i

Materials Science and

Engineering Laboratory

FY 2004 Programs and

Accomplishments

Ceramics

Division

Debra L. Kaiser, Chief

Ronald G. Munro, Deputy

NISTIR 7124

September 2004

National Institute of

Standards and Technology

Arden L. Bement, Jr.

Director

Technology

Administration

Phillip J. Bond

Undersecretary of

Commerce for Technology

U.S. Department

of Commerce

Donald L. Evans

Secretary
ii

Certain commercial entities, equipment, or materials may be identified in this document in order to

describe an experimental procedure or concept adequately. 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 entities, materials, or equipment are necessarily the best available for the purpose.
iii

Table of Contents

Table of Contents

Executive Summary ...................................................................................................................1

Technical Highlights...................................................................................................................3

Data and Standards Resources ...........................................................................................4

Advanced Measurement Capabilities .................................................................................7

Outreach for Advanced Technology Dissemination .........................................................10

Friction Scaling Artifact ....................................................................................................12

First-Principles Studies of Technologically Important

Dielectric Materials...........................................................................................................14

Anomalous Elastic Behavior for SrTiO3 Thin Films

Grown on Si(001) Observed by X-ray Diffraction ...........................................................16

Mapping Surface Chemistry and Molecular Orientation with

Combinatorial Near-Edge X-ray Absorption Fine Structure ............................................. 18

Advances in X-ray Powder Diffraction Quantitative

Analysis SRMs .................................................................................................................20

Advanced Manufacturing Processes ......................................................................................22

Synchrotron X-ray Measurements in Support of

Solid Oxide Fuel Cell Development ..................................................................................23

Nanometrology ........................................................................................................................24

Chemistry and Structure of Nanomaterials ......................................................................25

Thermochemistry and Metrology of Interfacial Interactions............................................ 26

Particle Metrology and Nanoassembly .............................................................................27

Mechanical Metrology for Small-Scale Structures ...........................................................28

Nanoindentation Methods and Standards .........................................................................29

Nanotribology and Surface Properties.............................................................................. 30

Materials for Electronics .........................................................................................................31

Combinatorial Tools for Materials Science .......................................................................32

Spectroscopy, Diffraction, and Imaging of Electronic Materials ......................................33

Phase Equilibria and Properties of Dielectric Ceramics...................................................34
iv

Table of Contents

Phase Relations of High Tc Superconductors................................................................... 35

Metrology and Standards for Optoelectronic Materials....................................................36

Experimental and Theoretical Influence

of Thin Film Texture on Ferroelectric Hysteresis.............................................................37

Theory and Modeling of Dielectric Materials................................................................... 38

Biomaterials .............................................................................................................................39

Controlled Size and Shape UHMWPE Particle SRM

for Bioactivity Testing ....................................................................................................... 40

Data, Reference Materials, and Measurement Methods ........................................................ 41

Ceramics Division FY04 Annual Report Publication List ....................................................... 45

Ceramics Division .................................................................................................................... 51

Research Staff.........................................................................................................................52

Organizational Charts ..............................................................................................................57
1

Executive Summary

Executive Summary

It has been a challenging yet productive year for

the Ceramics Division. Faced with an unexpected,

substantial budget cut, the division had to reassess

programs, re-evaluate priorities for personnel and

projects, and curtail and modify research plans. In the

midst of this uncertain and trying time, the excellence

and professionalism of our staff was easy to discern.

Through ingenuity, adaptation, and perseverance, hardpressed efforts often led to notable accomplishments.

In accord with the mission of NIST, the Ceramics

Division has maintained its balanced portfolio of

measurements, standards and data activities. Many of

these activities have been refocused to Nanometrology

and Materials for Electronics, two of the five program

areas in the Materials Science and Engineering

Laboratory (MSEL). The division also contributed to

Biomaterials and Advanced Manufacturing Processes,

two other MSEL program areas. Experimental,

theoretical and modeling approaches have been

employed to accomplish the advances described

for each program area.

It was a remarkable year for technology transfer,

led by our world class efforts in evaluated, scientific

databases. The Ceramics WebBook, providing data

online since 1997, remained the eleventh most visited

site at NIST. The renowned FIZ-NIST Inorganic

Crystal Structure Database issued two updates in one

year, and the longstanding ACerS-NIST Phase Equilibria

Diagrams project achieved new heights this year with

the release of a brand new, comprehensive CDROM

database product. These staples of core mission efforts

were crowned by our outreach activities that provided

critical mission support to federal agencies, CRADAs,

and consortia, including special contributions to the

U.S. Customs and Border Protection Directorate in the

Department of Homeland Security, NAVSEA in Defense,

and the U.S. Mint. These efforts and more are

described in our Highlights.

It was also a year of new beginnings. With

considerable celebration, NIST inaugurated its

new Advanced Measurement Laboratory (AML)

featuring extraordinary environmental controls.

We are extremely pleased to represent MSEL in this

new facility with two advanced capabilities: one

devoted to nanotribology, and the other to high

resolution x-ray metrology. Both of these new

facilities, as well as our unique synchrotron radiation

facilities at the National Synchrotron Light Source and

the Advanced Photon Source, are described in our

Highlight on Advanced Measurement Capabilities.

Several other particularly notable scientific

achievements are featured in our Highlights. We have

applied our novel nondestructive synchrotron-based

analytical tool for mapping bond chemistry and

molecular orientation to study in situ the creation of

self-assembled monolayer gradients. Our synchrotron

facilities were key to revealing fundamental aspects of

epitaxial growth of SrTiO3 thin films on Si, candidate

materials for next-generation Si transistor technology.

First-principles theoretical studies of dielectric materials

for electronic and wireless applications have provided

insight into the atomic interactions that dictate the

properties of these materials. With our advanced

nanofriction measurement capabilities in the AML,

we were able to identify and quantify an unintended

artifact of the measurement procedure that degraded

the measurement accuracy. We delivered the first

nominally-crystalline standard reference material for

quantitative analysis by powder diffraction methods

that is certified for amorphous content.

In all of these activities, our commitment to a

strong, productive future is clear. These projects and

many more, described in this report, are well on their

way to forming a foundation for next generation

research in nanomaterials and advanced ceramics.

Debra L. Kaiser

Chief, Ceramics Division

Figure 1: Synchrotron

materials research

contributed a cover

story for the journal

Advanced Materials.

Figure 2: Dr. Edwin R. Fuller, Jr.

was presented the American Ceramic

Society’s Robert D. Sosman Award

for his outstanding achievement in

basic ceramic science.
2
3

Technical Highlights

Technical Highlights

The Technical Highlights section of this Report

comprises eight examples of the exciting outputs of the

Ceramics Division. They are:

■ Data and Standards Resources

■ Advanced Measurement Capabilities

■ Outreach for Advanced Technology Dissemination

■ Friction Scaling Artifact

■ First-Principles Studies of Technologically

Important Dielectric Materials

■ Anomalous Elastic Behavior for SrTiO3 Thin Films

Grown on Si(001) Observed by X-ray Diffraction

■ Mapping Surface Chemistry and Molecular

Orientation with Combinatorial Near-Edge X-ray

Absorption Fine Structure

■ Advances in X-ray Powder Diffraction Quantitative

Analysis SRMs
4

Data and Standards Resources

Advances in technology and the vitality of basic

research have an unequivocal dependence on

reliable data. Indeed, the technology transfer

between research and application is facilitated

and sometimes enabled by the development and

accessibility of carefully designed and evaluated

databases. The MSEL Ceramics Division has

excelled in its leadership in data resources for

crystallography, phase equilibria diagrams, and

materials property data.

Ronald G. Munro, Terrell A. Vanderah, and

Vicky L. Karen

The issue of reliable data has been examined vigorously

in numerous studies over the last three decades.

Early assessments, such as Critical Surveys of Data

Sources (NBS SP 396-1, 1978), voiced concerns over the

availability of data, while other studies, such as Economic

Effects of Corrosion (NBS SP 511-1&2, 1978), noted the

influential role that data can perform as a component of

a sound economy. More recently, defense and security

concerns, Materials Research to Meet 21st Century

Defense Needs (NMAB-498, 2002), have continued to

stress the need for reliable data.

The Ceramics Division has made a substantial effort

to address the multiple needs for materials data, the

scientific fundamentals for data evaluation methodology,

and the technological issues involved in optimizing the

utility of the data resources. Programmatically, Figure 1,

the data and standards technology projects are well

attuned to NIST’s core mission and its strategic

focus efforts, and there is abundant evidence that our

objectives are being met with considerable success.

There are several technology transfer mechanisms

that can be used for data and standards work, including

traditional publications, internet distribution, software

products for personal computers, and standard reference

materials. The Division’s most readily visible mechanism

for data technology transfer is provided by the Ceramics

WebBook that is featured on the Division’s internet

Figure 1: Programmatic contributions of the Data and Standards

Technology Group to the NIST mission.

Figure 2: Activity seen by the Ceramics Division’s homepage,

showing the substantial attraction to property data.

Figure 3: The relative distribution of users downloading data

from the Ceramics WebBook.

website. This site provides evaluated data for the physical,

mechanical, and thermal properties of advanced

ceramics, particularly structural ceramics (NIST Standard

Reference Database Number 30) and high-temperature

superconductors (NIST Standard Reference Database

Number 62). The activity on this site, Figure 2, is a clear

indicator of both the strong interest and the persistent

need for materials data. The site attracts more than 11,000

page requests per month of which approximately 78 %

are data downloads (nearly 9000 data tables).

The distribution of users, Figure 3, shows that all

sectors of the ceramics community have a keen interest

in the evaluated data provided by NIST.

Another very important mechanism for technology

transfer is provided by the Standard Reference Data Act

(Public Law 90-3960, 1968). Under the SRD Act, NIST

can pursue technology transfer through partnerships that

broadly serve the public interest. These partnerships

Technical Highlights
5

Technical Highlights

typically involve costs in excess of our Congressionally

funded base operations and consequently result in

small charges for the data products. Two prominent

collaborations of this type between the Ceramics Division

and private sector nonprofit organizations have brought

considerable credit and recognition to NIST.

The ACerS–NIST database began with the publication

of 178 diagrams in 1933. Since then, the collection has

evolved, Figure 5, to contain nearly 20,000 diagrams.

Originally, the diagrams were distributed in printed

volumes, now amounting to thirteen regular book

volumes, four topical volumes, and three annual volumes

that serve as supplements to the regular volumes.

Today, both printed and computerized versions are

provided and are made available through ACerS.

The newest addition to the series, Figure 6, is the

special topical volume, Phase Diagrams for Electronic

Ceramics I, edited by Robert S. Roth. This collection

concentrates on the technically important oxides of

titanium, niobium, and tantalum. Additionally, a newly

updated Cumulative Index 2003 was published this year

providing comprehensive coverage of all the ACerS–NIST

content published to date. All of the new diagrams and

Figure 4: commentaries are included in the CD-ROM database. Phase Equilibria Diagrams CD-ROM Database

Version 3.0 (NIST Standard Reference Database Number 31),

released in March 2004, provides comprehensive coverage of

all diagrams and commentaries published to date in the twenty

printed volumes of the series.

Figure 5: Evolution of the compilation of phase diagrams in the

ACerS–NIST collaborative database.

The longstanding NIST collaboration with the American

Ceramic Society (ACerS) on phase diagrams provides a

clear example of the remarkable productivity that can result

from these partnerships. Now led by Dr. Terrell Vanderah,

the ACerS–NIST collaboration achieved one of its most

anticipated goals this year, Figure 4, the development of a

new computerized version of NIST Standard Reference

Database Number 31, Phase Equilibria Diagrams.

Phase equilibria diagrams are used throughout

the ceramics industry to understand and control the

complex phenomena which increasingly underlie

advanced processing and materials performance.

These diagrams provide maps of the equilibrium

chemical and structural behaviors exhibited by materials

and provide critical starting information for the rational

design of materials processing schemes, for quality

assurance efforts, and for the optimization of the

physical and chemical properties of advanced materials.

Figure 6: Recent ACerS–NIST printed data products include a

topical volume on electronic ceramics and an updated cumulative

index for all content published to date.

The mutual commitment of ACerS and NIST to

this collaboration was reaffirmed in May of this year

with the signing of a new five-year agreement.

The ability to develop partnerships in the public

interest also has enabled a successful collaboration,

led by Dr. Vicky Karen, between NIST and

Fachinformationszentrum Karlsruhe Gesellschaft

fur wissenshaftlich-techmische Information mbH

(FIZ). This collaboration, Figure 7, has resulted

in the development of NIST Standard Reference

Database Number 84, the comprehensive FIZ–NIST

Inorganic Crystal Structure Database.

Crystallographic information is critical to efforts

to visualize, explain, and predict behaviors of

chemicals and materials, as well as to establish

the identity of materials in forensic investigations.

Literally tens of thousands of structures have been

reported. Those reports, however, have varying

degrees of reliability and completeness. Consequently,

researchers and instrument manufacturers have a
Technical Highlights

critical need for evaluated data and the mathematical

tools capable of distinguishing good structures from

bad structures and compatible data from incompatible

data. Through NIST’s efforts, the use of standard

crystallographic cells, unique reduced cells, and

the powerful mathematical matrix methods for

the application of group theory have become

fundamental to the analysis and identification of

crystal structures.

Figure 8: NIST Recommended

Practice Guide, SP 960-11,

examines pivotal issues in

data evaluation.

Additional technology transfer has been achieved

through the distribution of NIST Recommended

Practice Guide, SP 960-11, Data Evaluation Theory

and Practice for Materials Properties, Figure 8.

This Guide presents a unique view of data evaluation

as a scientific discipline. A theoretical foundation is

developed from the formal underpinnings of materials

metrology, and an extensive collection of examples

is used to examine the issues of accessibility,

reproducibility, consistency, and predictability with

distinctions being made among definitive relations,

correlations, derived and semiempirical relations,

heuristic theories, and value estimates. Critical

discussions include the use of properties as parameters

in models, the interpretation of ad hoc parameters,

and the treatments of procedural properties, response

dependent properties, and system dependent data.

 Completed in FY2003 and printed in June 2003,

more than 1200 hard copies have been issued to

interested individuals, and an electronic version in

pdf format, available since January 2004, has resulted

in the distribution of another 1600 copies.

For a greater appreciation of the full range of data

and standards activities in the Ceramics Division, see

the tabulation of our products in the section, Databases

and Standards, later in this report.

For More Information on this Topic

P. Schenck, J. Harris, C. Sturrock (Ceramics

Division, NIST); A. Belsky (SRD, NIST Technology

Services); R. Roth, J. Hastie, M. Harne, A. Mighell

(Research Associates, Ceramics Division, NIST);

D. Watson (Cambridge Crystallographic DB);

M. Mecklenborg, J. You, C. Cedeno, E. Farabaugh,

K. Hill, N. Swanson, X.M. Wang (American

Ceramic Society); P. Luksch (FIZ); K. Rajan,

X. Li, A. Rajagopalan (RPI)

6

Figure 7: The FIZ–NIST Inorganic Crystal Structure Database

contains approximately 70,000 entries providing full structural,

three-dimensional crystallographic parameters.

The FIZ–NIST collaboration provides a

comprehensive compilation of three-dimensional

crystallographic data. The components of a typical

entry include data on the conventional cell, the reduced

cell, lattice type, space group, lattice parameters,

atomic coordinates, d-spacings, chemical name,

chemical formula, material class indicators, and

literature reference citations.

The collaboration is built on shared and

complementary responsibilities. NIST is responsible

for the essential scientific and informatic aspects

of the work, while FIZ provides data abstracting

and related interactions with the International Union

of Crystallography, particularly for bibliographic

information. Data evaluation is done jointly.

The latest version of the database, released this

year, contains more than 70,000 critically evaluated

data entries. The database is licensed to research

facilities, instrument manufacturers, educational

institutions, and individuals. Distributor license

agreements with instrument manufacturers are

propagated subsequently as user licenses to the

instrument buyers. As a result, these data are used

every day in defense, aerospace, electronic, petroleum,

chemical, and homeland defense related industries,

as well as in government and academic research

facilities worldwide.
7

Technical Highlights

Advanced Measurement Capabilities

conventional instruments are unsuitable for nanoscale

contacts. To resolve this issue, the newly designed

NIST apparatus, Figure 1, allows adhesion force

measurements between two surfaces at the nanoscale

level using the AFM force measurement principle.

In this device, capable of nanonewton force resolution,

a laser light is piped through a fiber-optic cable directed

at a quadrant photodetector. Because the length and

stiffness of the fiber can be modified easily, a wide

range of spring constants can be obtained, and the

measurement of adhesion forces can be achieved at

multiple force levels. Thus, the NIST apparatus has

established an exciting new opportunity to measure

the influence of surface forces on adhesion, molecular

interactions, and the compliance of surfaces, all critical

data to device manufacturing industries.

UHV STM/AFM

Enhanced by the superior vibration isolation and clean

room environment in NIST’s new Advanced Measurement

Laboratory (AML), our UHV STM/AFM system,

Figure 2, provides atomic imaging and force measurement

with an unprecedented resolution and accuracy.

The special role that NIST plays in measurement

metrology and standards often results in the

development of instruments and facilities, as well

as measurement methods, capable of probing

material characteristics in ways unavailable

elsewhere. These capabilities often provide

the context and observations necessary to the

development of a fundamental understanding

of the mechanisms of material behavior.

The Ceramics Division is privileged to have

an excellent staff and world leaders who are

responsible for the design and development of

many of these unique instruments and facilities.

Debra L. Kaiser

Nanometrology

Working with instrument makers, the Nanotribology

Group, directed by Dr. Stephen Hsu, has designed

and built a remarkable facility featuring a cluster of

equipment and instrumentation that establishes a new

state of the art for conducting measurements and

observations of nanoscale events. Included in this

facility are a nanoadhesion apparatus, a dual white-light

interferometer microscope, a multiscale friction tester,

and a multifunction apparatus combining an ultrahigh

vacuum scanning tunneling microscope with an atomic

force microscope (UHV STM/AFM). Together, these

instruments allow us to image, manipulate, and measure

adhesion, friction, and other nanomechanical properties

of materials from microscale to nanoscale dimensions.

Nanoadhesion Apparatus

Adhesion is an important issue in nanotechnology

as well as in device manufacturing industries.

Conventional adhesion measurement relies on large

interfacial areas and the accurate positioning of two

surfaces. Force measurements typically are performed

by strain gauges and transducers with force sensitivities

in the newton and millinewton ranges. These

Figure 1: Schematic operation of the NIST nanoadhesion apparatus.

Combined with our conventional AFM, equipped with

a “triboscope” attachment, we are able to image and

manipulate surface features and measure a wide range

of material characteristics and properties important in

nanodevice operation. As a result, we now are leading

fundamental metrological efforts, working with device

Figure 2: Ultrahigh vacuum STM/AFM apparatus.
8

Technical Highlights

and magnetic hard disk industries, as well as academic

institutions, to establish reliable measurement methods,

calibration artifacts, and infrastructural support for

current and future industries.

Multiscale Friction Tester

At the nanoscale level, friction between movable

components is a significant concern. To address this

issue, NIST and Hysitron, Inc. have collaborated to develop

a three-dimensional, capacitance based, force sensor.

The stiffness and position of the probe tips can be tightly

controlled to yield accurate information of the contact

area. Force measurements can be made in the range from

100 nN to 1 N in the z-direction, and 500 nN to 0.5 N in

the x,y-directions. Displacements can be measured from

0.2 nm to 5 μm in the z-direction, and 10 nm to 15 μm

in the x,y-directions. Consequently, accurate friction

measurements can be conducted at length scales ranging

from the nanometer scale to the micrometer scale. Already,

this instrument has enabled us to resolve apparent

disparities in nanofriction measurements and to understand

the nature of what had been thought to be anomalous

friction behavior. (See Friction Scaling in the Technical

Highlights section of this report.)

High Resolution X-ray Metrology

Powder and single crystal x-ray diffraction are widely

used in industry, research facilities, and academia as

one of the principal means of characterizing materials.

Both techniques yield a wealth of information on the

crystallographic and microstructural character of the

specimen. The powder diffraction method has the virtue

that it can probe a continuous sequence of crystallographic

reflections with a single scan in angular space, while

single crystal methods can be adapted to high resolution

analysis of materials such as thin films.

However, results from both powder and highresolution techniques are affected by a complex optical

aberration function that is specific to the diffraction

optics and goniometer assembly used in the experiment.

NIST Standard Reference Materials (SRMs) are the

recognized means by which these aberrations may

be characterized to achieve improved measurement

accuracy. To address these issues, Dr. James Cline of

the Data and Standards Technology Group conceived

and designed the Ceramics Division Parallel Beam

Diffractometer (CDPBD).

The CDPBD, Figure 3, was designed and built

specifically to perform traceable measurements on

powder and thin film specimens. Installed in the new

NIST Advanced Measurement Laboratory, this facility

provides the environmental and temperature controls

requisite for a new generation of NIST SRMs that will

enable unprecedented measurement accuracy in a highly

competitive, data conscious, materials research community.

Figure 3: The Ceramics Division Parallel Beam Diffractometer

in the AML.

X-ray Absorption Spectroscopy

Advances in our x-ray absorption spectroscopy

facilities have achieved an unrivaled capability enabling

our Characterization Methods Group (CMG) to address

a remarkably broad range of challenging structure and

chemistry issues at the forefront of materials science

research today. Through the application of a truly

unique combination of beamline facilities, we are able

to examine characteristics of surfaces, interfaces,

and bulk materials in a manner heretofore inaccessible.

To achieve this capability, CMG, led by Dr. Daniel

Fischer, brought together a suite of three unique highthroughput x-ray spectroscopy beamlines (designated

U7A, X24A, and X23A2). Housed in the National

Synchrotron Light Source located at Brookhaven

National Laboratory in New York, these beamlines,

taken together, can easily examine nearly all of the

naturally occurring elements in the entire periodic table.

This year, the capabilities of beamline U7A, used for

soft x-ray materials science applications, were

significantly enhanced by the addition of a 14 element,

state-of-the-art, Si (Li) fluorescence yield detector,

providing best in the world resolution. Further

enhancement of U7A, Figure 4, was achieved through

the installation of a 6-axis manipulator that enables the

exciting prospect of molecular alignment studies.
9

Technical Highlights

with large samples. In addition to topography,

radiographic and phase contrast imaging are available.

This instrument has recently been used to study

subsurface damage in 300 mm production silicon

wafers, defects in thin strained-silicon films, strain

around nanoindentations and dendrite growth in Sn/Bi

alloys. In the case of the strained-silicon films, by

using grazing incidence geometry we have been able to

directly image defects in a film ≈ 165 Å thick. These

defects have been shown to mimic the misfit dislocation

structure in the underlying relaxed Si/Ge virtual

substrate. Understanding how the substrate defects

propagate into the strained-silicon film is a critical issue

in the development of the next generation of strained

silicon electronic devices.

Ultrasmall-Angle X-ray Scattering

Our ultrasmall-angle x-ray scattering (USAXS)

instrument, constructed as part of the UNICAT facility,

is housed at the APS at ANL. The NIST effort is led by

Dr. Andrew Allen. The facility provides the most versatile

SAXS facility for materials science and engineering

research in the world. Using a single instrument

configuration, the representative microstructures within

a wide range of heterogeneous materials of technological

importance can be quantified over a scale range extending

from nanometers to micrometers. The continuously

tunable x-ray energy enables anomalous SAXS studies

to be made, allowing different microstructural

components within a composite system to be

distinguished. Microstructures also can be measured when

they possess an arbitrarily high anisotropy, such as those

encountered in some coating materials and membranes.

Recently, the high APS brilliance has been combined with

the instrument’s high-precision x-ray crystal optics to

provide a spatial resolution on the order of 10 μm for

resolving the microstructural gradients within solid

oxide fuel cell (SOFC) components.

The USAXS instrument serves microstructure

metrology needs in a wide class of technological

problems encountered in metals and alloys, structural

ceramics, thermal barrier coatings, fuel cells, biological

scaffolds, flowing nanoparticle suspensions, soot in

flames, and polymer gels. Furthermore, the intrinsic

absolute intensity calibration provided by this instrument

underpins our partnerships with others to develop

specialized SAXS instrumentation for interrogating

surface structures in electronic gate materials, or

to approach sub-micrometer spatial resolution in

SOFC research.

For More Information on this Topic

S. Hsu, J. Cline, D. Fischer, J. Woicik, D. Black,

A. Allen (Ceramics Division, NIST)

Figure 4: The soft x-ray spectroscopy station on beamline U7A.

Building on these capabilities, CMG has initiated

a long-term plan, co-funded with Sandia National

Laboratory, for establishing a variable energy XPS

(x-ray photoelectron spectroscopy) and NEXAFS/EXAFS

(near-edge/extended x-ray absorption fine structure)

scientific program utilizing beamline X24A. A new,

fully automated materials science end-station is planned,

modeled after the very successful high throughput attained

on U7A. The emphasis for this work will be on the

use of variable energy XPS for chemical depth profiling,

sub-surface chemistry, and interface chemistry.

X-ray Topography

The premier, dedicated, monochromatic topography

facility in the U.S. has been developed and implemented

at the Advanced Photon Source (APS) at Argonne

National Laboratory (ANL), Argonne, Illinois. X-ray

topography is used to study the defect microstructure

of single-crystal materials by imaging the diffracted

intensity from selected lattice planes of the sample.

The NIST effort, led by Dr. David Black, takes

advantage of the third-generation synchrotron x-ray

source to provide a spatially enlarged beam, up to

140 mm x 50 mm, with large-area real-time imaging

detectors to perform static and dynamic experiments
10

Technical Highlights

The core mission of NIST is focused on the needs

of U.S. industry and commerce. That focus leads

naturally to metrological capabilities having

substantial application and benefit not only to

industry, but also to every federal agency utilizing

advanced technology in its operations. Thus,

NIST has accrued a long history of providing

significant scientific and technical support to the

missions of federal and private sector jurisdictions

beyond the Department of Commerce.

Debra L. Kaiser

The Ceramics Division is a strong participant in

mission support activities. Current research

projects within our Division address issues of

importance to numerous agencies, including the

Departments of Defense, Energy, and Homeland

Security, the U.S. Mint, the National Science

Foundation, and the International Energy Association,

as well as consortia involving industry and academia.

Outreach for Advanced Technology Dissemination

Customs and Border

Protection (DHS)

The U.S. Customs and Border Protection

(CBP) is tasked with the responsibility of classifying

ceramic imports such as ceramic wares for laboratory,

chemical or other technical uses. This category

encompasses most technical, high-performance,

or advanced ceramic products including engine

components, bearings, and machine tools. The

classification of these articles is important because

the classification determines the import duty rates.

Consequently, CBP needs reliable assessment tools capable

of accurately determining the classification of the incoming

ceramic parts. Chapter 69 of the Harmonized Tariff

Schedule of the United States, subheading 6909.12,

describes these articles as having a hardness equivalent

to 9 or more on the Mohs scale. However, the Mohs

hardness test is a classical mineralogical scratch test that

is not sufficiently accurate for determining the hardness

of advanced ceramics. To resolve this issue, the U.S.

Customs Laboratory in San Francisco worked with

Division staff to identify a more appropriate test. Building

on the Division’s expertise in standards organizations and

independent studies, the NIST-Customs team determined

that a 15 GPa Knoop hardness test with an indentation

load of 9.8 N would provide the advanced ceramic

equivalent to the Mohs hardness specification in the Tariff

Schedule. The necessary reliability of the test was assured

by the availability of NIST Standard Reference Material,

SRM 2830, Knoop Hardness of Ceramics. This SRM

has a certified hardness of 14 GPa and is ideal for the

verification of proper machine and operator application

of the test. As a result of this collaboration, DHS

prepared an important new standard for its customs

operations, “U.S. Customs Laboratory Method 69-nn,

Procedure for Measuring the Hardness of Technical

Ceramic Products.”

Sandia National

Laboratory (DOE)

The Characterization Methods Group has initiated

a long-term plan co-funded with Sandia National

Laboratory for establishing variable kinetic energy

XPS for chemical depth profiling, and sub-surface

and interface chemistry for diverse materials science

problems. This new DOE partnership compliments

our existing, very successful collaboration with the

Brookhaven National Laboratory’s Materials Science

Department focused on the electronic structure of

high-temperature superconductors and lithium

battery oxides.

U.S. Navy

(DOD)

In work funded by the Indian Head Division of

the Naval Surface Warfare Center, Dr. G. Piermarini

(Guest Scientist, NSWC/IHDIV, Research and

Technology Department, Indian Head, Maryland),

is studying nano-structured reactive materials using

a high-temperature, high-pressure diamond anvil cell

developed at NIST. By sintering oxygen-passivated

nano-metals mixed with oxide mixtures, under suitable

conditions of pressure and temperature, it may be

possible to prepare a new class of composite materials

that have steel-like or ceramic-like properties,

but having the energetic reactivity of thermites.

If successful, this technology transfer will enable

the development of new materials tailored to

naval and other defense operations needs.
11

Technical Highlights

U.S. Mint

The Nanotribology Group is assisting the U.S. Mint to

enhance their control of coin fabrication processes and

surface finishes. With millions of coins in circulation and

millions of coin-operated devices, it is essential to the

mission of the U.S. Mint that the coins be both durable

and consistent in their fabrication. Our specialized

instrumentation enables a guest scientist from the U.S.

Mint to assess the surface chemistry and surface properties

of coins produced by various fabrication processes.

National Science

Foundation (NSF)

The MSEL Summer Undergraduate Research

Fellowships (SURF) program provides a joint opportunity

for NIST and NSF to provide undergraduates with

hands-on, rigorous research experiences in diverse areas

of materials research encompassing ceramics, metallurgy,

polymers, and measurement science. A core goal is to

open these opportunities to women, under-represented

minorities, and Americans with disabilities. The program’s

objective is to reach out at a critical point in the careers

of these under-represented students, who have often

been discouraged from careers in science, math, and

engineering. SURFing the Materials Science and

Engineering Lab has made progress toward these goals

by forging partnerships with colleges and universities that

demonstrate strong hands-on undergraduate science

curricula and a commitment to the education of women,

minorities and students with disabilities. The MSEL

SURF program was initiated in 1998 and is one of seven

spokes of the now site-wide activity, SURFing the

NIST Laboratories. The program has grown to include

approximately one hundred students each summer.

The overall demographic trends for the program are:

48 % female, 52 % male; 13 % African-American,

12 % Hispanic, and 14 % Asian.

CRADA

This year, the Characterization Methods Group

and the Dow Chemical Company celebrate the tenth

anniversary of a CRADA to establish and foster a

soft x-ray synchrotron radiation materials science

characterization facility (beamline) at the National

Synchrotron Light Source. Strategic research in

catalysis, polymers and polymer surfaces has been

enabled by the joint long-term commitment to new

detector development and high-throughput capabilities.

Consortium

As part of the Information Storage Industry

Consortium (INSIC), the Nanotribology Group

collaborates with 28 companies and 41 universities,

research institutes, and government laboratories to

provide nanotribology test methods that will enable the

development of ultra-high density storage technology.

We have participated in the Tribology Working Group

and have contributed to the development of technology

roadmaps to guide the development of next-generation

storage technology.

Versailles Project on Advanced

Materials and Standards (VAMAS)

The Nanotribology Group has taken the lead in

organizing the first international round-robin study on how

to calibrate cantilever spring constants in atomic force

microscopes (AFMs). In collaboration with research

laboratories in the UK, Germany, and Japan, this working

group on nanomaterials will determine an initial calibration

methodology and its associated statistics. Then the effort

will expand to other countries and participants around

the world leading to the development of consensus

standards and calibration artifacts.

International Energy

Agency (IEA)

DOE and NIST have signed an interagency agreement

to cooperate on pre-standardization research focused on

critical issues in the metrology of surfaces. As part of

that effort, the Nanotribology Group is organizing an

international round robin focused on information exchange

and cooperative research regarding surface texturing,

thin film coatings, and appropriate surface chemistry.

The work aims to provide the basis for international

standards that will contribute to the design of engine

components with reduced friction and increased durability

and, hence, will promote the conservation of energy.

This project is sponsored by the U.S. Department of

Energy, Office of Transportation Technologies.

For More Information on this Topic

G. Quinn, D. Fischer, S. Hsu, T. Vanderah

(Ceramics Division, NIST)
12

Technical Highlights

Nanofrictional forces are an important factor

in the design of nanodevices and assemblies of

nanoparticles. Literature data on nanofriction,

however, exhibit many discrepancies and

have a wide range of scatter. In a series of

well-controlled experiments, we have discovered

that a significant portion of this discrepancy may

actually be attributed to an unintended scratching

of the surface by the sharp tips used in making

the measurements themselves. Deviation of tip

shape from the “ideal” spherical shape is another

contributor to the disagreements found among the

literature data. This work sheds important insight

into the nature of nanoscale friction measurement.

Z. Charles Ying and Stephen M. Hsu

Accurate measurement of nanofriction is emerging

 as one of the critical issues in nanotechnology.

Manipulation of molecules, clusters, and nanoparticles

across surfaces to form a functional entity relies on the

ability to overcome the resistance of the particles to

motion across the surface. Further, reliable operation

of micro- and nano-devices often depends on an

accurate estimate of lateral loading. Literature data

on nanofriction, however, have shown wide ranges

of values depending on the length scale of the device.

Silicon friction, e.g., shows an order of magnitude

variation from 0.03 to 0.25. Such results have led to

speculations that there might be an intrinsic scaling

effect such that different friction levels would occur

across the nano-, micro-, and macro-scales. If proven

true, well established friction laws would be invalidated

for nanomaterials.

Given the broad technological significance of this

issue, we have undertaken a detailed investigation of

the nature of this discrepancy. Friction measurements

between non-adhering surfaces were carried out in both

elastic and plastic deformation regions. Diamond tips

of various sizes were used to measure nanofriction

forces on well-characterized substrates such as single

crystal silicon, silicon dioxide, and calcium fluoride.

Experiments were performed using a specially designed

multiscale friction tester developed jointly by NIST and

Hysitron Incorporated based on a capacitance probe

force transducer. In each experiment, the environment

was carefully controlled, and the tip penetration into the

substrate during sliding was continuously measured.

The size and shape of each tip were characterized

using a newly developed “replica technique.” Tips

were imprinted into a soft material, and the imprints

were scanned by AFM and digitally inverted to

Friction Scaling Artifact

Figure 1: 3D profiles, obtained using the replica technique, of the

tips used in the friction measurements.

“reconstruct” the tip in three-dimensional details.

Figure 1 shows images of two of the diamond tips

used in the experiments. The tip shown in Figure 1(a)

is spherical in shape with a 1.2 μm tip radius while

Figure 1(b) shows an ellipsoidal shape with nominal

radius of 4 μm. The detailed dimensional data are

crucial in determining the apparent contact areas and

isolating the influence of surface forces.

Figure 2: Coefficient of friction between Si (100) surface and a

diamond tip with radius R = 1.2 μm, as a function of mechanical

loading force.

Figure 2 shows the coefficient of friction (COF)

between a Si (100) surface and a diamond tip with tip

radius R = 1.2 μm.
13

Technical Highlights

path. Numerical integration of actual tip size and shape

over the sliding path is required. For the hypothesis of

“elastic plowing,” the calculation shows that the friction

force in this regime should be proportional to the projected

cross-sectional area in the direction of sliding. Figure 5

confirms this hypothesis for all three tips.

Figure 3: Image of the silicon surface after friction

measurements, showing scratches at 2.5 mN and higher load.

Figure 4: Coefficient of friction between Si (100) surface and

three diamond tips used in the experiments, as a function of mean

contact pressure.

Figure 5: Friction force as a function of projected cross-section

area in the direction of tip sliding.

Two distinct regions can be seen. Initially, the COF

is constant up to a load of 2.0 mN. For loads above

2.5 mN, the COF increases with load. This friction

transition is contrary to Amoton’s law. Subsequent

investigation revealed that this change in COF is caused

by unintended plowing of the tip into the substrate.

Atomic force microscopy, using a sharp tip on the

surface, suggests that the COF increase coincides with

the first appearance of plastic grooving. In the case

of silicon, a groove 5 Å deep and 2000 Å wide was

detected on the surface at a load of 2.5 mN (Figure 3).

This observation was repeated for different tips and

different substrates. At higher loads, deeper and wider

grooves were observed. These results suggested that

unintended scratching of the surfaces by the sharp tips

used in the friction measurements contributed to the

discrepancies among friction data in the literature.

The initiation of plastic grooving can be quantified in

terms of contact pressure. By determining the apparent

contact area using the digitally inverted tip method, the

transition contact pressures could be calculated for all

of the observed cases. All the results corresponded to

12 GPa which is approximately the hardness of silicon.

Elastic Plowing

Figure 4 shows the friction data for three tips in the

elastic region (no plastic grooving). The data for the two

spherical tips with radii R = 0.5 μm and 1.2 μm exhibit a

common value for the COF. However, a higher friction

value was observed for the 4 μm radius tip.

To explain this discrepancy, we tested the various

contact mechanics models which require the accurate

determination of the real contact areas. Considering a tip

plowing through an elastic substrate, the real area of

contact is the projected cross-section area of the tip in

the direction of sliding. This can be determined from the

tip geometry and “penetration depths” across the sliding

This work shows clearly that nanoscale friction, in

practice, is a complex result of both elastic and inelastic

strains and deformations, and accurate nanofriction

measurement will require careful accounting of all the

forces contributing to the phenomenon. The methodology

established in this work provides a substantial step towards

the data and understanding needed by industry.

For More Information on this Topic

Z.C. Ying, S.M. Hsu (Ceramics Division, NIST)
14

Technical Highlights

Dielectric materials are needed for diverse

applications ranging from gate dielectrics to

microwave resonator materials to transducer

and actuator materials. The specific materials

requirements depend on the application.

First-principles theoretical studies on dielectric

materials are revealing the roles of chemical

order and internal electric fields in controlling

the properties of these materials.

Eric Cockayne and Benjamin P. Burton

Current semiconductor technology uses amorphous

SiO2 as a gate dielectric material. As size has

decreased, however, the leakage current of SiO2 has

become a limiting factor. Finding an alternative gate

dielectric material is a “grand challenge” in the industry.

Alternative materials must have higher dielectric

constants than SiO2 to yield equivalent performance

with reduced leakage current. Hf-containing oxides

are a promising set of materials.

First-Principles Studies of Technologically Important

Dielectric Materials

Figure 1: HfO2 structure (Hf green, O blue).

Figure 2: First-principles-derived model for the dielectric

constant of (CaAl1/2Nb1/2O3)

1–x-(CaTiO3)x shows nonlinear

composition dependence, in agreement with experiment.

and temperature stability. In general, temperature stability

is achieved by forming solid solutions between end

member compounds with opposite signs of temperature

coefficient, for example, between CaAl1/2Nb1/2O3 (CAN)

and CaTiO3 (CT). We have used the FP-based model to

calculate the dielectric constant of arbitrary solid solutions

of -CaAl1/2Nb1/2O3-CaTiO3. The model is based on

cluster expansions of the interatomic forces and ionic

charges, which control the dielectric properties.

The model reproduces the experimentally measured

composition dependence of the dielectric constant of

CT-CAN very well (Figure 2).

Figure 3: Combined first-principles/empirical model for the

Raman spectrum of CaZrO3 shows semiquantitative agreement

with experiment.

Dielectric constants are related to the effective charges

of ions and to phonon-frequencies. First-principles (FP)

calculations show that the effective charge of Hf in HfO2

(Figure 1) is higher than the effective charge of Si in

SiO2, providing an explanation why Hf-containing oxides

should have, in general, higher dielectric constants than

silicates. By comparing the effective charge of Hf in the

experimental structure with that in hypothetical structures,

it was found that the effective charge of Hf depends on

its environment. Because amorphous gate dielectrics

are desirable, knowledge of how crystal environments

dictate effective ion-charges provides a basis for designing

gate dielectric materials.

Microwave resonator and filter materials typically

require a moderate dielectric constant, low dielectric loss,
15

Technical Highlights

Dielectric properties, and, therefore, the Raman

spectra, of solid solutions depend on chemical ordering

of ions as well as composition. To understand the

connection between local structure, composition,

dielectric properties, and spectroscopy, we are working

on computing Raman spectra directly from FP. The

idea is to create a spectroscopic/computational tool for

measuring short- and long-range chemical order via

Raman spectroscopy. Experiments have shown that

Raman spectra are sensitive to short- and long-range

order, but little is known quantitatively about the

relationship between Raman spectra and chemical order.

We have created a model, based on FP results, for the

Raman spectra of solids, and are applying it to study

the CAN-CT and CaZrO3-CaTiO3 (CZ-CT) solid

solution systems. Figure 3 shows that the Raman

spectrum of CZ is reproduced reasonably well

with only a few parameters. Both long-range

electrostatics and short-range covalent bonding

contribute to the Raman spectra, but not equally to

all peaks. This provides a natural explanation for

the experimental observation that different Raman

peaks can have different sensitivities to the amount

of long-range order. Evidence is also found that

small Ti or Zr concentrations create local vibrations

that produce significant, but broad, peaks in the

Raman spectrum.

Relaxor behavior is desirable, because it implies

high-dielectric constants and piezoelectric coefficients

over a broad temperature range, but it poses a

theoretical challenge because these properties are

sensitive to structural/chemical heterogeneities at many

length-scales. For example, PbSc1/2Nb1/2O3 (PSN)

exhibits normal ferroelectric behavior as a function of

temperature (e.g., a sharp dielectric peak) when Sc3+

and Nb5+ are ordered. However, when there is only

short-range order, such as nanoscale chemically

ordered domains in a disordered matrix, PSN exhibits

relaxor ferroelectric behavior (e.g., a broadened,

frequency-dependent dielectric peak). Similar changes

in dielectric properties are caused by the introduction

of Pb- and O-vacancies. We have constructed a

computational model for PSN, which allows these

structure–property issues to be explored in detail.

FP calculations show that Pb atoms move off their

ideal crystallographic positions, and that the dielectric

and piezoelectric response in PSN is dominated by the

dynamics of Pb-displacements. At low temperature,

Pb–Pb interactions favor coherent alignments

of Pb-displacements, but local electric fields, caused

by the charge difference between Sc3+ and Nb5+,

randomly bias individual Pb-displacements. Electric

fields generated by Pb- and O-vacancies are also

included in this model. Molecular dynamics simulations

on a 320,000 atom supercell yield a sharp dielectric

peak for ordered PSN, and successive broadening as

chemically ordered nanodomains and/or Pb vacancies

are added, in agreement with experiment.

The wide band-gap semiconductor system

AlN-GaN is used to make light emitting diodes, and

the wavelength of emitted light is adjusted by alloying.

First-principles phase diagram calculations for this

system predict the expected miscibility gap when

the excess vibrational entropy is excluded; but when

it is included, an ordered phase based on AlGaN2

stoichiometry is predicted. To our knowledge, this

is the first prediction of vibrational-entropy induced

atomic ordering, and it suggests a novel way to affect

band gaps: via ordering and alloying rather than

alloying alone.

For More Information on this Topic

E. Cockayne, B.P. Burton (Ceramics Division, NIST)

E. Cockayne, “First-principles Calculations of the

Dielectric Properties of Perovskite-Type Materials,”

J. Eur. Ceram. Soc. 23, 2375–2379 (2003).

U.V. Waghmare, E. Cockayne, and B.P. Burton,

“Ferroelectric Phase Transitions in Nano-scale

Chemically Ordered PbSc0.5Nb0.5O3 using a

First-principles Model Hamiltonian,” Ferroelectrics

291, 187–196 (2003).

Figure 4: Simulated dielectric constant of PbSc1/2Nb1/2O3

as a function of temperature and type of Sc-Nb ordering.

The broadening of the dielectric peak that occurs in the case of

ordered nanodomains is one characteristic of relaxor behavior.

Transducers used for sonar and medical imaging

applications typically require extremely high dielectric

and piezoelectric coefficients. Very large piezoelectric

coefficients are observed in Pb[Mg;Zn]1/3Nb2/3O3–

PbTiO3 solid solutions, based on the relaxor

ferroelectrics PbMg1/3Nb2/3O3 and PbZn1/3Nb2/3O3.
16

Technical Highlights

A major driving force of the semiconductor

industry is the integration of transition-metal

oxides with Si transistor technology. Much of

this effort has focused on the development of

SrTiO3 thin-film growth on Si(001). These films

have served successfully as the gate-oxide layer

for metal-oxide field-effect transistors and as

the buffer layer for III–V on Si semiconductor

technology. In addition, ferroelectric thin

films show promise for quantum computing

applications. However, these perovskite films

exhibit unusual features, and it is imperative

for future advances that the fundamental aspects

of the thin-film epitaxy be understood from

both an experimental and a theoretical view.

To address this issue, we are studying SrTiO3

as a model material representative of the

larger class of candidate oxides with the

perovskite structure.

Joseph C. Woicik

We have performed high resolution x-ray diffraction

measurements at the UNICAT beamline facility

at the Advanced Photon Source on a series of SrTiO3

thin films grown on Si(001) by Motorola. Figure 1

Anomalous Elastic Behavior for SrTiO3 Thin Films

Grown on Si(001) Observed by X-ray Diffraction

shows the results of our glancing-incidence x-ray

diffraction experiment performed around the

SrTiO3(220) diffraction for the in-plane and the

SrTiO3(002) diffraction for the out-of-plane SrTiO3

lattice parameters.

Because the crystal structure of SrTiO3 is simple

cubic (Figure 2), whereas the crystal structure of

Si is face-centered cubic, SrTiO3 films grow on

the Si(001) surface with their unit cell rotated 45°

around the Si(001) surface-normal direction.

Consequently, this choice of SrTiO3 reflections

determines accurately the SrTiO3 unit cell dimensions

relative to the underlying Si lattice and hence the

thin film epitaxy.

Our diffraction measurements find that all of the

thin films studied are under in-plane tensile strain.

This finding is counter to what is expected from the

bulk lattice constants of SrTiO3 and Si that predict

in-plane compressive strain for coherent SrTiO3

thin-film growth on Si(001). The observed

expansion of the in-plane SrTiO3 lattice constant

must therefore result from the much larger thermal

expansion coefficient of SrTiO3, compared to Si,

coupled with incoherent growth at the elevated

growth temperature.

Figure 1: In-plane and out-of-plane SrTiO3 lattice constants for

40 Å, 60 Å, 80 Å, and 200 Å SrTiO3 thin films grown on Si(001).

The horizontal lines show the bulk cubic lattice constants of

SrTiO3 and bulk Si.

Figure 2: Crystal structure of SrTiO3.
17

Technical Highlights

Even more surprising is the result that the SrTiO3

out-of-plane lattice constant increases with decreasing

film thickness, indicating a large negative Poisson’s

ratio for the thinnest films; i.e., the out-of-plane

lattice constant of the SrTiO3 is expanded more

than its in-plane lattice constant.

 To understand both the nature and driving

force of this anomaly, we performed polarization

dependent x-ray absorption fine-structure (XAFS)

measurements on the same samples. Together,

XAFS and x-ray diffraction determine uniquely the

degree of epitaxy and the local atomic distortions

that result.

Our XAFS measurements find significant p-d

hybridization for the thinner films. This hybridization

is allowed only for a non-centrosymmetric distortion

of the SrTiO3 unit cell. Polarization-dependent

measurements of the Ti-O bond lengths find one

Ti-O distance parallel to the SrTiO3 interface

and two Ti-O distances perpendicular to it.

The Ti-O radial splitting is ≈ 0.22 Å. The elastic

anomaly observed by diffraction is, therefore,

likely driven by the interfacial polarization of the

SrTiO3 layers.

To test this hypothesis, first-principles

density-functional calculations were performed

on periodic SrTiO3 supercells containing √2 x √2 x N

unit cells. The calculations were performed at the

Naval Research Laboratory Center for Computational

Materials Science. Figure 3 shows the results of

the calculations as a function of N, the number of

SrTiO3 layers. The in-plane lattice constant of the

supercells was constrained to equal the average

in-plane lattice constant of the SrTiO3 films as

determined by x-ray diffraction. To mimic the

polarization of the interface as determined by XAFS,

a single Ti-O layer was polarized in the normal

direction by constraining its z-coordinates to lie

0.22 Å apart. All other coordinates were

fully relaxed.

Remarkably, the out-of-plane lattice constant of

the supercells is found to expand in agreement with

Figure 3: Calculated out-of-plane SrTiO3 lattice constant as a

function of the number of SrTiO3 layers.

the measurement of the out-of-plane lattice constant

of the films. These results suggest that this behavior

may be common for hetero-epitaxial growth of

materials that possess an ionic polarizability; it arises

simply from the inequivalent perpendicular heights

of the anions and cations at the film/substrate

interface which drives the polarization of the film.

Additional calculations are being performed to

understand the role of Si diffusion and O vacancies,

and experiments are planned to study both the epitaxy

and interfacial structure of films grown under

different growth conditions.

For More Information on this Topic

F.S. Aguirre–Tostado, A. Herrera–Gomez

(CINVESTAV); R. Droopad, Z. Yu (Motorola);

D.G. Schlom (Pennsylvania State University);

P. Zschack, E. Karapetrova (UNICAT);

C.S. Hellberg (NRL)
18

Technical Highlights

The demands of preparing, processing and

characterizing novel materials and structures and

the need for full exploration of the typically broad

parameter space has led to the development of

combinatorial near-edge X-ray absorption fine

structure (NEXAFS). This is a new nondestructive

synchrotron-based analytical tool for mapping

the bond chemistry and molecular orientation of

self-assembled monolayer gradients and reaction

intermediates in catalyst arrays. Spatially resolved

NEXAFS maps reveal bond concentration,

rehybridization and orientation of the surfacebound molecules with sub-millimeter planar spatial

resolution and sub-monolayer molecular sensitivity.

Daniel A. Fischer and Jan Genzer (NCSU)

Most experimental combinatorial methods

concentrate on probing only a single material

property, such as chemical information, topography,

etc. For some applications, it is desirable that multiple

properties be probed simultaneously in a single

experiment. Particularly, information on the chemistry

and molecular organization of chemical groups on

surfaces is needed to shed light on the behavior of

amphiphilic surface modifiers or to characterize new

classes of catalysts. The chemistry (including bond

concentration and rehybridization) and molecular

orientation on chemically heterogeneous surfaces

and catalyst arrays can be obtained by simultaneously

utilizing synchrotron based near-edge X-ray absorption

fine structure (NEXAFS) spectroscopy and rastering

the soft X-ray beam on the probed specimen (Figure 1).

This rastering produces serial NEXAFS images in space

and X-ray energy with sub-millimeter planar spatial

resolution and sub-monolayer molecular sensitivity.

We call this technique combinatorial NEXAFS.

Mapping Surface Chemistry and Molecular Orientation with

Combinatorial Near-Edge X-ray Absorption Fine Structure

Figure 1: The principle of “combinatorial” NEXAFS.

Figure 2: Schematic illustrating the process of creating molecular

gradients on elastomeric substrates. The poly(dimethyl siloxane)

(PDMS) network sheet is cut into “dog bone”-like shapes, stretched

uniaxially and exposed briefly to ultraviolet/ozone treatment that

produces surface-bound hydroxyl groups (PDMS-UVO). After

exposing the substrate to a vapor of t-F8H2, a uniform t-F8H2

monolayer is generated on the surface PDMS-UVO. Upon

releasing the strain from the substrate, a two-dimensional

concentration gradient in t-F8H2 is generated.

Combinatorial NEXAFS spectroscopy was

used to map out the two-dimensional (2-D)

in-plane concentration variation of t-F8H2

(Perfluorodecyltrichloro-silane), gradient-forming

molecules. Such a 2-D gradient variant was produced

by utilizing “mechanically assembled monolayers”

(MAMs) technology on substrates in combination

with in-plane asymmetric stretching of elastomeric

substrates uniformly coated with organosilane

precursors. Figure 2 summarizes the technological

steps leading to the formation of 2-D gradients.

We first measured a fluorine K edge NEXAFS

spectrum from a sample covered with a dense

homogeneous monolayer of t-F8H2 on the stretched

“dog bone” elastomeric substrate. The spectrum

reveals the existence of two intense signals at 692.0 eV

and 694.5 eV, corresponding to the 1s to σ* C-F

excitations, respectively, superimposed on top of a

broad fluorine excitation edge. The stretched “dog

bone” substrates were then allowed to relax compacting

the t-F8H2 homogenous monolayer in an asymmetric

manner. We then performed the combinatorial

NEXAFS experiments two-dimensionally by scanning

the sample in the vertical and horizontal directions with

1 mm increments, at each step measuring the C-F σ*
19

Technical Highlights

peak (chemical bond) intensity, as shown in Figure 3.

The darker areas in the plot denote regions on the

substrate with higher concentration of the C-F bond.

The data in Figure 3 reveal that the concentration of

C-F bonds on the sample varies spatially. Specifically,

in sample S1, the concentration of C-F bonds is highest

in the middle of the sample and decays towards the

edges of the specimen. In sample S2, the edges of

the sample contain a larger number of the t-F8H2

molecules, relative to the center. The ratio between

the highest and lowest NEXAFS intensity signal in

samples S1 and S2 was 1.35 and 1.26, respectively.

The regions of the substrates with the highest C-F bond

signal correspond to the locus of the maximum strain

imposed after stretching the “dog bone” substrates in

two orthogonal ways. Importantly, there is a gradual

in-plane variation of the t-F8H2 concentration ranging

between the high and low t-F8H2 density regions on

the substrate. In order to correlate the results of the

combinatorial NEXAFS C-F bond mapping experiments,

the distribution of stresses in the S1 and S2 samples

were calculated using a commercial software package.

The results of the calculated stress distributions in

the samples are shown as contour plots in Figure 3;

strain increase is characterized by darker colors.

Comparing visually the results in Figure 3, we

conclude that the calculated results agree well

qualitatively with the estimated strain distributions

based on the sample contours and the concentration

of the t-F8H2 molecules measured by combinatorial

NEXAFS, respectively.

Figure 3: Top panel — C-F NEXAFS peak intensity maps,

samples S1 (left) and S2 (right) after strain release.

Darker regions indicate higher intensity of the C-F signal.

Bottom panel — Calculated strain maps in the stretched PDMS

sheets corresponding to samples S1 (left) and S2 (right). The

darker regions in the plots denote regions with larger strains.

We envision fluorescence yield combinatorial

NEXAFS as a useful method for catalyst discovery,

ultimately during an actual catalytic reaction.

Catalyst discovery may be accomplished by searching

for a desired chemical (i.e., spectral) change in

a combinatorial NEXAFS bond rehybridization

map of reaction intermediates formed on catalyst

library arrays. In a prototypical catalyst discovery

experiment, combinatorial NEAXFS was used to map

the rehybridization of propylene reaction intermediates

on zeolite catalyst arrays for measuring solid state

acidity and activity. Figure 4 shows a series of carbon

k edge NEXAFS spectra for this catalyst array and

the edge jump normalized intensity of the rehybridized

1 s to π* C=C peak. From the data, it appears that

the chemical activity of the zeolite decreases rapidly

as the silica to alumina ratio increases. Thus the

combinatorial NEXAFS method allows the chemist

to select the most acidic zeolite for this propylene

reaction accelerating catalyst discovery.

For More Information on this Topic

D. Fischer, S. Sambasivan (Ceramics Division,

NIST); J. Genzer, K. Efimenko, R. Bhat (NCSU)

Cover story, Adv.

Materials, 15, 1545–1547

(2003).

Figure 4: Inset shows a series of carbon K edge NEXAFS spectra

for zeolite catalyst array (silica to alumina ratio of 31, 50, 280).

The carbon K edge height (dashed) and the rehybridized 1 s to π*

peak intensity normalized by the carbon edge height (solid) versus

the silica to alumina ratio of the zeolites.
20

Technical Highlights

Powder diffraction methods offer the direct means

by which the components of crystalline mixtures

may be quantified. While this method has been in

use for decades, recent advances, particularly in

the area of data analysis, have increased the

accuracy of the technique to the point that the

issue of the amorphous component has come to

the fore. Requisite to addressing this measurement

issue for the materials science community is the

certification of NIST powder diffraction SRMs

with regards to crystalline phase purity.

Jim Cline

Quantitative analysis by powder diffraction methods

is based on the fact that the diffraction intensity

from a given phase is proportional to its concentration

in the specimen. Data analysis strategies to quantify

the concentrations may be considered in terms of two

categories: the first consists of the “conventional,”

single peak methods that are based on the Reference

Intensity Ratio, RIR, nomenclature; and the second

is Quantitative Rietveld Analysis, QRA, wherein a

reference diffraction pattern is computed using model

functions for crystallographic, microstructural, and

instrumental contributions. Parameters within these

functions are then varied within a least-squares

refinement to obtain an optimal fit between the

computed and observed patterns. This method, first

proposed for quantitative analyses in the mid-1980’s,

has raised the accuracy of the results to the extent that

discussions of the amorphous content issue have

become commonplace within the community.

Any finely divided solid possesses a large specific

surface area that constitutes a boundary to the crystal

structure. Due to relaxation and surface reactions, this

region includes an amorphous layer of material that

does not diffract like the bulk crystal. Its dimension,

or mass fraction, will vary with the crystallography,

chemistry, production history, and level of specific

surface of the material. The amorphous fraction is,

therefore, an innate characteristic of a powder that may

well have a fundamental impact on its properties.

The diffraction experiment “sees” only the

crystalline component of the specimen. If the

experimentalist can account for all the crystalline

phases in the unknown, then standardless analyses of

the crystalline components of the mixture are possible.

The results, however, will be reflective only of the

crystalline components in the specimen and may not

assess the mass fraction of the powder components

of the mixture accurately due to the presence of

amorphous layers. However, analysis of the nondiffracting amorphous component is possible when

an internal standard is admixed with the specimen.

The amorphous component is then determined from

the discrepancy between the mass fraction obtained

from the diffraction experiment, and that of the

weighing operation. Requisite to such analyses are:

1) accurate measurement methods and 2) standards

that have been characterized with respect to their

amorphous phase fraction.

The measurement accuracy and amorphous

content issues are inextricably linked; one cannot

assess the accuracy of a quantitative measurement

with a comparison to a weighing operation without

some a priori knowledge of the amorphous component.

This not being plausible, we construct an experimental

design utilizing two phase mixtures wherein the

amorphous component of one phase, the reference

phase, is varied in a systematic manner. With

this approach, results are based on the accurate

determination of the Bragg scattering intensity from

the two phases, as opposed to the weak diffuse

scattering for the amorphous component itself. The

design must also embody the means to verify results

through both internal and external consistency checks.

The primary NIST SRM for quantitative analysis

via powder diffraction is SRM 676, an alumina powder

originally certified in 1992. SRM 676 was used as the

base material in the present work, while the reference

phase was the intrinsic, float zone silicon used for the

feedstock of SRM 640c. SRM 640c has the highest purity

and the lowest defect concentration of any crystalline

silicon available. Implicit in our interpretation of the data

is that the silicon has no crystallographic or microstructural

defects, that all amorphous material associated with it is

Table 1: Microstructure data from the five lots of

silicon and SRM 640c (dL = particle size by laser

light scattering, σ = BET specific surface area,

and Dx = TOF extinction diameter)

Lot 1 640c 2 3 4 5

dL, μm 3.47 3.51 10.03 15.07 19.47 24.14

σ, m2/g 1.728 1.402 0.703 0.424 0.335 0.270

Dx, μm — 3.7 5.6 6.5 7.6 8.1

Advances in X-ray Powder Diffraction Quantitative

Analysis SRMs
21

Technical Highlights

confined to the crystallite surface, and that the amorphous

layer thickness is invariant with respect to crystallite size.

Five lots of silicon were prepared and characterized;

microstructural data for these and SRM 640c are shown

in Table 1. A series of 50–50 mass fraction mixtures of

silicon and SRM 676 were prepared. The mass fraction

of silicon, determined from the diffraction experiments

was then plotted relative to the surface area, or amorphous

content, of the silicon. These data were then extrapolated

to yield a value for mass fraction of silicon that would

possess “zero” amorphous content, thereby yielding the

mass fraction of alumina that would be determined using

an imaginary silicon sample of 100 % crystalline content.

Thus, the discrepancy between the mass fraction measured

via diffraction and that determined from the initial weighing

indicated the true amorphous content of the alumina of

SRM 676.

The powder diffraction methods used for this study

were chosen for their ability to overcome the factors

that typically confound the accurate measurement of

Bragg scattering intensity. Crucial to the success of the

experiment was the need to address the effects of extinction

that would, in particular, affect the scattering intensity

from the coarse grained silicon. Extinction can only be

considered with dynamical diffraction theory as a result

of destructive interference in the standing waves within

the crystal during the diffraction condition. Generally,

R = Q f(A), where R is the diffraction intensity, Q is the

diffraction intensity per unit volume, and f(A) is a function

of diffraction geometry:

A = (e2 λ F t)/(m c2V)

where λ is the wavelength, F is the Structure Factor,

t is the crystallite size, and V is the volume of the unit cell.

One can see that the parameter which may be varied to

address extinction effects is the radiation wavelength.

Two data collection methods were selected,

largely in the context of the radiation wavelengths

that they employed. The neutron time-of-flight, TOF,

powder diffraction method, using radiation that is

multi-wavelength in nature, permits a robust analysis

of the extinction domain size, and its correction, using

the Sabine model within the Rietveld analysis of the raw

data. The second approach is to reduce λ to the point

where the extinction effect is inoperative. The 56 keV

energy of the x-ray radiation used for the second set

of powder diffraction experiments met this condition.

Convergence of these two data collection and analysis

strategies ensures credibility of the final result.

The Rietveld analyses of the data were performed

in a single refinement of the suite of data from each method.

This approach permitted parameters to be constrained in

a physically valid manner consistent with crystallography

and microstructure of the specimens. The TOF data

included extinction domain size parameters that are shown

in Table 1. The phase fractions of the silicon are plotted

relative to its surface area in Figures 1 and 2. One can

The analysis of the y intercept leads to a certified

value of 8.25% ± 1.52% for the amorphous content of

SRM 676. Because the suite of NIST powder diffraction

quantitative analysis SRMs were certified relative to

SRM 676, they now can be certified for phase purity.

The amorphous value determined for SRM 676 is

a surprisingly large value, thought, for this alumina powder,

to be due to transition alumina impurities that were not

fully decomposed upon thermal processing during

manufacture. This value indicates that many powders

that offer “clean” diffraction patterns, with no discernable

diffuse scattering in the background, may actually be

≈ 95 % pure. Use of the suite of NIST SRMs resolves

this issue and provides the diffraction community with

the means of determining the amorphous layer thickness

of powders, a previously inaccessible characteristic.

For More Information on this Topic

NIST Standard Reference Materials,

http://ts.nist.gov/ts/htdocs/230/232/232.htm.

Figure 1: QRA of Si/SRM 676 data from TOF powder diffraction.

Figure 2: QRA of Si/SRM 676 data from high energy x-ray

powder diffraction.

observe in these data: 1) the expected decrease in the

phase fraction of silicon as its surface area increases

and 2) very good correlation between the two methods.

Results of a linear least-squares fit to the data shown in

the figures indicate that the y intercept values for these

two independent measurements are within acceptable

error bounds.
22

Program Overview

The competitiveness of U.S. manufacturers

depends on their ability to create new product concepts

and to speed the translation from concept to market

while decreasing product cost. This is equally true

for well-established “commodity” industries, such

as automotive and aerospace, and rapidly growing

or emerging industries, such as biotechnology and

nanotechnology. For existing products, manufacturing

is a critical step in reducing product cycle time. Rapid,

low-cost development of manufacturing processes is

needed to incorporate new materials into complex

product shapes with higher performance at equivalent

or lower cost as the competing, established materials

and methods. For innovative product concepts, new

materials with increasing functionality are needed to

translate these concepts to reality.

To realize such improvements in materials and

manufacturing, MSEL is developing robust measurement

methods, models, standards, and materials and process

data needed for design, monitoring, and control of

manufacturing processes. A growing challenge is being

able to design, monitor, and control such materials and

manufacturing processes at size scales from nanometers

to meters. The Advanced Manufacturing Processes

Program focuses on the following high-impact areas:

■ Combinatorial, high-throughput methods for materials

ranging from thin films and nanocomposites to

micro- and macroscale material structures;

■ Industry-targeted R&D centered on unique

measurement facilities in forming of lightweight

metals for automotive applications, polymer

processing, and high-speed machining;

■ Innovative testbeds for emerging materials,

including carbon nanotubes and fuel cells;

■ National traceable standards having a major impact

on trade, such as hardness standards for metals

and process standards for polymers; and

■ Innovative, physics-based process modeling tools.

Our research is often conducted in close

collaboration with industrial consortia and standards

organizations. These collaborations not only ensure

the relevance of our research, but also promote rapid

transfer of our research to industry for implementation.

Three projects focused on Advanced Manufacturing

Processes are highlighted below.

NIST Combinatorial Methods Center (NCMC)

The NCMC develops novel high-throughput

measurement techniques and combinatorial experimental

strategies specifically geared towards materials research.

Advanced Manufacturing Processes

These tools enable rapid acquisition and analysis of

physical and chemical data, thereby accelerating the

pace of materials discovery and knowledge generation.

By providing measurement infrastructure, standards, and

protocols, and expanding existing capabilities relevant

to combinatorial approaches, the NCMC lowers barriers

to the widespread industrial implementation of this new

R&D paradigm. MSEL uses a two-pronged strategy for

accelerating the development and implementation of these

approaches: an active intramural R&D program that

demonstrates the ability of combinatorial methods to

produce cutting-edge scientific research and an ambitious

outreach activity; key to this effort is the validation of

these approaches with respect to traditional “one at a time”

experimental strategies.

Forming of Lightweight Metals

Automobile manufacturing is a materials intensive

industry that involves about 10 % of the U.S. workforce.

In spite of the use of the most advanced, cost-effective

technologies, this globally competitive industry has major

productivity issues related to measurement science and

data. Chief among these is the difficulty of designing

stamping dies for sheet metal forming. An ATP-sponsored

workshop (“The Road Ahead,” June 20–22, 2000) identified

production of working die sets as the main obstacle to

reducing the time between accepting a new design and

actual production of parts. This is also the largest single

cost (besides labor) in car production. To benefit from

weight savings enabled by new high-strength steels

and aluminum alloys, a whole new level of formability

measurement methods, models, and data is needed,

together with a better understanding of the physics

behind metal deformation. MSEL is working with

U.S. automakers and their suppliers to fill this need.

Polymer Processing

Polymers have become ubiquitous in the modern

economy because of their processability, high functionality,

and low cost. However, these materials can exhibit

complex and sometimes catastrophic responses to the

forces imposed during manufacturing, thereby limiting

processing rates and the ability to predict ultimate

properties. The focus of our polymer research is on

microfluidics and microscale processing, modeling of

processing instabilities, and on-line process monitoring

of polymers. Our unique extrusion visualization facility

combines in-line microscopy and light scattering for the

study of polymer blends, extrusion instabilities, and the

action of additives. These measurements are carried out

in close collaboration with interested industrial partners.

Contact: Carol A. Handwerker (Metallurgy Division),

Andrew J. Allen (Ceramics Division)
23

Advanced Manufacturing Processes

Control of solid oxide fuel cell microstructure and

electrochemistry close to the electrode–electrolyteinterconnect interfaces is important for optimizing

fuel cell performance and lifetime. Quantifying

the associated gradients and degradation effects

during service life is needed to exploit fully the

underlying phenomena governing the material

properties. A combination of third-generation

x-ray synchrotron measurements at the Advanced

Photon Source seeks to address this need.

Andrew J. Allen

Solid oxide fuel cell (SOFC) systems are undergoing

rapid development for large-scale power applications.

We are addressing the long-term need to improve the

control and integrity of the gradient microstructures within

the cathode and anode close to, and at, the interfaces with

the dense electrolyte layer. At the typical SOFC operating

temperatures of 600 °C to 800 °C, this issue can influence

the in-service performance degradation and SOFC lifetime

during successive thermal cycles. The operative

electrochemistry at the electrolyte–electrode interfaces is,

itself, ultimately affected by these changes. A combination

of third-generation x-ray synchrotron measurements

at the Advanced Photon Source seeks to quantify the

microstructure and electrochemistry, and establish

the relationships between them.

Synchrotron X-ray Measurements in Support of

Solid Oxide Fuel Cell Development

Figure 1: USAXS.

Figure 1 presents spatial variations in the absolute

void volume fraction and surface area within a SOFC,

with respect to the electrolyte membrane position.

The data were obtained by ultrasmall-angle x-ray scattering

(USAXS), as were complete void size distributions.

A dense yttria-stabilized zirconia (YSZ) electrolyte layer

clearly separates the porous cathode (lanthanum strontium

manganate or LSM) and anode (Ni/YSZ cermet) layers.

An x-ray vertical beam dimension of less than 10 μm

was achieved to provide the needed spatial resolution.

Degradation or changes in the measured void variations,

as a function of fabrication process or service cycling,

would affect both the SOFC electrochemical performance

and structural integrity.

Figure 2: HE-WAXS.

Figure 2 shows high-energy wide angle x-ray scattering

(HE-WAXS) measurements of the complete x-ray

diffraction pattern at successive positions with respect to

the SOFC electrolyte layer. HE-WAXS and corresponding

high-energy small-angle x-ray scattering (HE-SAXS)

studies of the void surface area variation (calibrated by

cross-reference to USAXS) have been made with a 5 μm

x-ray beam size. At the 80 keV x-ray energy, both WAXS

and SAXS data can be obtained with similar measurement

geometries and at identical sample positions. Thus, the

spatial variations in void microstructure and phase can be

cross-referenced to infer the electrochemical behavior of

the electrode microstructures close to the interface with

the YSZ electrolyte.

Recently, the electrochemical issues have been

explored more directly through measurement of x-ray

fluorescent yield (FY) spectra. We have used an in-situ

heating chamber to study SOFC cathode layers under

controlled atmosphere conditions at temperatures

close to those encountered in an operating SOFC.

By combining the electrochemical data obtained for

specific interfaces with knowledge of the SOFC

microstructure and phase information above,

we seek to facilitate improved SOFC design.

Contributors and Collaborators

J. Woicik (Ceramics Division, NIST); J. Ilavsky,

J. Almer (Argonne National Laboratory); A. Virkar

(University of Utah); L. Wilson (NETL); P. Singh,

J. Stevenson (PNNL); J. Ruud (GE Corporate Research);

M. Seabaugh (NexTech Materials)
24

Program Overview

Nanometrology

in determining mechanical properties of thin films

and nanostructures, focuses on developing traceable

calibration methodologies and standard test methods.

We also use atomic force acoustic microscopy,

surface acoustic wave spectroscopy, and Brillouin light

scattering to measure the mechanical properties of

thin films. In addition, we are developing micro- and

nano-scale structures and test methods to measure

strength and fracture behavior of interfaces and

materials having very small volumes.

The chemical and structural characterization and

imaging utilize neutron and x-ray beam lines at three

facilities: the NCNR; the National Synchrotron Light

Source at Brookhaven National Laboratory; and

the Advanced Photon Source at Argonne National

Laboratory. Innovative scattering and spectroscopy

methods are advancing our ability to obtain a wide

range of chemical and structural information at the

nanoscale, including chemical bond identification and

orientation, polyelectrolyte dynamics, and equilibrium

structures. In collaboration with three other NIST

laboratories, we are developing electron microscopy

and spectroscopy instrumentation for quantitative,

3D chemical imaging at the nanoscale. Other

characterization projects include work on gradient

reference specimens for the calibration of advanced

scanning probe microscopy, and the application of

carbon nanotubes as physical probes of cell membranes.

Efforts in the fabrication and monitoring of

nanoscale processes and events include the study of

electrochemical and microfluidic methods for fabricating

nanostructures, novel approaches to nanocalorimetry

for the study of interfacial reactions, in situ observations

of nanoparticle and nanotube dispersion and alignment,

and advanced instrumentation for nanotribology

experiments.

Finally, we have extensive efforts in the theory,

modeling, and prediction of material properties and

behavior extending from nanoscale to macroscale

dimensions. Modeling efforts include large-scale finite

element methods, multiscale Green’s function methods,

classical atomistic simulations, first principles, and

quantum mechanical calculations using density

functional theory. Often, several modeling methods

must be combined into one study to accurately describe

the material behavior; thus, we pay great attention to

the correct interfacing between models operating at

different length scales, to ensure that our models

properly capture the physics of both components

and total systems.

Contact: Douglas T. Smith,

Stephen M. Hsu (Ceramics Division)

The burgeoning field of nanomaterials extends

across the full range of traditional material classes,

including all forms of metals, polymers, and ceramics.

No previous materials technology has shown so

prodigiously a potential for concurrent advances in

research and industry as does the field of nanomaterials

in mechanical devices, electronic, magnetic, and optical

components, quantum computing, tissue engineering

and other biotechnologies, and as-yet unanticipated

exploitations of as-yet undiscovered novel properties

of nanoscale assemblies of particles. Already, there

is growing excitement surrounding the ability of

some molecules or particles to self-assemble at

the nanoscale to form new materials with unusual

properties. Nanometrology, i.e., the ability to conduct

measurements at these dimensions, to characterize the

materials, and to elucidate the structure and nature of

these new and novel assemblies, is a requisite and

fundamental cornerstone that must be established

securely if this technology is to flourish.

NIST is uniquely positioned to lead the development

of the measurement methods, instrumentation, standards,

and reference materials that, together, will form the

metrological infrastructure essential to the success

of nanotechnology.

The MSEL Nanometrology Program incorporates

basic measurement metrologies to determine material

properties, process monitoring at the nanoscale,

nanomanufacturing and fabrication techniques, and

structural characterization and analysis techniques

such as advanced imaging and multiscale modeling.

The Program comprises 22 projects in the Ceramics,

Materials Reliability, Metallurgy, and Polymers

Divisions, and includes structural characterization

using neutron scattering at the NIST Center for

Neutron Research (NCNR). The projects cover a

wide range of measurement and characterization

methods grouped into the areas of mechanical

property measurement, chemical and structural

characterization and imaging, fabrication and monitoring

of nanoprocesses and events, and modeling of nanoscale

properties. In each area, we work to advance basic

measurement capabilities and lead the intercomparison,

standardization, and calibration of test methods. The

newly completed Advanced Measurement Laboratory

at the NIST Gaithersburg site provides an incomparable

environment for accurate nanoscale metrology.

In the area of mechanical property measurement,

we are developing and standardizing techniques for

determining nanoscale elastic properties (elastic moduli,

Poison’s ratio, and internal stress), plastic deformation,

density, adhesion, friction, stiction, and tribological

behavior. Work in nanoindentation, used extensively
25

Nanometrology

Chemistry and Structure of Nanomaterials

Successful nanoscale materials fabrication is

empowered by a detailed knowledge of the chemistry

and structure of surface bound molecules; e.g.,

the optimization of self-assembled monolayers,

molecular templates, micro-electro-mechanical

system lubricants, and functionalized nanotubes.

Near-Edge X-ray Absorption Fine Structure

(NEXAFS) spectroscopy is ideally suited to measure

non-destructively chemical bond concentration,

rehybrization, and orientation with sub-monolayer

molecular sensitivity in diverse nanoscale materials.

Furthermore, NEXAFS can distinguish chemical

bonding in the light elements, measure the orientation

of interfacial molecules, and separately measure

surface versus bulk chemistry simultaneously.

Daniel A. Fischer

Materials having low energy surfaces are used in

many applications, for example, in non-wetting

surfaces or fouling resistant marine coatings. We have

produced a photo-responsive polymer surface by

combining the reversible photo-switching nature of

azobenzene with the self-assembly nature and low

surface energy properties of semi-fluorinated segments,

to create a fluoroazobenzene molecule surface.

Upon UV exposure, this surface reorients between

hydrophobic and less hydrophobic states, as shown

in Figure 1 (left upper and lower panels). For such

surfaces, one could imagine applications ranging from

low cost surface patterning to polymer surfaces that

would adsorb biological macromolecules on cue.

Figure 1: UV light reorients fluorobenzene semi-fluorinated

segments (green) downwards, i.e., to a less hydrophobic state.

We have utilized NEXAFS to observe, verify, and

quantify the reversible cis-trans molecular conformation

transformation from hydrophobic to less hydrophobic

states. The right panels of Figure 1 (upper and lower)

show polarization dependent NEXAFS anisotropy

behavior of the C–F and C–C peaks which reverse with

in situ UV light exposure highlighting the reorientation

of the semi-fluorinated segments.

Figure 2: Carbon NEXAFS of oxidized/functionalized nanotubes.

Figure 3: Model of peroxide functionalization of nanotubes.

Application of NEXAFS spectroscopy to the study of

electronic structure and chemical composition is illustrated

in Figure 2 for various chemically functionalized, singlewalled, carbon nanotubes. Upon peroxide functionalization,

the C=C ring resonance is greatly diminished on extensive

sidewall functionalization indicating loss of extended

conjugation and disruption of nanotube electronic

structure. The C= O peak intensity is greatest for peroxide

chemistry. NEXAFS spectroscopy supports a model

of peroxide funtionalization, shown in Figure 3.

Contributors and Collaborators

S. Samabasivan (Ceramics Division, NIST);

X. Li, C.K. Ober (Cornell); A. Hexemer, E.J. Kramer

(UCSB); S. Banerjee, T. Benny, S.S. Wong (SUSB);

J.A. Misewich (BNL)
26

Nanometrology

Reactions occurring at interfaces during the

high-temperature processing of complex electronic

materials involve diverse chemical compositions.

To optimize the design and control of these

interfaces, we are developing a generic

thermodynamic/kinetic model for interfacial

interactions. The model includes modification

of bulk reaction and mass transport parameters

to accommodate nanoscale observations.

Lawrence P. Cook, Winnie Wong-Ng,

and Igor Levin

State-of-the-art electronic devices contain complex

materials with chemical constituents ranging widely

over the periodic table; furthermore, new materials are

continually being added. Many electronic packaging

materials consist of metals, ceramics, and semiconductors,

with bi-phasic interfaces of several types. Processing

temperatures may extend up to 900 oC where diffusion

and reaction can be significant. Two principal

problems arise in the treatment of such interactions:

1) the application of equilibrium thermodynamic data

to the non-equilibrium growth of interfacial reaction

zones, and 2) the transition from micro-scale (bulk

dominated), to nanoscale (surface dominated) phenomena.

To address these issues, we have instituted a combined

thermodynamic/kinetic approach to investigate the model

system Ag-Bi2O3-Nb2O5-O, as outlined in Figure 1.

Thermochemistry and Metrology of Interfacial Interactions

Progress includes determination of a preliminary

phase diagram at 850 oC, and development of a

provisional thermodynamic model. Subsequent

construction of a chemical potential diagram has

allowed us to predict alternative diffusion and reaction

paths. Observations on Ag/BiNb5O14 reaction couples

(Figure 2) confirm the relatively high thermodynamic

mobility of Ag. Thermogravimetric data on the

interfacial reaction require more than a simple parabolic

rate law, due to the rapid initial spread of Ag along

reaction site surfaces. By comparison with particulate

interfacial systems, a two-step reaction model is

proposed, for which rate constants can be obtained.

Data for the model system are of direct interest

to the electronics community because Ag is an

important metallization component in many dielectric

ceramics. It is anticipated that continued work

on Ag-Bi2O3-Nb2O5-O will lead to the goal of a

comprehensive thermodynamic/kinetic model.

The model will be tested, iteratively refined, and

extended to other systems.

Contributors and Collaborators

M.D. Vaudin, P.K. Schenck, T. Vanderah, M. Green

(Ceramics Division, NIST); W. Luecke (Metallurgy

Division, NIST); C. Randall, M. Lanagan (Center for

Dielectric Studies, Pennsylvania State University)

Figure 2: Ag Lα X-ray map of Ag/BiNb5O14 reaction zone

(≈ 80 μm wide) produced by annealing in air for 10 h at 850 oC,

with an applied uniaxial compression of ≈ 1 MPa.

Figure 1: Flow chart for development of interfacial model based

on Ag-Bi2O3-Nb2O5-O.
27

Nanometrology

As technology migrates toward smaller physical

dimensions, new analytical approaches are

required to characterize material properties and

to investigate critical issues. Our primary focus is

the application of metrology and the development

of new methods and standards for measuring the

physical and surface properties of nanostructured

particle systems. Applications include functional

materials and devices for catalysis, power

generation, and microelectronic, pharmaceutical,

and biotechnology industries.

Vince Hackley

Nanocrystalline oxides of alkaline-earth cations

produced by a supercritical drying process exhibit

unique and highly reactive surface chemistries. As a

result, these materials have been studied extensively as

destructive adsorbents, catalysts, and bioactive agents.

Investigations were concluded regarding the role of

cation size on the evolution of microstructure in these

materials and on the dispersion properties in aqueous

NaCl solution. A series of small-angle neutron

scattering (SANS) experiments were performed at

the NIST reactor in collaboration with researchers

at Kansas State University. These results indicate a

complex picture for structure formation during the

drying and annealing processes, with string-like gel

morphology giving way to fractally rough particulate

assemblies of compacted nanocrystals.

Particle Metrology and Nanoassembly

Figure 1: Maximum entropy fit to SANS data for annealed

MgO aerogel.

Data were analyzed using the Unified Model of

Beaucage and the maximum entropy method (see

Figure 1). The scale of the finest structural features

increases with increasing cation size for the annealed

product. Analysis indicates the absence of mass fractal

structures but the presence of surface fractal-like

objects. A broad correlation peak in the data for

heat-treated Mg and Ca oxides gives evidence for

some local ordering of the nanocrystals. This data

will help provide a more complete understanding of

the structural development in this complex and

technologically important system.

Figure 2: Schematic diagram of capillary flow cell.

A capillary flow-cell (Figure 2) was developed and

commissioned for the ultra-small-angle x-ray scattering

(USAXS) instrument on the UNICAT beam line at the

Advanced Photon Source. This new capability will

permit in situ investigations of complex multiphase

particulate systems under controlled flow conditions.

Initial applications include the dispersion of single-wall

carbon nanotubes in collaboration with Rice University

and depletion effects in binary colloidal suspensions.

Contributors and Collaborators

A. Allen, L. Lum (Ceramics Division, NIST);

D. Ho (NIST Center for Neutron Research);

K. Klabunde (Kansas State University); M. Pasquali

(Rice University); P. Jemian (University of Illinois)
28

Nanometrology

Myriad industrial and biological systems are

composed of small-scale structures for which the

mechanical behavior is not accurately known.

Optimizing the performance and reliability of

these systems requires either mechanical property

measurements on specimens of these structures

harvested from the appropriate phases or

interfaces of the system, or the ability to test these

structures in situ. We are developing standardized

testing configurations and methodologies for

localized measurements of strength and fracture

toughness of materials and interfaces at the

micro- to nanometer-length scale.

Edwin R. Fuller, Jr. and George D. Quinn

This project aims to: (1) measure mechanical

properties of microstructures for myriad industrial

and biological systems that cannot be fabricated in bulk

samples; (2) study small-scale phenomena that may

be controlled by surface effects, e.g., the influence of

surface stresses on crack nucleation and extension; and

(3) obtain quantitative mechanical property data of materials

and interfaces for designing small-scale structures and

components and for assessing their mechanical reliability.

To address these goals, well-characterized testing

configurations must be developed for small-scale

measurements of strength and crack extension. We are

pursuing four tasks: (1) configuration design and finite

element analysis; (2) specimen fabrication; (3) mechanical

testing and fracture analysis (fractography); and (4) length

and force metrology. Work in the Ceramics Division

this year has focused on the first and third areas. Two

collaborations were established in the fabrication task:

one with James A. Beall of the Quantum Electrical

Metrology Division (817) in NIST Boulder, and one with

Northwestern University. Work in the fourth task will

Mechanical Metrology for Small-Scale Structures

come in subsequent years, most likely in collaboration

with the Manufacturing Engineering Laboratory.

Significant progress has been made in the design of a

compressively loaded test configuration with a welldefined, tensile gage section. Such a specimen can be

loaded using a depth-sensing nanoindenter as a universal

testing machine, thereby giving a record of both applied

load and load-point displacement. One of these specimens,

fabricated by James Beall from a silicon wafer by

deep reactive ion etching, is shown in the right-side of

Figure 1. The configuration is similar to a theta specimen,

except that the geometry is hexagonal. When a load

(per unit thickness) is applied to the top beam, a uniform

uniaxial tensile stress results in the middle gage section.

Finite element analysis gives (horizontal) gage section

stresses on the order of 1.25 GPa for 50 mN/μm of applied

load. For a 2 N applied load, these 100 mm-thick

specimens generate 500 MPa of tensile stress in the gage

section. The left-side of Figure 1 shows a reconstructed

failed specimen. The insert shows the fracture surface

of the gage section, and the two [111] cleavage facets

that were formed. Alternate geometries, including a

round theta specimen, are also being considered.

Figure 1: Prototype specimen design.

To extend this technique to a wide variety of

materials and systems, general fabrication procedures

need to be developed. Towards this objective, focusedion-beam (FIB) milling is being explored in collaboration

with Northwestern University. Figure 2 shows our first

attempt at producing a hexagonal theta specimen by

FIBing. It has been scaled-down by about a factor

of 10, and is fabricated from a lamellar directionally

solidified eutectic of Ni0.5Co0.5O and ZrO2.

Contributors and Collaborators

D. Xiang, D.T. Smith (Ceramics Division, NIST);

A. Jillavenkatesa (Standards Services Division, NIST);

J.A. Beall (Quantum Electrical Metrology Division,

NIST); N. Alem, V.P. Dravid (Northwestern University)

Figure 2: Hexagonal theta specimen by FIBing.
29

Nanometrology

Nanoindentation has rapidly become the method of

choice for quantitative determination of mechanical

properties of thin films and small volumes of material,

but standardization efforts have lagged far

behind the application of the technique in industrial

research and development. Over 1000 commercial

nanoindentation instruments from a variety of

manufacturers are currently in use, with no traceable

force calibration and an extremely limited choice of

standardized test methods. We work with standards

groups and National Measurement Institutes around

the world to develop standard reference materials

(SRMs), traceable calibration transducers, and

robust, reliable methods for obtaining and analyzing

nanoindentation data, so that nanoindentation

results can be used with confidence in product design

and specification.

Douglas T. Smith

Nanoindentation is the most commonly used method

for determining hardness and elastic properties of

small volumes of materials. In this technique, a diamond

indenter is pushed into a specimen surface, and the force

on and displacement into the surface are recorded. The

technique is capable of providing information on the elastic

and plastic deformation of a specimen for indentations as

shallow as 5 nm to 10 nm, and requires minimal specimen

preparation effort. It is routinely used to measure the

mechanical properties of thin films. However, there

are only a very limited number of accepted test methods

available, and no means to traceably calibrate or verify

the performance of nanoindentation instruments.

This leads to large interlaboratory variations in results,

particularly for hard, high modulus materials, and prevents

the use of nanoindentation in thin film or coating

product specifications.

In many mechanical test methods, including

nanoindentation, a force is applied to a specimen, and

some displacement is measured. Traceable displacement

measurement by interferometry is well established. Force

measurement is more problematic, however, because the

SI unit for force is still based on an artifact kilogram mass.

The Microforce Competence Program at NIST has

developed a primary realization of force, traceable to

electronic and length SI units, for force calibration in

the range 1 mN to 10 nN. As part of this program,

transfer force cells are being developed that will allow

force calibration, traceable to NIST, for commercial

nanomechanical test equipment such as nanoindentation

machines and atomic force microscopes. One such

Figure 1: The error in the force applied to a specimen by a

commercial nanoindentation instrument, as referenced to a

traceably calibrated NIST force cell.

Nanoindentation Methods and Standards

transfer force cell was calibrated against the NIST primary

force balance to an uncertainty less than 0.5 % for forces

in the range 0.05 mN to 5.0 mN. That cell was then

mounted, as if it were a specimen, in a popular commercial

nanoindentation instrument that had been recently

calibrated by its manufacturer using their recommended

force calibration procedure. The figure shows the error

in the nanoindentation force recorded by the instrument,

relative to the traceable force cell reading. For forces

above 2 mN, the recorded force is within the 1 %

uncertainty required by most draft standards for

nanoindentation machines. However, for lower applied

force, the error increases dramatically, and at 0.05 mN,

the recorded force is almost 18 % below the actual

applied force.

We are also working with both ASTM (E28.06.11)

and ISO (TC 164/SC 3) on a wide range of standard

test methods for nanoindentation, and an ISO document

for the one method has now been approved (ISO

14577). In addition, the Ceramics and Materials

Reliability Divisions at NIST are working with the

Bundesanstalt für Materialforschung und–prüfung

(BAM) in Germany to develop joint thin film SRMs

(CRMs, or Certified Reference Materials, in Europe)

for use in nanoindentation machine verification.

Contributors and Collaborators

D. Xiang, B. Hockey, G. Quinn (Ceramics Division,

NIST); R. Machado (INMETRO, Brazil); J. Pratt

(Manufacturing Engineering Laboratory, NIST);

D. Hurley (Materials Reliability Division, NIST);

U. Beck (BAM, Germany)
30

Nanometrology

Accurate adhesion and friction measurements

at the nanoscale are emerging as critical issues

in device industries and nanotechnology.

Measurements characterizing nanometer-thick

molecular assemblies and surface textures to

control surface properties and to ensure reliability

and durability are also needed. Working with

device and magnetic storage industries and other

agencies, we have designed and built instruments

to meet these needs. These instruments are housed

in NIST’s new Advanced Measurement Laboratory.

The facility features vibration isolation, class 1000

clean room standards, and temperature control.

Stephen M. Hsu

The nanotribology and surface properties project

was initiated as a part of the MSEL Nanotechnology

Initiative. The project aims to develop measurement

capability for adhesion, friction, and surface forces

at the nanoscale. We interact extensively with many

industries and research centers in the U.S. and around

the world to promote advances in measurement

science and seek consensus standard harmonization

in three areas: nanocontacts, nanolubrication, and

surface texturing.

Nanocontacts

Adhesion and friction measurements at nanocontacts

require accurate detection of normal and lateral forces

at nanonewton levels. Scanning probe microscopes

use sensitive cantilevers and laser diodes to detect these

forces, but this approach introduces rotation of the tips

and crosstalk among the xyz planes. To understand

the influence of surface forces, many of which are

functions of contact area, attention must be focused

on determining the real area of contact.

To resolve some of the instrumental challenges,

we have engaged instrument makers, such as

Hysitron, Veeco, and others, to solicit their inputs and

collaborations. At the same time, we have established

our own capability in tip fabrication, cantilever spring

constant calibration, and tip characterization. Three

new instruments were successfully installed as a result

of these collaborations: the NIST–Hysitron multiscale

friction tester, the NIST nanoadhesion apparatus, and

the first prototype of an interferometer microscope

from Veeco. We are continuing to work with our

partners to develop next-generation instruments as

suggested by the Nanometrology Grand Challenges

Workshop (NIST, January 2004).

Nanotribology and Surface Properties

The overall objective of the nanocontacts activity

is to develop the constitutive equation of adhesion

and friction including the various components

of surface forces. With our new adhesion and

nanofriction apparatus, we are quantifying the effects

of plowing and electrostatic charge on measurements.

We continue to work with our external academic

partners (UC Berkeley, UC Davis, and Ohio State U)

under the Nanotechnology Extramural Initiative to

develop friction measurement via three approaches:

friction measuring MEMS devices, AFM methods,

and ultrahigh vacuum friction measurement. These

efforts have been successful, and we have gained

considerable understanding of how meniscus forces

and electrostatic forces can exert significant effects on

nanofriction measurements. A NIST special publication

summarizing these findings is under preparation.

Nanolubrication

Molecular assemblies can be organized to impart

hydrophobicity, anti-adhesion, and friction control

characteristics on device surfaces. Supported by other

agencies and the magnetic storage industry, this activity

focuses on how to measure the effects of controlled

composition and spacing on properties of nanometerthick films. An ultrahigh vacuum scanning tunneling

microscope-atomic force microscope was installed in

May 2004 to provide imaging capability at the molecular

level. A micro-tribometer was also developed to measure

the durability of these films. The synchrotron facility

operated by the Division’s Characterization Methods

Group at Brookhaven National Laboratory continues to

be vital in characterizing these complex molecular mixtures.

Surface Texturing

Surface texture increasingly is being considered as

a tool to control surface energy, polarity, adhesion, and

friction. Supported by other agencies and industries,

we are pioneering the use of specific surface features

such as dimples, triangles, and ellipses at microand nanoscale dimensions to supplement molecular

assemblies to control surface properties of surfaces.

An international cooperative study under the auspices

of International Energy Agency (IEA) is underway.

Contributors and Collaborators

C. Ying, R. Gates, J. Chuang, J. Larson–Basse,

L. Ives, D. Fischer (Ceramics Division, NIST); B. Bhushan

(Ohio State U.); K. Komoupoulas (UC Berkeley);

G. Liu (UC Davis); Y.T. Hsia (Seagate); J. Sengers

(U. of Maryland); O. Warren (Hysitron); C. Su (Veeco)
31

Program Overview

Materials for Electronics

The U.S. electronics industry faces strong

international competition in the manufacture of smaller,

faster, more functional, and more reliable products.

Many critical challenges facing the industry require

the continual development of advanced materials

and processes. The NIST Materials Science and

Engineering Laboratory (MSEL) works closely with

U.S. industry covering a broad spectrum of sectors

including semiconductor manufacturing, device

components, packaging, data storage, and assembly,

as well as complementary and emerging areas such as

optoelectronics and organic electronics. MSEL has a

multidivisional approach, committed to addressing the

most critical materials measurement and standards

issues for electronic materials. Our vision is to be

the key resource within the Federal Government for

materials metrology development and will be realized

through the following objectives:

■ Develop and deliver standard measurements and data;

■ Develop advanced measurement methods needed by

industry to address new problems that arise with the

development of new materials;

■ Develop and apply in situ as well as real-time, factory

floor measurements, for materials and devices having

micrometer- to nanometer-scale dimensions;

■ Develop combinatorial material methodologies for

the rapid optimization of industrially important

electronic materials;

■ Provide the fundamental understanding of the

divergence of thin film and nanoscale material

properties from their bulk values;

■ Provide the fundamental understanding of materials

needed for future nanoelectronic devices, including

first principles modeling of such materials.

The NIST/MSEL program consists of projects led

by the Metallurgy, Polymers, Materials Reliability, and

Ceramics Divisions. These projects are conducted in

collaboration with partners from industrial consortia

(e.g., International SEMATECH), individual companies,

academia, and other government agencies. The program

is strongly coupled with other microelectronics

programs within the government such as the National

Semiconductor Metrology Program (NSMP). Materials

metrology needs are also identified through the

International Technology Roadmap for Semiconductors

(ITRS), the IPC Lead-free Solder Roadmap, the

National Electronics Manufacturing Initiative (NEMI)

Roadmap, the Optoelectronics Industry Development

Association (OIDA) Roadmap, IPC (the International

Packaging Consortium), and the National [Magnetic

Data] Storage Industry Consortium (NSIC) Roadmap.

In each of these areas, MSEL researchers have made

substantial contributions to the most pressing technical

challenges facing industry, from new fabrication methods

and advanced materials in the semiconductor industry, to

advanced packaging materials, to magnetic data storage.

Below are just a few examples of MSEL contributions

over the past year.

Advanced Gate Dielectrics

To enable further device scaling, the capacitive

equivalent thickness (CET) of the gate stack thickness

must be 0.5 nm to 1.0 nm. This is not achievable with

existing SiO2/polcrystalline Si gate stacks. Given the

large number of possible choices for these new layers,

the only feasible approach to understanding the complex

materials interactions that result at the gate dielectric/

substrate and gate dielectric/metal gate electrode

interfaces is through the application of combinatorial

methodologies. This same methodology and apparatus

are applicable to a wide variety of problems in the

electronic materials field.

Sub-100 nm Nanofabrication

The continual decrease in feature size has been the

driving force for advances in the semiconductor industry.

Current structures have 90 nm dimensions with planned

nodes at 65 nm and 35 nm structures. Advanced

measurements of the patterning materials (photoresists),

are needed to enable future large scale manufacturing of

smaller devices. MSEL utilizes advanced x-ray and

neutron tools to provide insight into the feasibility

and optimization of these important processes.

Advanced Metallization

Electrodeposited copper is rapidly replacing aluminum

for on-chip “wiring” because of its lower electrical

resistivity, superior electromigration behavior, and the

ability to fill fine features without the formation of seams

or voids. As feature dimensions go below 100 nm,

difficulties in maintaining performance are anticipated.

These issues are addressed through a combination of

modeling and experimental efforts.

Test Methods for Embedded Passive Devices

Significant advantages arise if passive devices are

integrated directly into the circuit board as embedded

passive devices rather than discretely attached with

automated assembly. New metrology methods were

developed to address the needs of the electronic industry.

Two test methods were completed and have received

wide acceptance by industry as new methods to accelerate

the development of embedded passive device technology.

Contact: Martin L. Green (Ceramics Division),

Eric K. Lin (Polymers Division)
32

Materials for Electronics

Combinatorial materials science has rapidly

become a new paradigm for the acceleration

of materials research. It is a fast and efficient

methodology for materials optimization and

discovery, characterized by high throughput,

parallel experiments, automated analysis, and

massive data sets. NIST’s industrial stakeholders

are identifying it as the only viable technique for

understanding complex materials science systems

in a competitive timeframe. Its application to

a critical materials science problem in the Si

microelectronics industry, the replacement of the

gate stack, is expected to drive an inorganic

combinatorial materials science program at NIST.

Martin L. Green

NIST/MSEL is poised to play several important roles

in developing combinatorial materials methodologies,

especially as they pertain to industrially important, advanced

inorganic materials. Included in this class are materials

such as thermoelectrics, dielectric and metal layers

for advanced Si CMOS gate stacks, multiferroics,

magnetic semiconductors for spintronics, transparent

semiconductors, and fuel cell and H2 storage materials.

NIST/MSEL has an opportunity to take a lead position

in the use of combinatorial methodologies for:

■ New, combinatorially-friendly (rapid, local,

microscopic measurements) metrologies;

■ Materials optimization and development;

■ Means of experimentally verifying computed

materials properties;

■ Tools for determining phase diagrams and other

property data; and

■ “Data on demand,” or “just-in-time-data.”

The advanced gate stack application for Si CMOS

is a good example. International Sematech (ISMT) is

currently faced with major materials challenges to further

miniaturization. Figure 1 schematically illustrates a metal

oxide-semiconductor field effect transistor (MOSFET),

showing the advanced gate stack which consists of the

high-κ (κ = dielectric constant) gate dielectric and the

metal gate electrode. To enable further device scaling,

the capacitive equivalent thickness (CET) of the gate stack

thickness must be 0.5 nm to 1.0 nm. This will not be

achievable with existing SiO2/polycrystalline Si gate stacks.

Given the large number of possible choices for these

new layers, the only feasible approach to understanding

the complex materials interactions that result at the

gate dielectric/substrate and gate dielectric/metal gate

electrode interfaces is through the application of

combinatorial methodologies.

The acquisition of a state-of-the-art combinatorial

synthesis tool is expected be one of the cornerstones

of the NIST/MSEL effort. In addition, we plan to

acquire combinatorially-friendly tools such as a

micro-x-ray diffractometer, and to develop new

metrologies such as nanocalorimetry for the

detection of phase transformations in thin films.

Figure 1: MOSFET device with advanced gate stack.

Figure 2: Combinatorial ternary and binary film libraries.

Combinatorial Tools for Materials Science

The new combinatorial synthesis tool will be capable

of depositing entire ternary and binary libraries in areas

as small as 6.5 cm2 (1 in2), as is shown in Figure 2.

Contributors and Collaborators

L. Cook, W. Wong-Ng, P. Schenck (Ceramics

Division, NIST); L. Bendersky, A. Davydov (Metallurgy

Division, NIST); S. Semancik (CSTL, NIST);

J. Suehle, E. Vogel (EEEL, NIST); T. Chikyow

(NIMS, Japan); B. Murto (International Sematech);

I. Takeuchi (U. of Maryland)
33

Materials for Electronics

Modern electronic devices have reached the point

where fundamental materials properties now limit

continued improvement in device performance.

Consequently, new materials, their synthesis, their

properties, and their interactions with established

materials and technologies are in continuous need

of development and investigation. The Ceramics

Division operates a suite of synchrotron beamlines,

at the Advanced Photon Source and at the National

Synchrotron Light Source, designed to address

critical issues focused on these next-generation

materials, including the electronic and structural

properties of materials used in advanced

electronic applications.

Joseph C. Woicik

The electronics industry is seeking to increase device

performance by increasing carrier mobility in silicon

by introducing a small tensile strain into the silicon

lattice. This is accomplished by the epitaxial growth

of a thin silicon layer on a virtual crystalline substrate

of relaxed Si1–xGex with x typically between 10 % and

50 %. A critical aspect of this process is the control of

defects in the SiGe-alloy layer and the propagation of

these defects into the strained-Si film.

Spectroscopy, Diffraction, and Imaging of Electronic Materials

Figure 1: Radial diffraction scan for a strained-Si/SixGe1–x /Si(001)

semiconductor layered structure.

We have utilized x-ray diffraction and x-ray

topography at the UNICAT beamline facility at the

Advanced Photon Source to image defects in the SiGe

film and to study how these defects propagate into the

strained-Si overlayer. Figure 1 shows a high-resolution

x-ray diffraction scan around the Si(004) Bragg

condition from a 500 Å Si film grown on a relaxed

3 μm thick SiGe film with a Ge content of 20 %.

The relaxed SiGe film was grown on top of a SiGe

layer that was grown on a Si(001) substrate and

graded in composition from 0 % to 20 % Ge content

over a thickness of 2 μm.

The diffraction from the SiGe is seen near

2θ = 60.4°; it appears as a doublet due to a slight

composition variation due to the intermediate

planarization process. Diffraction from the grade

is also apparent. The sharp peak near 2θ = 60.9° is

diffraction from the Si substrate, and the much weaker

peak near 2θ = 61.3° is diffraction from the strained-Si

film. The Si film has a smaller perpendicular lattice

constant than the crystalline Si substrate because it is

under in-plane tensile strain due to its epitaxy with the

SiGe layer that possesses a larger cubic lattice constant.

The differences in lattice constants between the

strained-Si film, SiGe layer, and Si substrate make it

possible to image the diffraction from each component

separately. Figure 2 shows the (113) x-ray topographs

recorded with an x-ray energy of ≈ 8.9 keV. This

diffraction geometry was chosen because it is within

Si total external reflection and, therefore, limits the

x-ray penetration depth into the sample.

The microstructure of the substrate and film are

nearly identical, demonstrating that the misfit-dislocation

structure responsible for the relaxation of the SiGe

layer acts as a template for the microstructure of the

strained-Si film. The crystallographic nature of these

defects and their contribution to the ultimate relaxation

of the strained-Si film are currently under investigation.

Contributors and Collaborators

D. Black, I. Levin (Ceramics Division, NIST);

M. Erdtmann, T.A. Langdo (AmberWave)

Figure 2: (113) x-ray topographs of the SiGe film and the

strained-Si overlayer.
34

Materials for Electronics

Ceramic compounds with exploitable dielectric

properties are widely used in technical applications

such as actuators, transducers, capacitors, and

resonators or filters for microwave communications.

Phase equilibria determination integrated with

systematic chemistry–structure-property studies

contribute toward the fundamental understanding

and rational design of these technologically

important materials with improved properties

and/or reduced processing costs.

Terrell A. Vanderah, Igor Levin, and

Michael W. Lufaso

Cost and performance are the primary and secondary

drivers, respectively, for today’s commercial needs

in the area of dielectric ceramics. For example, component

suppliers and builders of 2 GHz cellular infrastructure are

critically impacted by the high cost of tantalum-containing

ceramics needed for dielectric resonators: only a single

ceramic material, perovskite-like Ba3ZnTa2O9 (BZT),

is available with the needed properties. Interest is keen

to reduce its processing costs or to find an alternative,

less-expensive substitute. The results of an experimental

phase equilibria study of the system (Figure 1) revealed

that BZT ceramics must be processed so that ZnO

volatilization occurs along the two-phase join between

BZT and Ba8ZnTa6O24 (8L) to prevent the formation of

deleterious air-sensitive compounds high in BaO content,

or dielectrically poor “TTB” type phases.

Phase Equilibria and Properties of Dielectric Ceramics

Figure 1: Phase equilibria diagram determined for the system

containing the important commercial ceramic Ba3ZnTa2O9 (BZT).

Figure 2: Phase equilibria diagram determined for the system

containing Ba3ZnNb2O9 (BZN), a possible BZT alternative.

A potential replacement for BZT is the analogous

compound with less costly niobium, Ba3ZnNb2O9.

The phase equilibrium diagram determined for this

system (Figure 2) provides processing information

for this ceramic and clearly indicates that its dielectric

loss cannot be improved by liquid-phase sintering in

the presence of low-melting, electrically acceptable

ZnNb2O6, because the two compounds do not occur

in equilibrium with each other. Such mixtures, instead,

will form dielectrically poor impurity phases.

Systematic studies of the Ba3MNb2–xSbxO9

(M =Mg,Ni,Zn), system were carried out to manipulate

the crystal chemistry and high-frequency (> 2 GHz)

dielectric properties by progressive substitution of Sb5+

(d10) for Nb5+ (d0). The results showed that control of

permittivity and tuning of the temperature coefficient to

zero was possible with appropriate substitution. Optimal

dielectric losses were obtained for specimens with low

x-values and 2:1-type ordered perovskite structures.

Figure 3: HRTEM image of 50:50 LaMg1/2Ti1/2O6-La2/3TiO3.

Dark crosses denote La vacancies, deduced from image simulations

(insert). Short-range order of La vacancies is revealed as pairs

of dark crosses in both the [001] and [100] directions and causes

diffuse superlattice reflections in the diffraction pattern.

Detailed structural studies of the LaMg1/2Ti1/2O6-

La2/3TiO3 solid solution were carried out to elucidate

the origin of the anomalous changes in permittivity and

temperature coefficient near 50:50. The results showed

that the abrupt changes in properties were accompanied

by the disappearance of one octahedral tilting mode and

the onset of short-range ordering of La vacancies.

Contributors and Collaborators

W. Wong-Ng, R.S. Roth, B. Burton, E. Cockayne

(Ceramics Division, NIST); J.E. Maslar (Process

Measurements Division, NIST); R. Geyer

(Radio Frequency Technology Division, NIST);

S. Bell (TCI Ceramics)
35

Materials for Electronics

Phase equilibria data are needed for quality control,

cost reductions, performance enhancements, and

optimal processing in high Tc technology. These

needs are being addressed through studies of the

phase equilibria and kinetics of Ba2YCu3O6+x

formation from barium fluoride amorphous

precursor films, determination of Ba2RCu3O6+x

(R=Dy,Yb) phase diagrams, and investigations

of superconductor/buffer layer interactions:

all play critical roles in the development of

RABiTS/IBAD coated conductor technology.

Winnie Wong-Ng, Lawrence P. Cook,

and Igor Levin

Phase diagrams serve as “blue prints” for successful

processing of high Tc superconductor materials.

In the past year, as an integral part of the DOE intensive

R&D program on high Tc wire and cable applications, we

have continued to provide critical data for the development

of practical superconductors. Our research was related

to two groups of superconductors: (1) Ba2RCu3O7

(R=Dy, Yb) coated conductors produced by rolling

assisted biaxially textured substrate/ion beam assisted

deposition (RABiTS/IBAD); and (2) MgB2.

Our main effort has been focused on the determination

of BaO-R2O3-CuOx phase relations as a function of oxygen

pressure, pO2, and choice of lanthanides. These studies

were completed under carbonate-free conditions, to match

better the processing conditions of RABiTS/IBAD

conductors. This year we have completed the study of

the two systems with R = Dy and Yb. A trend in phase

formation and tie-line Ba2RCu3O7 relationships was

observed in the present work which provides a general

correlation for R = Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, and Yb

with respect to the size of the lanthanides. In collaboration

with Brookhaven National Laboratory and California

Institute of Technology, an understanding of the effect of

strain on the trend of the orthorhombic to tetragonal phase

transition temperature of Ba2RCu3O7 was obtained

through modeling. By mixing the smaller lanthanides

R ́ with the larger R in the Ba2–x(R1+x–yR ́y)Cu3O6+z

superconductor, both flux-pinning and melting properties

can be tailored and optimized. A trend in solid solution

extent as related to the size of R was observed in

Ba2–x(R1+x–yYy)Cu3Oz (R = Sm, Eu and Gd).

The “BaF2 ex-situ” process is a promising method

for production of Ba2YCu3O7 superconducting wire

and cable. Previously, using a controlled-atmosphere

apparatus, we determined the presence of low-temperature

liquids in the multicomponent reciprocal Ba-Y-Cu//O,F

system. This year, we identified YOF (Figure 1) as an

Figure 1: Schematic of the YOF rhombohedral structure (left,

showing layers of [OY4 ] and [FY4 ] tetrahedra) and the cubic

fluorite structure (right).

Phase Relations of High Tc Superconductors

important intermediate phase in the system with a low

temperature reversible order–disorder phase transition near

the initial melting of fluoride-rich melts. These more

detailed studies have allowed better definition of the region

of low-temperature melting. Also, phase diagrams of

the pertinent subsystems of BaO-Y2O3-CeO2-CuOx

representing the interaction of product Ba2YCu3O7

with the CeO2 buffer layer were determined.

To control film properties, it is important to

understand the details of Ba2YCu3O7 formation from

“BaF2” films. High temperature x-ray diffraction and

transmission electron microscopy have been applied

to compare the detailed conversion mechanism of

films prepared with different precursors on SrTiO3

substrates and on RABiTS substrates (both provided

by ORNL). A phase with a Ba(OxFy)-based superlattice

has been found to be involved as an intermediate

product. Its presence may prove to be an important

factor influencing the kinetics of Ba2YCu3O7 formation.

Studies on MgB2 also continued with measurements

of the enthalpy of formation (by solution calorimetry) and

vapor pressure (by thermogravimetric effusion). Attention

was focused on the significant sources of variability in

these properties. These data are essential for reproducible

processing of MgB2 films, wire and cable.

Contributors and Collaborators

Q. Huang (NIST Center for Neutron Research);

M. Vaudin, P. Schenck (Ceramics Division, NIST);

R. Shull (Metallurgy Division, NIST); R. Klein

(Biotechnology Division, NIST); R. Feenstra, A. Goyal

(ORNL); T. Holesinger (LANL); M. Rupich (ASC);

J. Kaduk (BP-Amoco); T. Haugan (U.S. Air Force);

P. Canfield (Ames Lab); R. Meng (U. of Houston);

D. Welch (BNL), H.B. Su (Caltech)
36

Materials for Electronics

The optoelectronics industry needs measurement

techniques and accurate materials property data

to calibrate their deposition processes and to

evaluate both prototype and finished devices.

Recent work has focused on the electronic band

structure of InGaAsN films (for infrared detectors

and solar cells) and calibration of strain in

ultrathin AlxGa1–xAs films and optical properties

of GaN and ZnO nanowire structures.

Albert J. Paul and Lawrence H. Robins

I

nyGa1–yAs1–xNx semiconductor alloy films show

promise for infrared optoelectronic devices.

Data on the electronic band structure are needed to

facilitate device design and simulation. We examined

Si-doped InyGa1–yAs1–xNx films with x < 0.012 and

0.052 < y < 0.075 by photoreflectance (PR) spectroscopy,

supplemented by secondary ion mass spectroscopy

(SIMS) and energy dispersive x-ray spectroscopy (EDS,

for composition), XRD (strain), and Hall effect (electrical

properties). The composition and carrier concentration

dependence of the critical point energies, designated

E– (fundamental gap), E–+∆SO (split-off valence band

to conduction band), and E+ (valence band to nitrogen

impurity band) was successfully explained by a band

anti-crossing and free-carrier band-filling model with a

small number of adjustable parameters.

Metrology and Standards for Optoelectronic Materials

Figure 1: PR critical-point energies: data and modeling.

The measured critical-point energies (symbols)

and the best-fit model (dashed curves) are plotted as

functions of N mole fraction (x) in Figure 1(a), and Hall

carrier concentration (ne) in Figure 1(b).

We are continuing to develop methods for

quantifying optical measurements of stress and strain

in III–V semiconductors. By calibrating the shift of

the Raman and PL peaks with known applied stress

in a load cell, we are able to measure stresses due to

differential thermal expansion, film-substrate lattice

mismatch, and device packaging. As an example,

the stress induced by bonding of a 10 mm × 10 mm

Al0.2Ga0.8As-on-GaAs sample (grown as a composition

SRM) to a stainless steel disk was measured by this

technique. Results from selected locations on the

bonded sample and, for comparison, an unbonded

piece cut from the same wafer, are shown in Figure 2.

A large tensile stress is seen to occur near the center

of the bonded piece, but not in the unbonded piece.

Stress measurements of ultrathin (5 nm to 30 nm)

AlGaAs films have been initiated to compare spatially

resolved measurements of stress near the edges of

ultrathin films with the quantitative predictions of

Object-Oriented Finite Element (OOF) modeling.

Contributors and Collaborators

E. Fuller, Y.-S. Kang, G. White (Ceramics Division,

NIST); K.A. Bertness, N.A. Sanford (Optoelectronics

Division, NIST); A.V. Davydov, A.J. Shapiro (Metallurgy

Division, NIST); D. Chandler–Horowitz (Semiconductor

Electronics, NIST); M.M.E. Fahmi, S.N. Mohammad

(Howard University)

Figure 2: Tensile stress distributions in two Al0.2Ga0.8As

structures, obtained from calibrated PL measurements.
37

Materials for Electronics

Commercial ferroelectric thin film devices are rapidly

approaching the same nanoscale dimensions as

individual grains, yet little is known about the

influence of grain boundaries and local texture

on ferroelectric properties. Accordingly, several

complementary experimental and theoretical

techniques are being developed to assess

the local ferroelectric response. By combining

quantitative piezoelectric force microscopy (PFM),

electron backscattering diffraction (EBSD), and

two-dimensional object oriented finite-element

modeling (OOF), various individual crystallographic

distributions with either beneficial or detrimental

effects can be identified and eventually predicted.

Bryan D. Huey, R. Edwin García and

John E. Blendell

Crystallographic orientation can now be determined

with nanometer scale lateral resolution using the

newly installed electron backscattering diffraction system

(EBSD), allowing the orientation of individual ferroelectric

grains to be mapped as indicated in Figure 1a.

Experimental and Theoretical Influence

of Thin Film Texture on Ferroelectric Hysteresis

Figure 1: (a) Measured surface orientation of PZT thin film and

(b) predicted strain normal to the surface for the same grains

when biased with an electrode as indicated. Bar = 20 μm.

Figure 2: Measured piezoelectric hysteresis areas of several

grains/boundaries.

Recent advances in two-dimensional (2-d) object

oriented finite element modeling (OOF) have made it

possible to predict the piezoelectric response of a

polycrystalline thin film with full consideration of the

sample texture as determined by EBSD. Figure 1b

demonstrates the strain normal to the surface for an

applied bias of 1 V across a 100 nm thick film using

a 100 nm diameter electrode, where the electrode

is positioned across multiple grains of differing

orientations. The local response is strongly dependent

on texture, in some cases oppositely oriented.

Piezoelectric force microscopy (PFM) was

employed to determine experimentally the ferroelectric

properties of the same grain and grain boundary regions

considered by EBSD and OOF. This AFM-based

technique is widely used, but can be significantly

hindered by several instrumental artifacts that were

identified and overcome during this work. The area

of piezoelectric hysteresis loops determined using the

newly developed quantitative methods is indicated in

Figure 2 for several distinct grains and boundaries. The

measured hysteresis variations correlate with grains and

grain boundaries of differing misorientation as measured

by EBSD and correlates with strains calculated by OOF.

Key accomplishments and conclusions include:

1) Novel methods for identifying and overcoming artifacts

in piezoelectric force microscopy to allow quantitative

local piezoelectric hysteresis measurements;

2) Unique 2-d simulations of converse-piezo actuation

with complete incorporation of true thin-film texture;

3) The importance of uniform texture for optimal

ferroelectric properties when device dimensions

approach the lateral grain size; and

4) The likelihood of domain pinning or even crack

initiation at certain grain boundaries and intersections

as a result of local orientation.

Results from this work were presented at the SPIE

Ferroelectrics conference, American Ceramic Society

annual meeting, European Congress on Nanoscale

Materials (Nano-04), IEEE Ferroelectrics and Ultrasonics

joint meeting, and several invited seminars at NIST and

various universities. Publications in the Journal of the

American Ceramic Society, Journal of Electroceramics,

and Journal of Applied Physics are under review.

Contributors and Collaborators

M.D. Vaudin, E.R. Fuller, Jr. (Ceramics Division,

NIST); S. Hong (Samsung)
38

Materials for Electronics

Dielectric ceramics are widely used in applications

such as semiconductor gate dielectrics, actuators,

capacitors, and resonators or filters for microwave

communications. For simple systems, first-principles

(FP) methods allow direct calculations of

low-temperature dielectric constants. For complex

systems, and for rational new materials design,

larger scale modeling is required. Multiscale

effective Hamiltonian (EH) models derived from

FP calculations retain high accuracy and allow

phenomena caused by chemical ordering, defects,

and changes in temperature to be explored. The EH

provides a bridge from FP calculations (≤ 100

atoms) to the needed computations with hundreds

of thousands of atoms. We are developing a

methodology to enable automatic EH generation

for real three-dimensional systems.

Eric Cockayne and Benjamin P. Burton

Materials that are optimized for industrial

applications are generally solid solutions in which

the configuration of ions on mixed ion sites strongly

affects the physical properties. To model these

phenomena, detailed FP calculations are performed

on a variety of perfectly ordered systems. For example,

PbMg1/3Nb2/3O3 (PMN) is the main component of

recently discovered materials with ultrahigh piezoelectric

constants. PMN presents a singular challenge, because

the details of Mg-Nb ordering are not fully known.

To better understand PMN, we studied various

PMN composition supercells with 15 to 30 atoms.

A comparison of fully relaxed structures predicts a

ground state ordering different from that previously

assumed. The two lowest-energy structures found are

most compatible with the “random site model” of PMN

deduced from experiment. Calculated infrared spectra

(directly related to the dielectric function) also show

that the two lowest energy structures are most similar

to experiment.

For the (CaAl1/2Nb1/2O3)1–x–(CaTiO3)x (CAN-CT)

system of microwave dielectric interest, a cluster

expansion EH model for the low temperature dielectric

constant was developed to calculate the dielectric

constant for an arbitrary CAN-CT configuration as

a function of x and Ti-Al-Nb ordering. Work is in

progress to parameterize similar models for other solid

solution systems.

Temperature dependent dielectric properties can

be modeled with Monte Carlo and molecular dynamics

simulations based on EHs. The EH for a heterovalent

solid solution includes the random local electric fields

Theory and Modeling of Dielectric Materials

Figure 1: Predicted ground-state ordering of Mg (red) and

Nb (blue) in PbMg1/3Nb2/3O3.

generated by mixing differently charged ions in an

alloy. We compiled a catalog of the possible local field

directions in the nearest-neighbor approximation.

By including local fields in an EH for PbSc1/2Nb1/2O3

(PSN), we can reproduce the experimental observation

that the dielectric peak of PSN, as a function of

temperature, is broadened when nanoscale ordered

domains are present.

Defects also affect physical properties. We computed

the dipole moment of a Pb-O divacancy in PbTiO3

from FP. Its moment is 2.28 e times the distance between

the original Pb and O sites. The large electric fields

produced by such defects have been incorporated into

our EH for PSN.

Effective Hamiltonians for dielectrics and ferroelectrics

are based on an efficient “lattice Wannier function” (LWF)

description of the lattice dynamics of these systems. We

have found a principle for automatically generating LWF

and have demonstrated that it works on one-dimensional

model systems. The method works equally well for

chemically ordered systems, disordered systems, and

systems with defects. This is a highly promising step

towards automatic generation of effective Hamiltonians

for real three-dimensional systems, which will make

these EH methods accessible to non-experts.

Contributors and Collaborators

I. Levin, M. Lufaso, S. Tinte (Ceramics Division,

NIST); P. Gehrig (NIST Center for Neutron Research,

NIST); A. van de Walle (Northwestern U.); S.A.

Prosandeev (Rostov State U.); U.V. Waghmare (JNCASR)
39

Program Overview

New materials and devices are radically changing

the treatment of injury and disease, yet it is clear that

within this rapidly evolving segment of the materials

industry, a basic measurement infrastructure does

not exist. The Biomaterials Program develops

measurement methods, standards, and fundamental

scientific understanding at the interface between the

materials and biological sciences. For the health care

industry, we focus on dental and medical sectors that

apply synthetic materials for replacement, restoration,

and regeneration of damaged or diseased tissue.

Three primary foci exist within this program:

biocompatibility, biomaterials characterization, and

materials measurements applied to biological systems.

Whether the medical issue involves implanting

a hip- or knee-joint prosthesis, a synthetic bone graft,

or a tissue engineering scaffold into the human body,

one primary issue is biocompatibility. Using our

expertise in materials science, we have developed

suitable Reference Materials (RM) for investigating

biocompatibility and implant suitability. Research has

focused on measuring cellular response to powders

and bulk materials that are candidates for implants;

recently, we produced a realistic wear particle Standard

Reference Material (SRM® 2880) for bioactivity testing.

Work on quantitative methods of biomaterials

characterization includes assays for adhesion,

viability, proliferation, and differentiation of bone

cells, 3-dimensional structural/functional imaging

of tissue in-growth, and biochemical assays to

quantify inflammatory responses to synthetic materials.

The focus of this effort is bridging the gap between

fundamental knowledge and the product development

needs in industry. For example, in collaboration with

the Chemical Science and Technology Laboratory,

we are developing measurement methodologies and

reference materials to assess interactions in complex

systems of living cells with synthetic materials.

The expected outcome of this work includes reference

substrates that induce specific cellular responses,

and engineered DNA vectors to act as fluorescent

reporters of cellular responses.

Another example of our effort to bridge this gap

is our collaboration with the dental industry, which

is primarily composed of small manufacturers with

limited R&D capability. Collaborations with the

American Dental Association Foundation (ADAF)

develop improved materials and materials measurements

techniques, patent and license these inventions, and,

most importantly, provide a technical foundation.

Research focuses on improved understanding of the

synergistic interaction of the phases of polymer-based

composites and the mechanisms of adhesion to dentin

Biomaterials

and enamel. This approach will ultimately lead to

materials with improved durability, toughness, and

adhesion to contiguous tooth structure. We also

collaborate with the ADAF to develop metrology

for the biocompatibility of synthetic bone grafts.

In this era of interdisciplinary research,

we provide an added dimension. By taking a

physical/mechanical approach to how cells function,

respond, and remodel in interaction with synthetic

materials, we provide skill sets typically absent in the

biomedical community. Mechanical properties issues

also arise when considering synthetic bone grafts

and tissue engineering scaffolds. Complementing

traditional bulk mechanical property measurements,

combinatorial approaches are being developed to

identify compositions and surface features that

affect properties such as biocompatibility and

mechanical durability.

Our mechanical property metrology extends further

to biological systems that span the range from individual

neurons and muscle cells to complete pulmonary

arteries. This necessitates the development of unique

mechanical testing platforms and application of a

materials science approach to understanding integrated

properties. Recently, we have developed a bioreactor

capable of applying biaxial stresses and allowing

monitoring of the stress and strain of a two-dimensional

scaffold sheet during tissue growth.

Fundamental to the Biomaterials program is

recognition of the need for an integrated systems

approach. Collaborations among and between project

teams are critical to progress against the ambitious

goals of this program.

Contact: Eric J. Amis (Polymers Division),

Stephen M. Hsu (Ceramics Division)
40

Biomaterials

The average life of an artificial human joint

replacement is about ten to fifteen years. Failures

of these joints have been traced to adverse human

bioactivity towards wear particles generated inside

the body from joint movements. The detailed

mechanism of this bioreactivity is well understood,

especially the size and shape influence. Conclusions

from several industrial workshops held at NIST in

the last several years have suggested a strong need

for a realistic wear particle reference material

for bioactivity testing. We have responded to this

need by producing a controlled size and shape

UHMWPE wear particle Standard Reference

Material, SRM 2880, to be made available in

September 2004 for bioactivity testing.

Stephen M. Hsu

To generate wear particles of controlled size and

shape, random particle generators such as

cryogenic grinding and wear testing cannot be used.

Instead, we tested the idea of using surface texturing

to provide controlled abrasion. As a preliminary test,

we textured a stainless steel surface using abrasives

to produce linear and cross-hatched grooves.

Subsequent rubbing of ultrahigh molecular weight

polyethylene (UHMWPE) pins against the surface

produced promising results, but the particle size and

shape distributions were too wide. We then used a

semiconductor microfabrication technique to produce

specific cutting edges of controlled dimensions using

silicon covered with a thin film of chromium for

wear resistance. This process, Figure 1, successfully

generated suitable particles in distilled water.

Controlled Size and Shape UHMWPE Particle SRM

for Bioactivity Testing

Figure 1: Polyethylene pins rubbing on a textured surface to

generate wear particles.

Figure 2: Surface texture features and the resulting particles.

Different surface texture patterns were designed to

generate particles of various sizes and shapes. Prof. Paul

Wooley of Wayne State University carried out air pouch

bioactivity tests in mice and found that elongated particles

were more highly reactive than small round particles.

The results, published in a biomaterials journal, generated

considerable interest in the scientific community.

 Using this method, different size and shape particles

were produced in large quantity under sterile conditions.

Two different types of particles were produced: round

particles and elongated particles with three different

sizes. The particles were packaged in sealed amber

ampoules under an inert atmosphere, to avoid oxidation,

and were certified in terms of average diameter, aspect

ratio, and the minimum number of particles per ampoule.

To avoid potential cell culture influence, no dispersant

was used in the SRM, but a dispersant that can be used

to provide a more accurate particle count per ampoule

was recommended.

A unit package of SRM 2880 consists of two

sets of ampoules: one containing round particles

and the other containing elongated particles. This

SRM is scheduled to be available for distribution

(https://srmors.nist.gov/) in September 2004.

Contributors and Collaborators

Y. Liang, P.P. Kavuri, H-W. Fang (Ceramics

Division, NIST); J. Tesk (Polymers Division, NIST);

D. Schroder (Biomet); C. Merrit (FDA); P. Wooley

(Wayne State University); J. Sangers (U of Maryland)
41

Data, Reference Materials, and Measurement Methods

NIST Standard Reference Database 31

NIST/ACerS Phase Equilibria Diagrams. Produced

jointly by NIST and the American Ceramic Society;

thirteen regular book volumes, four topical volumes,

three annual volumes, and a computerized database on

CD ROM; more than 53,000 units have been sold; the

current CD contains approximately 20,000 critically

evaluated diagrams and 15,000 expert commentaries.

(Free demo CD available from NIST.) Available for

purchase at http://www.nist.gov/srd/nist31.htm.

Data, Reference Materials, and Measurement Methods

NIST Standard Reference Database 15

NIST/Sandia/ICDD Electron Diffraction Database.

Chemical, physical, and crystallographic information for

more than 81,500 materials, including minerals, metals,

intermetallics, and general inorganic compounds; the

database and associated software enable highly selective

identification procedures for microscopic and

macroscopic crystalline materials. Available for

purchase at http://www.nist.gov/srd/nist15.htm.

NIST Standard Reference Database 83

NIST Structural Database. Crystallographic and

atomic position information for metallic crystalline

substances, including alloys, intermetallics and

minerals; the database is distributed in an ASCII

format, convenient for reading into a variety of

database management systems or processing by

independent software routines. Available for

purchase at http://www.nist.gov/srd/nist83.htm.

NIST Standard Reference Database 84

FIZ/NIST Inorganic Crystal Structure Database,

Release 2004/1 (February 2004); produced

cooperatively by the Fachinformationszentrum

Karlsruhe (FIZ) and NIST; a comprehensive

collection of full structural crystallography data

of inorganic compounds; contains more than

70,000 entries. Available for purchase at

http://www.nist.gov/srd/nist84.htm.

NIST Standard Reference Database 30

Structural Ceramics Database. Physical,

mechanical, and thermal properties; more than

38,000 numeric values. Available online at

http://www.ceramics.nist.gov/srd/scd/scdquery.htm.

NIST Standard Reference Database 62

High Temperature Superconductors. Physical,

mechanical, thermal, and superconducting properties;

more than 30,000 numeric values. Available online at

http://www.ceramics.nist.gov/srd/hts/htsquery.htm.

The Ceramics Division has been a vigorous

participant in support of NIST’s core mission

as a Measurement Standards Institute. The Division

has made significant contributions to all aspects of

standard reference databases, standard reference

materials, and standard measurement methods and

practices. As may be observed here, the products

established by the Division provide a substantial

resource spanning a considerable sector of

materials metrology.

DATABASES

Crystallography

NIST principal investigator:

V.L. Karen

Phase Equilibria

Diagrams

NIST principal investigator:

T.A. Vanderah

Materials Properties

NIST principal investigator:

R.G. Munro
42

NIST Property Data Summaries

Focused studies with comprehensive property

sets for specific materials and topical studies focused

on one property for a wide range of materials.

Available as follows:

■ Alumina, http://www.ceramics.nist.gov/srd/

summary/scdaos.htm

■ Silicon Carbide, http://www.ceramics.nist.gov/srd/

summary/scdscs.htm

■ Titanium Diboride, http://www.ceramics.nist.gov/

srd/summary/scdtib2.htm

■ Yttrium Barium Copper Oxide, http://

www.ceramics.nist.gov/srd/summary/htsy123.htm

■ Elastic Moduli Data, http://www.ceramics.nist.gov/

srd/summary/emodox00.htm

■ Fracture Toughness Data, http://

www.ceramics.nist.gov/srd/summary/ftmain.htm

■ Fracture Data for Oxide Glasses, http://

www.ceramics.nist.gov/srd/summary/glsmain.htm

Standard Reference Material 1018b

Glass Beads — Particle Size Distribution, a particle

size standard for size range 220 μm to 750 μm.

Standard Reference Material 1019b

Glass Beads — Particle Size Distribution, a particle

size standard for size range 750 μm to 2450 μm.

Standard Reference Material 659

Particle Size Distribution for Sedigraph Calibration,

a particle size standard for size range 0.2 μm to 10 μm.

Standard Reference Material 8010

Sand for Sieve Analysis.

Standard Reference Material 1982

Zirconia Thermal Spray Powder — Particle Size

Distribution, a particle size standard for size range

10 μm to 150 μm.

Standard Reference Material 1984

Thermal Spray Powder — Particle Size Distribution,

Tungsten Carbide/Cobalt (Acicular), a particle size

standard for size range 9 μm to 30 μm.

Standard Reference Material 1985

Thermal Spray Powder — Particle Size Distribution,

Tungsten Carbide/Cobalt (Spheroidal), a particle size

standard for size range 18 μm to 55 μm.

Characterization of Fracture Origins

Provides an efficient and consistent methodology

to locate and characterize fracture origins in

advanced ceramics. May be used in conjunction

with ASTM standard C-1322. Available online at

http://www.ceramics.nist.gov/webbook/fracture/

fracture.htm.

STANDARD REFERENCE MATERIALS

SRMs produced by the Ceramics Division are

available for purchase at http://ts.nist.gov/ts/htdocs/

230/232/232.htm.

Data, Reference Materials, and Measurement Methods

Standard Reference Material 1021

Glass Beads — Particle Size Distribution, a particle

size standard for size range 2 μm to 12 μm.

Standard Reference Material 1003c

Glass Beads — Particle Size Distribution, a particle

size standard for size range 20 μm to 50 μm.

Standard Reference Material 1004b

Glass Beads — Particle Size Distribution, a particle

size standard for size range 40 μm to 150 μm.

Standard Reference Material 1017b

Glass Beads — Particle Size Distribution, a particle

size standard for size range 100 μm to 400 μm.

Fractography

NIST principal investigator:

G.D. Quinn

Particle Size

Metrology SRMs

NIST principal

investigator:

J. Kelly
43

Standard Reference Material 2830

Knoop Hardness of Ceramics.

Standard Reference Material 2831

Vickers Hardness of Ceramics and Hardmetals.

Standard Reference Material 2100

Fracture Toughness of Ceramics.

Standard Reference Material 640c

Silicon Powder Line Position/Profile SRM, silicon

powder, used for calibration of line position and

characterization of the instrument profile function,

certified with respect to lattice parameter.

Standard Reference Material 660a

LaB6 Powder Line Position/Profile SRM, LaB6

powder, used to characterize the instrument profile

function and calibrate line position, certified with

respect to lattice parameter.

Standard Reference Material 675

Mica Powder Line Position (Low Angle) SRM,

synthetic fluorophlogopite mica powder, used to

characterize the instrument line position at low

two-theta angle, certified with respect to lattice parameter.

Standard Reference Material 1976a

Instrument Response, a sintered alumina plate,

certified with respect to lattice parameter and

diffraction intensity as a function of two-theta angle

(texture), used for general calibration of diffraction

equipment, with respect to line position and intensity,

via conventional data analysis methods.

Standard Reference Material 676

Alumina Powder for Quantitative Analysis, high

purity alumina powder for general quantitative analyses

via powder diffraction methods, certified with respect

to lattice parameter.

Standard Reference Material 1878a

Quantification of Alpha Quartz, respirable (5 μm)

powders, certified with respect to amorphous content,

used primarily by the industrial hygiene community for

quantification of quartz in airborne dust.

Standard Reference Material 1879a

Quantification of Cristobalite, respirable (5 μm)

powders, certified with respect to amorphous content,

used primarily by the industrial hygiene community for

quantification of cristobalite in airborne dust.

Standard Reference Material 674b

Quantitative Analyses, four powders, Cr2O3, CeO2,

TiO2 and ZnO, allows the user to match the linear

attenuation of the standard to that of the unknown,

certified for phase purity using neutron time-of-flight

diffraction. Supplemental information will include the

reference intensity ratio (RIR) or I/Ic value and the

lattice parameters as determined with conventional

x-ray diffraction.

Standard Reference Material 656

Si3N4 Powder for Quantitative Analysis, two samples

of high purity silicon nitride powder, one high in the

alpha phase while the other is high in the beta phase,

for quantitative analyses via powder diffraction

methods, certified with respect to phase purity

and the alpha to beta phase ratio.

Standard Reference Material 2910

Calcium Hydroxyapatite, calcium hydroxyapatite

powder for use in evaluating calcium apatites, primarily

in the field of biological research, certified with respect

to lattice parameters and phase purity.

Standard Reference Material 1979

Crystallite Size/Line Broadening, CeO2 and

ZnO powder which exhibits diffraction line profile

broadening due to crystallite size effects, certified with

respect to particle size via XRD line profile analysis,

applicable to a range of materials research and industrial

interests concerned with crystallite size determination

via powder diffraction techniques.

Data, Reference Materials, and Measurement Methods

Mechanical

Properties SRMs

NIST principal

investigator:

G.D. Quinn

X-Ray Metrology

SRMs

NIST principal

investigator:

J. Cline
44

STANDARD TEST METHODS

Data, Reference Materials, and Measurement Methods

ASTM C 1211 (2002)

Standard Test Method for Flexural Strength of

Advanced Ceramics at Ambient Temperature.

ISO Standard 14704 (2000)

Fine Ceramics (Advanced Ceramics, Advanced

Technical Ceramics) — Test Method for Flexural

Strength of Monolithic Ceramics at Room

Temperature.

ISO Standard 18756 (2003)

Fine Ceramics (Advanced Ceramics, Advanced

Technical Ceramics) — Determination of Fracture

Toughness of Monolithic Ceramics at Room

Temperature by the Surface Crack in Flexure

(SCF) Method.

ISO Standard 17565 (2004)

Fine Ceramics (Advanced Ceramics, Advanced

Technical Ceramics) — Test Method for Flexural

Strength of Monolithic Ceramics at Elevated

Temperature.

ASTM C 1161 (2002)

Standard Test Method for Flexural Strength of

Advanced Ceramics at Ambient Temperature.

ASTM C 1322 (2002)

Standard Practice for Fractography and Characterization

of Fracture Origins in Advanced Ceramics.

ASTM C 1326 (2003)

Standard Practice for Knoop Hardness of Advanced

Ceramics.

ASTM C 1327 (2003)

Standard Practice for Vickers Hardness of Advanced

Ceramics.

ASTM F 2094 (2001)

Standard Specification for Silicon Nitride Bearing Balls.

This standard addresses the basic quality, physical

and mechanical properties, and test requirements for

silicon nitride balls used for ball bearings and other

specialty applications.

Mechanical

Property

Test Methods

NIST principal

investigator:

G.D. Quinn
45

Ceramics Division FY04 Annual Report Publication List

Ceramics Division FY04 Annual Report Publication List

Abraham, D.P., R.D. Twesten, M. Balasubramanian,

J. Kropf, D. Fischer, J. McBreen, I. Petrov, and K. Amine,

“Microscopy and Spectroscopy of Lithium Nickel Oxide

Based Particles used in High-Power Lithium-Ion Cells,”

Journal of the Electrochemical Society 150 [11],

pp. A1450–A1456 (2003).

Antipov, Y.A., T.-J. Chuang, and H. Gao, “On the

Integro-Differential Equation associated with Diffusive

Crack Growth Theory,” Quarterly Journal of Applied

Math. and Mechanics 56 [2], pp. 289–310 (2003).

Banerjee, S., T. Hemraj–Benny, M. Balasubramanian,

D.A. Fischer, J.A. Misewich, and S.S. Wong, “Ozonized

Single-walled Carbon Nanotubes Investigated using

NEXAFS Spectroscopy,” Chemical Communications,

Issue 7, pp. 772–773 (2004).

Bhushan, B., H. Liu, and S.M. Hsu, “Adhesion

and Friction Studies of Silicon and Hydrophobic and

Low Friction Films and Investigation of Scale Effects,”

ASME J. of Tribology 126, pp. 1–8 (2004).

Burnett, D.J., A.M. Gabelnick, D.A. Fischer,

S.M. Yalisove, and J.L. Gland, “Defect Enhanced

Carbon Monoxide Oxidation at Elevated Oxygen

Pressures on a Pt/Al2O3 Thin Film,” J. Phys. Chem. B

108, pp. 5314–5323 (2004).

Burton, B.P., E. Cockayne, and U. Waghmare,

“Random Fields in A(B1/2

3+B’1/25+)O3 and

A(B1/3

2+ B2/35+) O3 Relaxor Ferroelectrics,” TMS

Letters 1, pp. 29–30 (2004).

Claessen, R., W. Drube, L. Kover, P. Lefevre,

V.N. Strocov, J.C. Woicik, and J. Zegenhagen,

“High-Energy Photoelectron Spectroscopy,”

PETRA III Technical Design Report (TDR),

http://www-hasylab.desy.de/facility/upgrade/

petra_tdr.htm, Hasylab, Hamburg, Germany (2004).

Claeys, C.L., W. Wong-Ng, and K.M. Nair, eds.,

Proceedings of Electrochemical Society/American

Ceramic Society Symposium on Low Temperature

Electronics and Low-Temperature Cofired Ceramics

Based Electronic Devices, October 12–17, 2003,

Orlando, FL, Electrochemical Society/American

Ceramic Society (2003).

Cockayne, E., “First Principles Calculations of the

Dielectric Properties of Perovskite-Type Materials,”

Journal of the European Ceramic Society 23,

pp. 2375–2379 (2003).

Cockayne, E., and B.P. Burton, “Dipole Moment

of a Pb-O Vacancy Pair in PbTiO3,” Phys. Rev. B

69, Art. No. 144116 (2004).

Devadoss, C., Y. Wang, R. Puligadda, J.L. Lenhart,

E.L. Jablonski, D.A. Fischer, S. Sambasivan,

E.K. Lin, and W.L. Wu, “Investigation of BARC-resist

interfacial interactions,” Proceedings of SPIE

Optical Microlithography, February 25–28, 2003,

Santa Clara, CA, SPIE Vol. 5040, pp. 912–922 (2003).

Dobbins, T.A., A.J. Allen, J. Ilavsky, G.G. Long,

P.R. Jemian, A. Kulkarni, and H. Herman, “Recent

Developments in the Characterization of Anisotropic

Void Populations in Thermal Barrier Coating using

Ultra-Small Angle X-ray Scattering,” Ceramic

Engineering and Science Proc. 24 [3], edited by

H.-T. Lin and S. Mrityunjay, American Ceramic

Society, pp. 517–524 (2003).

Fahmi, M.M., A. Khan, J.A. Griffin, G.L. Harris,

L.H. Robins, A.G. Birdwell, Y.S. Kang, D.T. Smith,

T. Steiner, and S. Noor Mohammad, “Nitrogen-Activated

Bowing of Dilute InyGa1–yAs1–xNx based on

Photoreflectance Studies,” J. Appl. Phys. 94,

pp. 7576–7580 (2003).

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“A Study of the Mechanism of UHMWPE Particle

Generation with Microfabricated Surface Features:

In situ Observation of Single-Tip Sliding Tests,”

Proceedings of the 7th World Biomaterials Congress,

Sydney, Australia, May 17–21, 2004, Society for

Biomaterials, pp. 341 (2004).

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“Analysis of UHMWPE Particle Shape Effects

on Bioactivity from the Physical Viewpoint of

Phagocytosis Process,” Proceedings of the 7th World

Biomaterials Congress, Sydney, Australia, May 17–21,

2004, Society for Biomaterials, pp. 1328 (2004).

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“Generation of Narrowly Distributed Ultra-High

Molecular Weight Polyethylene Particles by Surface

Texturing Techniques,” J. of Biomedical Materials

Research 67B, pp. 741–749 (2003).

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“Surface-Texture Design to Generate Narrowly

Distributed UHMWPE Particles with Specific Sizes and

Shapes,” Proceedings of the 7th World Biomaterials

Congress, Sydney, Australia, May 17–21, 2004,

Society for Biomaterials, pp. 1131 (2004).

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“Surface texture design to generate specific sizes and

shapes of UHMWPE wear particles,” Mat.-wiss. u.

Werkstofftech 34 [10/11], pp. 976–988 (2003).
46

Ceramics Division FY04 Annual Report Publication List

Fang, H.-W., S.M. Hsu, and J.V. Sengers,

“Ultra-High Molecular Weight Polyethylene Wear

Particle Effects on Bioactivity,” NIST-SP 1002 (2003).

Fischer, D.A., K. Efimenko, R.R. Bhat, and

S. Sambasivan, “Mapping Surface Chemistry and

Molecular Orientation with Combinatorial Near-Edge

X-ray Absorption Fine Structure,” Macromolecules

Rapid Communications 25, pp. 141–149 (2004).

Genzer, J., D.A. Fischer, and K. Efimenko,

“Fabricating Two-Dimensional Molecular Gradients

via Asymmetric Deformation of Uniformly-Coated

Elastomer Sheets,” Advanced Materials 15,

pp. 1545–1547 (2003).

Hackley, V.A., “Techniques for Measurements in

Concentrated Systems: Applications of Electromagnetic

Scattering and Ultrasound,” Concentrated Colloidal

Dispersions: Theory, Experiment and Applications,

edited by P. Somasundaran and B. Markovic, American

Chemical Society, Washington D.C., Chapter 5,

pp. 52–68 (2004).

Hackley, V.A., L. Lum, V. Gintautas, and

C.F. Ferraris, Particle Size Analysis by Laser

Diffraction Spectrometry: Application to Cementitious

Powders, NIST Interagency Report 7097, DoC

Technology Administration, National Institute of

Standards and Technology, Gaithersburg, MD, (2004).

Haugan, T.J., J.M. Evans, J.C. Tolliver,

I. Maartense, P.N. Barnes, W. Wong-Ng, L.P. Cook,

and R. Shull, “Flux Pinning and Properties of Solid

Solution (Y,Nd)1+xBa2–xCu3O7–d Superconductors

Processed in Air and Partial Oxygen Atmospheres,”

Fabrication of Long-Length & Bulk HTS Conductors,

Ceramic Transactions 149, edited by R. Meng, A. Goyal,

and W. Wong-Ng, 105th Annual Meeting of the

American Ceramic Society (ACerS), April 27–30, 2003,

Nashsville, TN, pp. 151 (2004).

Hexemer, A., E. Sivaniah, E.J. Kramer, M. Xiang,

X. Li, D.A. Fischer, and C.K. Ober, “Managing

Polymer Surface Structure Using Surface Active Block

Copolymers in Block Copolymer Mixtures,” Journal

of Polymer Science, Part-B Polymer Physics 42,

pp. 411–420 (2003).

Hsu, S.M., “Molecular Basis of Lubrication,”

Tribology International 37 [7], pp. 553–559 (2004).

Hsu, S.M., “Nanolubrication: Concept and Design,”

Tribology International 37 [7], pp. 537–545 (2004).

Ilavsky, J., P.R. Jemian, A.J. Allen, and G.G. Long,

“Versatile USAXS (Bonse-Hart) Facility for Advanced

Materials Research,” Proceedings of Eighth

International Conference on Synchrotron Radiation

Instrumentation, San Francisco, CA, edited by

T. Warwick, et al., American Institute of Physics,

pp. 510–513 (2004).

 Jablonski, E.L., J.L. Lenhart, S. Sambasivan,

D.A. Fischer, R.L. Jones, E.K. Lin, W.L. Wu,

D.L. Goldfarb, K. Temple, M. Angelopoulos, and H. Ito,

“NEXAFS Measurements of Chemically Amplified

Photoresists: Surface versus Bulk Chemistry,”

Proceedings of 2003 International Conference on

Characterization and Metrology for ULSI Technology,

March 24–28, 2003, NIST, Gaithersburg, MD,

Vol. 683, pp. 439–443 (2003).

Jablonski, E.L., V.M. Prabhu, S. Sambasivan,

E.K. Lin, D.A. Fischer, D.L. Goldfarb, M. Angelopoulos,

and H. Ito, “NEXAFS Measurements of 157 nm

Photoresist Blends: Surface v. Bulk Chemistry,”

J. Vac. Sci. Technol. B 21, pp. 3162–3165 (2003).

Jablonski, E.L., S. Sambasivan, E.K. Lin,

D.A. Fischer, C. Devadoss, and R. Puligadda,

“NEXAFS Measurements of the Interface between

Bottom Anti-reflective Coatings and a Model

Deprotected Photoresist,” J. Vac. Sci. Techno. B

21, pp. 3153–3156 (2003).

Jang, M.-H., W. Wong-Ng, R. Shull, L.P. Cook,

and D.S. Suh, “Flux Loss Measurements of

Ag-Sheathed Bi-2223 Tapes,” American Ceramic

Society, Nashville, TN (2003). Fabrication of

Long-Length & Bulk HTS Conductors, Ceramic

Transactions 149, edited by R. Meng, A. Goyal, and

W. Wong-Ng, 105th Annual Meeting of the American

Ceramic Society (ACerS), April 27–30, 2003,

Nashsville, TN, pp. 83 (2004).

Kaduk, J.A., W. Wong-Ng, and G.S. Nolas,

“X-ray Diffraction Patterns of two Germanium

Clathrates, Sr8Ga16Ge30 and Cs8Na16Ge136:

Promising Candidates for Thermoelectric Applications,”

The Rigaku Journal 20, pp. 2–11 (2003).

Karen, V.L., and A. Belsky, “FIZ/NIST Inorganic

Crystal Structure Database,” NIST Standard Reference

Database 84, NIST, Gaithersburg, Maryland and FIZ,

Karlsruhe, Germany, Release 2003/2 and 2004/1.

Kulkarni, A., A. Goland, H. Herman, A.J. Allen,

J. Ilavsky, G.G. Long, C.A. Johnson, and J.A. Ruud,

“Microstructure-Property Correlations in Industrial

Thermal Barrier Coatings,” J. Am. Ceram. Soc 87 [7],

pp. 1294–1300 (2004).
47

Ceramics Division FY04 Annual Report Publication List

 Kulkarni, A., J. Gutleber, S. Sampath, A. Goland,

W.B. Lindquist, H. Herman, A.J. Allen, and B. Dowd,

“Studies of the Microstructure and Properties of

Dense Ceramic Coatings Produced by High-Velocity

Oxygen-Fuel Combustion Spraying,” Mater. Sci.

Eng. A 369, pp. 124–137 (2004).

Larsen-Basse, J., X. Wang, L.K. Ives, and

S.M. Hsu, “Some Friction Experiments with Textured

Surfaces,” Proceedings of the 11th Nordic Symposium

on Tribology, Harstadt, Norway, June 1–5, 2004,

pp. 751 (2004).

Lee, J., S. Lee, V.A. Hackley, and U. Paik,

“Influence of [Ba + Ca]/[Ti + Zr] Ratio on the

Interfacial Property of (Ba,Ca)(Ti,Zr)O3 (BCTZ)

Powders in an Aqueous Medium,” Journal of the

American Ceramic Society 86 [6], pp. 1034–1036

(2003).

Lee, S., U. Paik, V.A. Hackley, Y-G. Jung, and

K-J. Yoon, “Microstructure and Permittivity of Sintered

BaTiO3: Influence of Particle Surface Chemistry in

an Aqueous Medium,” Materials Research Bulletin 39,

pp. 93–102 (2004).

Lenhart, J.L., D.A. Fischer, S. Sambasivan, E.K. Lin,

C.L. Soles, R.L. Jones, W.L. Wu, D.L. Goldfarb,

and M. Angelopoulos, “Utilizing Near Edge X-ray

Absorption Fine Structure to Probe Interfacial Issues

in Photolithography,” Polymers for Microelectronics

and Nanoelectronics, ACS Symposium Series 874,

edited by Qinghuang Lin, pp. 98–117 (2004).

Lenhart, J.L., D.A. Fischer, S. Sambasivan, E.K. Lin,

R.L. Jones, C.L. Soles, W.L. Wu, D.L. Goldfarb, and

M. Angelopoulos, “X-ray Absorption Spectroscopy

for Probing Interfacial Issues in Photo-lithography,”

Proceedings of SPIE Advances in Resist Technology

and Processing XX, February 25–28, 2003,

Santa Clara, CA, SPIE Vol. 5039, pp. 343 (2003).

Levin, I., T.G. Amos, L. Farber, S.M. Bell,

R.S. Roth, T.A. Vanderah, and B.H. Toby, “Phase

Equilibria, Crystal Structures, and Dielectric Anomaly

in the BaZrO3-CaZrO3 System,” J. Solid State Chem.

175, pp. 170–181 (2003).

Levin, I., R.D. Leapman, M. Kovler, and Y. Roizin,

“Beam-Induced Nitrogen Segregation During EELS

Measurements on the Silicon Oxide-Nitride-Oxide

Stacks,” Appl. Phys. Lett. 83 [8], pp. 1548–1550

(2003).

 Lufaso, M.W., “Crystal Structure, Modeling,

and Delectric Property Relationships of 2:1 Ordered

Ba3MM ́2O9 (M = Mg, Ni, Zn; M ́ = Nb, Ta)

Perovskites,” Chemistry of Materials 16,

pp. 2148–2156 (2004).

Marsh, A.L., D.J. Burnett, D.A. Fischer, and

J.L. Gland, “Benzene Intermediates and Mechanisms

during Catalytic Oxidation on the Pt (111) Surface

Using Soft X-ray Fluorescence Methods,” J. Phys.

Chem. B 107, pp. 12472–12479 (2003).

Marsh, A.L., D.J. Burnett, D.A. Fischer, and

J.L. Gland, “Soft X-ray Studies of Toluene Catalytic

Oxidation on the Pt(111) Surface,” Journal of

Physical Chemistry B 108, pp. 605–611 (2004).

Meng, R., A. Goyal, and W. Wong-Ng, eds.,

Fabrication of Long-Length & Bulk HTS Conductors,

Ceramic Transactions 149, 105th Annual Meeting

of the American Ceramic Society (ACerS),

April 27–30, 2003, Nashsville, TN (2004).

Mighell, A.D., “The Normalized Reduced Form

and Cell: Mathematical Tools for Lattice Analysis —

Symmetry and Similarity,” J. Res. Natl. Inst. Stand.

Technol. 108, pp. 447–452 (2003).

Mighell, A.D., W. Wong-Ng, and G.J. Piermarini,

“Howard McMurdie: Going Strong at 98, 60 Years

with JCPDS/ICDD and 75 years at NBS/NIST,”

Powd. Diffr. 18 [3], pp. 271–272 (2003).

Munro, R.G., Ceramics WebBook, Evaluated Data,

http://www.ceramics.nist.gov/webbook/

evaluate.htm, Gaithersburg, Maryland (2004).

Paik, U., S. Lee, and V.A. Hackley, “Influence

of Barium Dissolution on the Electrokinetic Properties

of Colloidal BaTiO3 in an Aqueous Medium,”

Journal of the American Ceramic Society 86 [10],

pp. 1662–1668 (2003).

Prosandeev, S.A., E. Cockayne, and B.P. Burton,

“The Energetics of Li Ion Displacements in

K1–xLixTaO3: First Principles Calculations,”

Physical Review B 68, Art. No. 014120 (2003).

Prosandeev, S.A., E. Cockayne, and B.P. Burton,

“First-Principles Calculations of Ionic Vibrational

Frequencies in PbMg1/3Nb2/3O3,” Fundamental

Physics of Ferroelectrics 2003, AIP Conference

Proceedings Series 637, edited by Peter K. Davies

and David J. Singh, pp. 46–151 (2003).

Quinn, G., “Reference Materials Available for

Ceramics and Hard Metals,” Journal of Thermal Spray

Technology 13 [2], pp. 171–171 (2004).

Quinn, G.D., J. Eichler, U. Eisele, and J. Rodel,

“Fracture Mirrors in Nanoscale 3Y-TZP,” Journal

of the American Ceramics Society 87 [3],

pp. 513–516 (2004).
48

Ceramics Division FY04 Annual Report Publication List

Ren, W., S. Yang, H. Fang, S.M. Hsu, and

P.H. Wooley, “Distinct Gene Expression of Nuclear

Activator of Nuclear Factor-kB and Rank Ligand in

the Inflammatory Response to Variant Morphologies

of UHMWPE Particles,” J. of Biomaterials 24 [26],

pp. 4819–4826 (2003).

Ridley, A.K., M.L. Machesky, V.A. Hackley,

M.P. Finnegan, and J.F. Banfield, “Surface Charge

Phenomena of Nanocrystalline Anatase,” Geochimica

et Cosmochimica Acta 67 [18], pp. A398–A398 (2003).

Roth, R.S., and T.A. Vanderah, “Experimental

Deterimination of Phase Equilibria Diagrams in

Ceramic Systems,” Proceedings of the 9th Asian

Conference on Solid State Ionics, June 6–11, 2004,

Jeju Island, South Korea, World Scientific, Singapore,

pp. 3–18 (2004).

 Sahiner, M.A., P. Ansari, M.S. Carroll,

C.W. Magee, S.W. Novak, and J.C. Woicik, “XAFS

as a Direct Local Structural Probe in Revealing the

Effects of C Presence in B Diffusion in SiGe Layers,”

Proceedings of the Materials Research Society,

April 12–16, 2004, San Francisco, CA, MRS

Proceedings 810, C11.10.1 (2004).

Sahiner, M.A., C.W. Magee, D.F. Downey,

E. Arevalo, and J.C. Woicik, “The Role of Ge in

Cluster Formation in B and BF2 Implanted Si Wafers

after Ge Pre-amorphization,” Proceedings of the

Materials Research Society, December 1–5, 2003,

Boston, MA, MRS Proceedings 792, R7.3.1 (2004).

Sambasivan, S., D.A. Fischer, M.C. Shen, and

S.M. Hsu, “Molecular Orientation of Ultra-high

Molecular Weight Polyethylene Induced by Various

Sliding Motions,” Journal of Biomedical Materials

Research Part B: Applied Biomaterials 70 [2],

pp. 278–285 (2004).

Sanford, N.A., L.H. Robins, A.V. Davydov,

A. Shapiro, D.V. Tsvetkov, A.V. Dmitriev, S. Keller,

U.K. Mishra, and S.P. DenBaars, “Refractive Index

Study of AlxGa1-xN Films Grown on Sapphire

Substrates,” J. Appl. Phys. 94, pp. 2980–2991 (2003).

Schenk, P.K., D.L. Kaiser, and A.V. Davydov,

“High Throughput Characterization of the Optical

Properties of Compositionally Graded Combinatorial

Films,” Applied Surface Science 223, pp. 200–205

(2004).

Siegrist, T., and T.A. Vanderah, “Combining

Magnets and Dielectrics: Crystal Chemistry in the

BaO-Fe2O3-TiO2 System,” European J. Inorg.

Chem. 8, pp. 1483–1501 (2003).

Swider, J.R., V.A. Hackley, and J. Winter,

“Characterization of Chinese Ink in Size and Surface,”

Journal of Cultural Heritage 4, pp. 175–186 (2003).

Tang, Z., A.F. Bower, and T.–J. Chuang,

“Numerical Simulations of the Growth and Deflection

of a Stress-Corrosion Notch on the Interface between

Two Reactive Solids,” International Journal of

Fracture 127 [1], pp. 1–20, (2004).

Tewari, Y.B., P.D. Gery, M.D. Vaudin, A.D. Mighell,

R. Klein, and R.N. Goldberg, “Saturation Molalities and

Standard Molar Enthalpies of Solution of Cytidine(cr),

Hypoxanthine(cr), Thymidine(cr), Thymine(cr),

Uridine(cr), and Xanthine(cr) in H2O(l),” J. Chem.

Thermodynamics 36, pp. 645–658 (2004).

Vanderah, D.J., T. Parr, V. Silin, C.W. Meuse,

R.S. Gates, H. La, and G. Valincius, “Isostructural

Self-Assembled Monolayers, 2, Methyl

1-(3-Mercaptopropyl)Oligo(Ethylene Oxide)s,”

Langmuir 20, pp. 1311–1316 (2004).

Vanderah, T.A., V.L. Miller, I. Levin, S.M. Bell,

and T. Negas, “Phase Relations, Crystal Chemistry,

and Dielectric Properties in Sections of the

La2O3-CaO-MgO-TiO2 System,” J. Solid State

Chem. 177, pp. 2023–2038 (2004).

Vanderah, T.A., T. Siegrist, R.S. Roth,

A.P. Ramirez, and R.G. Geyer, “Crystal Structure and

Properties of Ba11FeTi27O66.5,” Eur. J. Inorg. Chem.

2004, pp. 2434–2441 (2004).

Waghmare, U.V., E. Cockayne, and B.P. Burton,

“Ferroelectric Phase Transitions in Nano-Scale

Chemically Ordered PbSc0.5Nb0.5O3 using a

First-Principles Model Hamiltonian,” Ferroelectrics

291, pp.187–196 (2003).

Wittberg, T.N., P.S. Wang, and S.M. Hsu, “Surface

Oxidation Kinetics of SiC Powders in Wet and Dry Air

Studied by X-Ray Photoelectron Spectroscopy and

Bremsstrahlung-Excited Auger Electron spectroscopy,”

Surface and Interface Analysis 35, pp. 773–778

(2003).

Woicik, J.C., “Site-Specific Valence X-ray

Photoelectron Spectroscopy,” Synch. Rad. News

17, pp. 48–53 (2004).

Woicik, J.C., “Site-Specific X-ray Photoelectron

Spectroscopy: A New Method to Measure Partial

Density of Valence States,” Fundamental Physics

of Ferroelectrics 2003, February 2–5, 2003,

Williamsburg, VA, edited by P.K. Davies and

D.J. Singh, AIP Conference Proceedings 677, 261

(2003).

Wong-Ng, W., L.P. Cook, J. Suh, R. Coutts,

J.K. Stalick, I. Levin, and Q. Huang, “BaO-Nd2O3-CuOx

Subsolidus Equilibria Under Carbonate-Free Conditions

at pO2=100 Pa, and at pO2=21 kPa,” J. Solid State

Chem. 173, pp. 476–488 (2003).
49

Ceramics Division FY04 Annual Report Publication List

Wong-Ng, W., L. Swartzendruber, J.A. Kaduk, and

L.H. Bennett, “Magnetic and Structural Properties of

the ‘Brown Phase’ Solid Solution Ba(Nd2–xLax)CuO5,”

Physica C 390, pp. 213–220 (2003).

Wong-Ng, W., L.P. Cook, J. Suh, R. Coutts,

J. Stalick, I. Levin, and Q. Huang, “BaO-Nd2O3-CuOx

Subsolidus Equilibria Under Carbonate-Free Conditions

at pO2 = 100 Pa and at pO2 = 21 kPa,” J. Solid State

Chem. 173, pp. 476–488 (2003).

Wong-Ng, W., L.P. Cook, and J. Suh, “Phase

Relation in the BaO-R2O3-CuOx Systems,” Fabrication

of Long-Length & Bulk HTS Conductors, Ceramic

Transactions 149, 105th Annual Meeting of the

American Ceramic Society (ACerS), April 27–30, 2003,

Nashsville, TN, pp. 163–175 (2003).

Wong-Ng, W., L.P. Cook, J. Suh, and J.A. Kudak,

“Phase relationships in the BaO-Sm2O3-CuOx system

under 100Pa O2,” Physica C 405, pp. 47–58 (2004).

Wong-Ng, W., L.P. Cook, and J. Suh, “Phase

Relations in the Ba-R-Cu-O (R = Nd, Sm, Eu, Gd, Ho,

Y, and Er) Systems Prepared Under AtmosphericallyControlled Conditions,” Proceedings of Frontiers in

Superconducting Materials-New Materials and

Applications, December 1–5, 2003, Boston, MA,

Materials Research Society (MRS), EE8.27 (2003).

Wong-Ng, W., L.P. Cook, I. Levin, M. Vaudin,

J. Suh, and R. Feenstra, “Coated Conductors: Phase

Relations in the Ba-Y-Cu-F-O-H System,” Proceedings

of Frontiers in Superconducting Materials-New

Materials and Applications, December 1–5, 2003,

Boston, MA, Materials Research Society (MRS),

EE2.9 (2003).

Wong-Ng, W., “The 2003 Material Research

Society (MRS) Fall Meeting Report,” Powd. Diffr.

19 [2], pp. 206–208 (2004).

Wong-Ng, W., “Seventh International Conference

on Materials and Mechanisms of Superconductivity

and High Temperature Superconductors (M2S-Rio),”

Powd. Diffr. 19 [2], pp. 209–210 (2004).

Wu, W., S. Sambasivan, C. Wang, W.E. Wallace,

J. Genzer, and D.A. Fischer, “A Direct Comparison

of Surface and Bulk Chain-Relaxation in Polystyrene,”

Euro Physics J. E 12, pp. 127–132 (2003).

Yoon, W.S., M. Balasubramanian, X.Q. Yang,

Z. Fu, D.A. Fischer, and J. McBreen, “Soft X-ray

Absorption Spectroscopic Study of a LiNi0.5Mn0.5O2

Cathode during Charge,” Journal of the Electrochemical

Society 151 [2], pp. A246–A251 (2004).

Yoon, W.S., M. Balasubramanian, X.Q. Yang,

D.A. Fischer, and J. McBreen, “A Combined NMR

and XAS Study on the Local Environments and

Electronic Structures of the Electrochemically Li-ion

Deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 Electrode

System,” Electrochemcial and Solid-State Letters

7 [3], pp. A53–A55 (2004).

 You, J., X. Wang, P. Schenck, T. Vanderah,

M. Harne, C. Cedeno, N. Swanson, and E. Farabaugh,

“Phase Equilibria Diagrams CD-ROM Database,”

NIST Standard Reference Database 31, The American

Ceramic Society, Westerville, OH, Version 3.0

(March 2004).

Zhang, K., G. Rosenbaum, R. Liu, C. Liu,

and D.A. Fischer, “Development of Multilayer

Analyzer Array Detectors for X-ray Fluorescence

at the Third Generation Synchrotron Source,”

Proceedings Synchrotron Radiation Instrumentation:

Eighth International, edited by T. Wawick, et al.,

August 25–29, 2003, San Francisco, CA.,

pp. 957–960 (2004).
50
51

Ceramics Division

Ceramics Division

Chief

Debra L. Kaiser

Phone: 301–975–6119

E-mail: debra.kaiser@nist.gov

Deputy Chief

Ronald G. Munro

Phone: 301–975–6127

E-mail: ronald.munro@nist.gov

Group Leaders

Characterization Methods

Daniel A. Fischer

Phone: 631–344–5177

E-mail: daniel.fischer@nist.gov

Data and Standards Technology

Ronald G. Munro

Phone: 301–975–6127

E-mail: ronald.munro@nist.gov

Electronic and Optoelectronic Materials

Martin L. Green

Phone: 301–975–8496

E-mail: martin.green@nist.gov

Nanomechanical Properties

Douglas T. Smith

Phone: 301–975–6020

E-mail: douglas.smith@nist.gov

Nanotribology

Stephen M. Hsu

Phone: 301–975–6120

E-mail: stephen.hsu@nist.gov
52

Research Staff

Research Staff

Allen, Andrew

andrew.allen@nist.gov

Small-angle x-ray scattering

Small-angle neutron scattering

Ceramic microstructural analysis

Black, David

david.black@nist.gov

Defect microstructures

X-ray imaging

Blendell, John

john.blendell@nist.gov

Ceramic processing

Sintering and diffusion-controlled processes

Burdette, Harold

harold.burdette@nist.gov

X-ray optics

X-ray diffraction imaging

Instrumentation

Burton, Benjamin

benjamin.burton@nist.gov

Calculated phase diagrams

Dielectric ceramics

Chuang, Tze-Jer

tze-jer.chuang@nist.gov

Finite-element modeling

Lifetime predictions

Nanocontact mechanics

Cline, James

james.cline@nist.gov

Standard reference materials

High-temperature x-ray diffraction

Microstructural effects in x-ray diffraction

Rietveld refinement of x-ray diffraction data

Cockayne, Eric

eric.cockayne@nist.gov

First-principles methods

Phase equilibria and properties of dielectrics

Cook, Lawrence

lawrence.cook@nist.gov

High-temperature chemistry

Phase equilibria

DeSanto, Peter

peter.desanto@nist.gov

Electronic ceramics

Solid oxide catalysts

Crystal structure/property relationships

Fischer, Daniel

daniel.fischer@nist.gov

Soft x-ray absorption fine structure

X-ray scattering

Surface science

Fuller, Edwin

edwin.fuller@nist.gov

Microstructural modeling and simulation

Microstructure effects on physical properties

Nanomechanical testing and properties

Toughening mechanisms

Gates, Richard

richard.gates@nist.gov

Tribo-chemistry of ceramics

Chemical analysis of ceramics

Nanometer film thickness measurements

Green, Martin

martin.green@nist.gov

Si microelectronic materials

Electronic ceramics

Combinatorial materials science

Hackley, Vincent

vince.hackley@nist.gov

Particle characterization

Particle dispersion and interface chemistry

Visco-elastic properties of suspensions

Harris, Joyce

joyce.harris@nist.gov

Data acquisition

Digitization and data entry

Hockey, Bernard

bernard.hockey@nist.gov

Transmission electron microscopy

Nanoindentation

Microstructural and defect characterization

Structure and composition of interfaces

Hsu, Stephen

stephen.hsu@nist.gov

Nanotribology

Nanolubrication

Magnetic hard disk interface

MEMs stiction

Huey, Bryan

bryan.huey@nist.gov

Atomic force microscopy

Domain stability

Ferroelectricity
53

Research Staff

Kaiser, Debra

debra.kaiser@nist.gov

Electronic ceramics

Combinatorial material analysis

Karen, Vicky

vicky.karen@nist.gov

Crystallographic databases

Materials informatics

Lattice theory

Structural analysis

Kelly, James

james.kelly@nist.gov

Quantitative scanning electron microscopy

Image analysis

Microstructural analysis

Powder standards

Levin, Igor

igor.levin@nist.gov

Phase transitions in electronic ceramics

Crystal structure determination

Electron microscopy

Lufaso, Michael

michael.lufaso@nist.gov

Crystal structure–physical property correlation

Modeling and prediction of crystal structures

Lum, Lin-Sien

lin-sien.lum@nist.gov

Particle characterization

Instrumentation

Munro, Ronald

ronald.munro@nist.gov

Materials properties of advanced ceramics

Data evaluation and validation

Analysis of data relations

Paul, Albert

albert.paul@nist.gov

Laser physics

Residual stress measurement

Quinn, George

george.quinn@nist.gov

Mechanical property test standards

Standard reference materials

Fractography

Robins, Lawrence

lawrence.robins@nist.gov

Defect identification and distribution

Cathodoluminescence imaging/spectroscopy

Photoluminescence spectroscopy

Raman spectroscopy

Saylor, David

david.saylor@nist.gov

Microstructural characterization

Microstructural imaging

Grain boundary analysis

Schenck, Peter

peter.schenck@nist.gov

Emission and laser spectroscopy

Thin film deposition

Computer graphics and image analysis

Combinatorial materials analysis

Scotch, Adam

adam.scotch@nist.gov

Interfaces

Microstructural evolution

Sintering and grain growth

Electronic ceramics

Smith, Douglas

douglas.smith@nist.gov

Nanomechanics

Instrumented indentation

Surfaces forces

Adhesion

Sturrock, Charles

charles.sturrock@nist.gov

Materials informatics

Adaptive learning methods

Predictive data mining

Vanderah, Terrell

terrell.vanderah@nist.gov

Solid-state chemistry

Phase equilibria of microwave dielectrics

Vaudin, Mark

mark.vaudin@nist.gov

Electron microscopy

X-ray and electron diffraction

Modeling of grain-boundary phenomena

Dielectric films

Wagner, Richard

richard.wagner@nist.gov

Nanoindentation

Modeling of phase transformation

Atomistic modeling of nanomechanics

White, Grady

grady.white@nist.gov

Residual stress measurements

Mechanical reliability

Raman spectroscopy
54

Windover, Donald

donald.windover@nist.gov

High-resolution x-ray diffraction

X-ray reflectometry

Standard reference materials

Woicik, Joseph

joseph.woicik@nist.gov

UV photoemission

X-ray standing waves

Surface and interface science

Wong-Ng, Winnie

winnie.wong-ng@nist.gov

X-ray crystallography and reference patterns

Phase equilibria/crystal chemistry

High temperature superconductors

Yoder, Derek

derek.yoder@nist.gov

Soft x-ray absorption fine structure

X-ray scattering

Surface science

Ying, Charles

charles.ying@nist.gov

Atomic force microscopy

Nanofriction

Adhesion

Research Associates

Armstrong, Nicholas

University of Technology, Sydney, Australia

Bai, Mingwur

Tohoku University

Bartsch, Marian

Institute for Materials Research,

German Aerospace Center

Boukari, Hacene

University of Maryland

Bryson, Damian

Howard University

Cedeno, Christina

American Ceramic Society

Cha, Kum-hwan

Yousei University

Chae, Young-Hun

Kyungpook University

Coutts, Rachel

University of Maryland

Dapkunas, Stanley

Consultant

Dillingham, Jermey

University of Maryland

Evans, Howard

Smithsonian Institution

Fang, Hsu-Wei

University of Maryland

Farabaugh, Edward

American Ceramic Society

Haller, Wolfgang

Consultant

Harne, Mary

Consultant

Hastie, John

Consultant

Henins, Albert

Consultant

Hill, Kimberly

Consultant

Ilavsky, Jan

Purdue University

Jang, Mi-Hye

Yonsei University

Kang, Youn-Seon

Korea Advanced Institute of Science

and Technology

Kim, Jang Yul

Hanyang University

Kim, Min-Soo

Korea Advanced Institute of Science

and Technology

Kim, Yin Yong

Seoul National University

Kulkarni, Anand

State University of New York

Li, Xiang

Rensselaer Polytechnic Institute

Research Staff

54
55

Liang, Yanang

Universided Oviedo, Spain

Long, Gabrielle

Argonne National Laboratory

Luong, Mario

University of Maryland

Mighell, Alan

Consultant

Ozmen, Yilmaz

Pamukkale University, Turkey

Pei, Patrick

Consultant

Peiris, Suhithi

Naval Research Laboratory

Piermarini, Gasper

Naval Surface Warfare Center

Prosandeev, Serguei

Rostov State University

Przedlacki, Marcin

Warshaw University of Technology

Purushotham, Kavuri

Swinbourn University

Rajagopalan, Arun

Rensselaer Polytechnic Institute

Rau, Christoph

Purdue University

Ritter, Joseph

Consultant

Roth, Robert

Viper Group

Seo, Chang-Eui

Korea Advanced Institute of Science

and Technology

Suh, Julia

Consultant

Swanson, Nils

American Ceramic Society

Texter, John

National Science Foundation

Turchinskaya, Marina

Consultant

Wang, Xiao-lei

Tohoku University

Wang, Xuemin

American Ceramic Society

Wolfenstine, Jeffrey

U.S. Army Research Laboratory

Yang, Seung Ho

Korea Advanced Institute of Science

and Technology

Yeager, Glenn

Trak Ceramics, Inc.

Ying, Tony

U.S. Mint of the Treasury Department

You, Jim

American Ceramic Society

Research Staff
56
57

Organizational Charts

Organizational Charts

Materials Science and Engineering Laboratory

Polymers

E.J. Amis, Chief

C.R. Snyder, Deputy

Metallurgy

C.A. Handwerker, Chief

F.W. Gayle, Deputy

Ceramics

D.L. Kaiser, Chief

R.G. Munro, Deputy

Materials Reliability

A.F. Clark, Chief

T.A. Siewert, Deputy

NIST Center for

Neutron Research

P.D. Gallagher, Director

Director

Deputy Director

National Institute of Standards and Technology

Director

Boulder Laboratories

Baldrige National Quality

Program

Director for

Administration

& Chief Financial

Officer

Technology

Services

Advanced

Technology

Program

Manufacturing

Extension

Partnership

Manufacturing

Engineering

Laboratory

Chemical Science

and Technology

Laboratory

Materials Science

and Engineering

Laboratory

Electronics and

Electrical Engineering

Laboratory

Information

Technology

Laboratory

Physics

Laboratory

Building and

Fire Research

Laboratory

L.E. Smith, Director

S.W. Freiman, Deputy Director
58
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