP proposals that score well in this technical review go on to a further evaluation of potential economic impact, evidence of

significant commitment to the project on the part of the proposer, and

other business-related factors affecting the likelihood that successful

results will be commercialized.

The scientific and technical reviewers are primarily federal and academic

experts to avoid conflict-of-interest problems and protect proprietary

information. Business reviews are conducted primarily by business

experts from the private sector who agree to avoid conflicts of interest and

abide by non-disclosure requirements. Semifinalists receive in-depth oral reviews. Proposals are ranked according to published selection criteria,

and funding is awarded on the basis of the ranking. This merit-based

selection process has been fully tested and refined and is essential to the effectiveness of the ATP. '.

140
The ATP provides direct support to for-profit companies of all sizes.

Commercial firms know best how to commercialize a promising new

technology. With this in mind, the ATP funds for-profit companies.

Small, medium, and large companies, and joint ventures led by two or more companies, are eligible for direct funding. Successful ATP project

sponsors range in size from start-up companies with a handful of

employees to major industrial firms with international scope. Universities,

federal laboratories, and non-profit independent research organizations

participate in many ATP projects, but as subcontractors or as members of

joint ventures (non-profit independent research organizations may

administer joint ventures).

The ATP has a comprehensive plan for monitoring and

evaluating its performance.

From the start, the ATP has strongly embraced program evaluation and

considers it critical to the development and operation of a results-oriented,

efficiently run program. Early on, an evaluation plan was developed and

measurable goals were identified against which to track performance.

ATP Competitions

The ATP conducts competitions each year to select R&D projects for support. Only project proposals submitted in response to a formal

competition are considered. (Competitions are announced in the Federal

Register, in Commerce Business Daily, and by direct mail, among other

channels.)

Projects are evaluated against a list of criteria, including:

the scientific and technical merit of the proposal,

the potential for broad-based economic benefits to the United

States,

the quality of the proposer's plans for eventual commercialization

of the technology—the ATP does not fund product development, but

the proposer should have plans for capitalizing on a successful

project,

the level of commitment of the proposer and the adequacy of their organizational structure, and

the experience and qualifications of the proposer.

Since 1994, the bulk of ATP funding has been applied to focused

program areas—multiyear efforts of approximately $20 million to

141
$50 million per year, targeted at specific, well-defined technology and

business goals. Often, these involve the parallel development of a suite of

interlocking R&D projects. By managing groups of projects that complement and reinforce each other, the ATP can have the greatest

possible impact on technology and the economy.

In addition to focused program competitions, which are open only to projects relevant to the program topic, the ATP sponsors at least one

"general" competition each year, open to all technology areas. Past general competition awards have covered a broad spectrum of

technologies in agriculture, biotechnology, microelectronics and

electronics manufacturing, machine tools, advanced automotive

manufacturing, advanced materials, information and communication

technology, chemical processing, and other areas.

Regardless of whether a project is selected as part of a program or a general competition, awards to individual companies are limited to $2 million over 3 years and can be used only for direct R&D costs. Awards to joint ventures can be for up to 5 years, and joint ventures must

provide more than 50 percent of the resources for the project.

Industry Input

The process of selecting program areas to focus ATP support is critical to success. Ideas for possible focused program areas come in from all sources, but particularly from industry: individual companies, trade associations, and professional societies. Universities and federal laboratories also have submitted "white papers" proposing possible ATP

program areas.

Setting research priorities is a constant, ongoing process, beginning with

submission of a program idea. If there appears to be sufficient industry

interest in a particular program, the ATP generally hosts a public

workshop to discuss and further refine the program concept. Other

mechanisms for getting industry's input include:

advice from senior industry technical and business managers;

input from industry associations, trade groups, and professional

societies; and

analysis of proposals submitted to ATP in previous competitions.

Since every program has a fixed lifespan, there will be a constant turnover of programs as some are completed and others started.

142
PROJECTS" VS. ""PROGRAMS

Make sure you understand the distinction between an ATP project and an ATP

programl

An ATP Program:

describes a major research direction for the ATP, with technology and business,

goals that generally involve a broad range of specific technology development

tasks; may be proposed to the ATP at any time;

involves multiple projects by single companies and joint ventures; provides a framework for one or more ATP competitions to solicit project

proposals in support of the program goals—programs are not funded, projects

are;involves no legal agreements between the proposer(s) and the ATP; and

involves no proprietary information.

An ATP Project:

is a specific research project;

is proposed only in response to a formal ATP competition;

receives ATP funds;

involves a legal agreement between the proposer(s) and the ATP; and

generally involves sharing proprietary information (which is legally protected

from disclosure) with the ATP.

.

Each idea for a focused program is evaluated against four key criteria:

the potential for a significant impact on the U.S. economy,

including the credibility of the program's proposed pathways to economic growth, the importance of the existing or potential

sector(s) affected, and the probability of subsequent

commercialization;

good technical ideas that are "cutting edge," high-risk,

strategically important, and based on sound scientific and technical

concepts;

a strong industry commitment to participate, including breadth

and depth of interest and willingness to share costs and to work with

the ATP and other partners; and

143
an opportunity for the ATP to make a major difference by

supporting work that is unique or complementary to other industrial and government efforts, that offers timely and significant

acceleration of research progress, and that requires a critical mass of

funding that the ATP can provide.

Economic Returns

Early results indicate that the ATP is successfully improving the

capability of the nation's businesses to capture economic returns from

scientific and technological innovations. Two independent studies of

projects funded in FY 1991 revealed substantial, early beneficial impacts on participating companies, including:

expanded R&D activity, particularly the ability to engage in high-risk, long-term research with high-payoff potential;

cost and time savings, improved productivity, and other benefits

from industry-industry, industry-government, and industry-university

collaborations;

improved competitive standing;

formation of valuable strategic business alliances;

improved ability to attract investors;

assistance in converting from defense to commercial applications;

and

acceleration of technology development, leading to improved

market share.

Additional independent studies of the results of early ATP projects are under way.

New Strategies

Since FY 1994, the ATP has worked to reinforce its impact on the U.S.

economy with several new strategies:

The ATP is taking a more active role in building cooperative programs

among businesses, universities, and government agencies. Because of its global view and broad sources of information, the ATP is in a unique

position to spot potentially advantageous alliances and bring them to the

attention of its industrial partners. For example, the ATP might bring to the attention of a joint venture an outside company whose proposed work

appears to mesh well with that of the joint venture. Or the ATP might

suggest a strategic alliance between a single-company applicant proposing

to develop a new technology and a potential end user of that technology,

if such an alliance would increase the chances of a project's success.

144
Although the final decisions about such alliances will always lie with the companies, recognizing such opportunities gives the program an

additional tool to increase the chances of success for its projects and to exploit promising opportunities that emerge.

The ATP will assist interested companies in planning for future commercialization and in developing linkages with investors. Many of the companies participating in the ATP—particularly small companies—are stronger in their R&D planning and implementation of the R&D plan than

they are in their business planning and implementation of that plan. The

early-stage, preliminary business plans developed by these companies

often lack sufficient detail to provide the clear path to commercialization

required by the ATP and may jeopardize many highly promising projects.

The ATP will contract with private firms to provide business

development support to ATP-funded companies that need such assistance.

The commercialization assistance program will be run initially on a trial basis. Several awardees have expressed interest in working with the pilot

program. Its performance will be monitored and evaluated, and, if successful, it will be continued and expanded to serve all companies that wish to participate.

The ATP is intensifying its outreach efforts. While most of the larger

technology-oriented companies in the United States are familiar with the ATP, the program is less well known or understood by thousands of

small, entrepreneurial companies that play a critical role in technology

development and might benefit from its programs. To remedy this, an

intensified outreach program has been started to increase awareness of the program. The outreach program will be coordinated closely with state and

local economic development organizations that are in a good position to identify small companies that might have an interest in the ATP.

Planning for success. President Clinton has proposed major increases in ATP funding to increase the number of awards made each year and the breadth of cutting-edge technologies covered. The expansion will allow

the program to have a truly national impact on economic growth. The

program's ultimate success will depend on an expanding relationship with

U.S. industry to ensure a steady supply of good technical ideas and

willing research partners to transform those ideas into successful new

technologies with ATP support.

Contact: Advanced Technology Program

(800) ATP-FUND [(800) 287-3863]

email: atp@micf.nist.gov

fax: (301) 926-9524

A430 Administration Building

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

October 1994

«L'.?. GOVER-NMENT PRINTING OFFICE : 1 99 5 - 3 8 6 - 6 2

' / 3 7 9 0 7

145

Technical Publications

Periodical

Journal of Research of the National Institute of Standards and Technology—Reports NIST research and development in those disciplines of the physical and engineering sciences in which the Institute is active. These include physics, chemistry, engineering, mathematics, and computer sciences. Papers cover a broad range of subjects, with major emphasis on measurement methodology and the basic technology

underlying standardization. Also included from time to time are survey articles on topics closely related to the Institute's technical and scientific programs. Issued six times a year.

Nonperiodicals

Monographs—Major contributions to the technical literature on various subjects related to the

Institute's scientific and technical activities. Handbooks—Recommended codes of engineering and industrial practice (including safety codes) devel- oped in cooperation with interested industries, professional organizations, and regulatory bodies. Special Publications—Include proceedings of conferences sponsored by NIST, NIST annual reports, and

other special publications appropriate to this grouping such as wall charts, pocket cards, and bibliographies.

National Standard Reference Data Series—Provides quantitative data on the physical and chemical

properties of materials, compiled from the world's literature and critically evaluated. Developed under a worldwide program coordinated by NIST under the authority of the National Standard Data Act (Public

Law 90-396). NOTE: The Journal of Physical and Chemical Reference Data (JPCRD) is published

bimonthly for NIST by the American Chemical Society (ACS) and the American Institute of Physics (AIP).

Subscriptions, reprints, and supplements are available from ACS, 1 155 Sixteenth St., NW, Washington, DC

2(X)56.

Building Science Series—Disseminates technical information developed at the Institute on building

materials, components, systems, and whole structures. The series presents research results, test methods, and

performance criteria related to the structural and environmental functions and the durability and safety

characteristics of building elements and systems.

Technical Notes—Studies or reports which are complete in themselves but restrictive in their treatment of

a subject. Analogous to monographs but not so comprehensive in scope or definitive in treatment of the subject area. Often serve as a vehicle for final reports of work performed at NIST under the sponsorship of

other government agencies.

Voluntary Product Standards—Developed under procedures published by the Department of Commerce

in Part 10, Title 15, of the Code of Federal Regulations. The standards establish nationally recognized

requirements for products, and provide all concerned interests with a basis for common understanding of

the characteristics of the products. NIST administers this program in support of the efforts of private-sector

standardizing organizations.

Order the following NIST publications—FIPS and NlSTIRs—from the National Technical Information

Service, Springfield, VA 22161.

Federal Information Processing Standards Publications (FIPS PUB)—Publications in this series

collectively constitute the Federal Information Processing Standards Register. The Register serves as the

official source of information in the Federal Government regarding standards issued by NIST pursuant to the Federal Property and Administrative Services Act of 1949 as amended. Public Law 89-306 (79 Stat.

1 127), and as implemented by Executive Order 1 1717 (38 FR 12315, dated May 11, 1973) and Part 6 of

Title 15 CFR (Code of Federal Regulations).

NIST Interagency Reports (NISTIR)—A special series of interim or final reports on work performed by

NIST for outside sponsors (both government and nongovernment). In general, initial distribution is handled

by the sponsor; public distribution is by the National Technical Information Service, Springfield, VA 22161,

in paper copy or microfiche form.
U.S. Department of Commerce

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

Official Business

Penalty for Private Use $300