i

Materials Science and

Engineering Laboratory

FY 2003 Programs and

Accomplishments

Ceramics

Division

Debra L. Kaiser, Chief

NISTIR 7014

September 2003

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
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iii

Table of Contents

Table of Contents

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

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

Ultra-Small-Angle X-ray Scattering (USAXS)

Imaging of Human and Artificial Tissues............................................................................4

Data Evaluation Theory and Practice .................................................................................6

Inorganic Crystal Structure Database:

Accessibility in Support of Materials Research and Design ..............................................8

Crystal Chemistry of Novel Wireless Dielectrics:

Bi-Zn-Nb-O Pyrochlores ..................................................................................................10

Biaxial Stress Dependence of Raman and

Photoluminescence Lines in AlxGa1–xAs ..........................................................................12

Nanoscale Measurement of the Amount of Complex

Hydrocarbon Molecules on Magnetic Hard Disks ...........................................................14

Combinatorial Methods............................................................................................................ 16

Combinatorial Tools for Materials Science .......................................................................17

Data and Data Delivery ..........................................................................................................18

Crystallographic and Phase Equilibria Databases.............................................................19

Evaluated Materials Property Data ..................................................................................20

Phase Equilibria and Properties of Dielectric Ceramics...................................................21

Phase Relationships in High Temperature Superconductors ............................................22

Materials for Micro- and Opto-Electronics .............................................................................23

Nano- and Micro-Electronic Materials Characterization ..................................................24

Wide Band Gap/Optoelectronic Materials .......................................................................25
iv

Table of Contents

Materials Property Measurements ..........................................................................................26

Mechanics of Materials ....................................................................................................27

Materials Structure Characterization ...................................................................................... 28

Diffraction Metrology and Standards ...............................................................................29

Small-Angle Scattering and Imaging .................................................................................30

Synchrotron Beam Line Operation and Development ......................................................31

Nanocharacterization ...............................................................................................................32

Nanomechanics and Standards .........................................................................................33

Nanotribology and Surface Properties..............................................................................34

Particle Metrology and Standards.....................................................................................35

Ceramics Division Databases and Standards..........................................................................37

Ceramics Division FY03 Annual Report Publication List .......................................................39

Ceramics Division ....................................................................................................................47

Research Staff......................................................................................................................... 48

Organizational Charts .............................................................................................................. 53
1

Executive Summary

Executive Summary

Ceramic materials — inorganic nonmetals — have

diverse functionality and chemical and mechanical

robustness that makes them attractive candidates for

integration in devices and components for high-end

applications including electronics, telecommunications,

and biotechnology. Once used predominantly in

bulk, monolithic form, ceramic materials are now

increasingly used in microscale or even nanoscale

forms, such as multilayers, composites, particulates,

fibers, and tubes. The NIST Ceramics Division in

the Materials Science and Engineering Laboratory

(MSEL) is increasingly focusing on the measurements,

standards, and data needs for advanced applications

of ceramics, particularly in the nanoscale realm.

This report of the Ceramics Division’s technical

activities in FY 2003 (October 1, 2002–September 30,

2003) contains brief synopses of our projects related

to six of the nine umbrella programs in MSEL —

Combinatorial Methods, Data and Data Delivery,

Materials for Micro- and Opto-Electronics, Materials

Property Measurements, Materials Structure

Characterization, and Nanocharacterization.

Six particularly significant accomplishments are

described in more detail in the Technical Highlights

section of this report.

The first highlight showcases our division’s

unique synchrotron radiation facilities at the Advanced

Photon Source, specifically, an ultra-small-angle x-ray

scattering (USAXS) imaging technique developed by

MSEL scientists. Recent results demonstrate that

USAXS imaging is a powerful method for obtaining

three-dimensional microstructural information on

human and artificial tissues that cannot be obtained

by conventional x-ray imaging methods.

Critical evaluation of data and data delivery

continue to be a cornerstone of the division’s activities.

The next technical highlight describes the recently

published NIST Recommended Practice Guide,

Data Evaluation Theory and Practice for Materials

Properties, the first comprehensive treatise ever written

on this subject. In this Guide, formal principles of data

evaluation are first established and then applied in an

extensive collection of examples drawn primarily from

work in the Ceramics Division. Another technical

highlight in evaluated data concerns the Inorganic

Crystal Structure Database (ICSD), a compendium

of three-dimensional crystal structure information for

inorganic compounds that was jointly developed with

our partners in FIZ-Karlsruhe, Germany. The first

release of the Windows-based product for the ICSD

earlier this year will greatly increase the accessibility

of the information to researchers and instrument

manufacturers for materials design, compound

identification, and property prediction.

The next two technical highlights focus on

research results relevant to the use of ceramic

materials for information technology systems.

The first of these highlights describes a detailed

analysis of the crystal chemistry and the structural

origin of the dielectric response in bismuth-based

pyrochlores, attractive candidate materials for

wireless consumer devices. A new crystal–chemical

mechanism for the accommodation of small cations

in these compounds was established, and the new

principle was applied to pyrochlore structures in other

materials systems of interest for communications.

The other highlight focuses on metrology for local

residual stress determination in III-V multilayer thin

film systems for optoelectronics and microelectronics.

A novel approach, coupling Raman spectroscopy and

photoluminescence measurements, was successfully

used to simultaneously determine composition and

biaxial stress state in AlxGa1–xAs films.

The final highlight describes a novel master

calibration technique for determining the average

molecular thickness of a complex hydrocarbon

lubricant mixture on magnetic hard disks. The

approach may be applied to a variety of engineered

surfaces protected by complex hydrocarbon films.

Those who wish to obtain further information

about our technical activities may refer to the list of

publications following our project synopses, or you

may contact the staff or guest researchers listed at

the back of this report. Please contact me if you

are interested in postdoctoral research positions or

collaborative research opportunities. Thank you

for your interest in the NIST Ceramics Division.

Debra L. Kaiser

Chief, Ceramics Division
2
3

Technical Highlights

Technical Highlights

The Technical Highlights section of this Report

comprises six examples of the exciting outputs of the

Ceramics Division. They are:

■ Ultra-Small-Angle X-ray Scattering (USAXS)

Imaging of Human and Artificial Tissues

■ Data Evaluation Theory and Practice

■ Inorganic Crystal Structure Database: Accessibility

in Support of Materials Research and Design

■ Crystal Chemistry of Novel Wireless Dielectrics:

Bi-Zn-Nb-O Pyrochlores

■ Biaxial Stress Dependence of Raman and

Photoluminescence Lines in AlxGa1–xAs

■ Nanoscale Measurement of the Amount of Complex

Hydrocarbon Molecules on Magnetic Hard Disks
4

Technical Highlights

Ultra-Small-Angle X-ray Scattering (USAXS) Imaging of

Human and Artificial Tissues

Just as three-dimensional (3D) imaging has

revolutionized clinical medicine, microscale

3D imaging of human and artificial tissues

will substantially improve our microstructural

understanding of these materials and potentially

enable us to develop useful man-made

biomaterials. The ultimate goal of tissue

engineering is to coax cells into regenerating

missing or damaged tissue such as bones or

cartilage. This research focuses on obtaining

high-contrast real-space images and statistical

measures of the microstructures of both of

these classes of materials.

Gabrielle G. Long and Lyle E. Levine

Ultra-small-angle x-ray scattering (USAXS) imaging

is a high-contrast x-ray technique –– developed by

MSEL scientists –– that provides three-dimensional

(3D) microstructural information that is unobtainable

using conventional x-ray imaging methods. While the

intensity of small-angle scattering as a function of angle

provides a measure of the sizes, shapes, and number

distributions of the scattering objects, it does not tell

us how the scattering objects are arranged. USAXS

imaging provides direct information on how the

scattering objects are distributed in space, and, thus,

can serve as a guide for selected-volume USAXS

measurements. Together, USAXS imaging and USAXS

data analysis deliver complementary information

on the sizes, size distributions and morphology of the

microstructures, and how they are arranged in the

material. The goal of this research is the nondestructive

observation of critical structures responsible for

the properties of natural and man-made tissues.

This Highlight describes our most recent results

from USAXS imaging and USAXS data analysis on

human ankle cartilage and man-made tissue scaffolds.

USAXS imaging greatly expands the usefulness

of conventional small-angle scattering in four ways.

First, it provides direct images of the shapes and 3D

arrangements of the scattering objects. Second, the

local scattering intensity can be measured as a function

of scattering vector, q (where q = (4π/λ) sin θ, λ is

the x-ray wavelength, and 2θ is the angle of scatter),

by comparing images produced at different q values.

Third, USAXS imaging greatly extends the size

range over which spatial information is obtained.

Our USAXS instrument can explore real-space

structures from about 1 nm to over 1 μm in size.

USAXS imaging extends this range to mm-sized

structures. Fourth, USAXS imaging can identify the

source of observed scattering. Since the only x-rays

that contribute to the image are those produced by

small-angle scattering, the image is a direct map of

the origin of USAXS within the sample.

USAXS images are produced by angle-filtering

the x-rays scattered by density variations within a

sample, thus providing exceptionally high contrast.

While USAXS imaging can provide contrast in cases

where radiography and phase–contrast imaging are

unsuccessful, the images produced at different

scattering angles also may highlight different

microstructural features within the same volume,

thus providing additional capabilities for exploring

complex microstructures.

Our USAXS instrument is located on the UNICAT

Sector 33 insertion device beam line at the Advanced

Photon Source at Argonne National Laboratory. A pair

of silicon {111} crystals selects the energy of the

x-rays impinging on the sample, and a pair of mirrors

removes higher-order harmonics. Another pair of

silicon {111} crystals analyzes the scattered intensity.

While the instrument can measure intensities on both

sides of the diffraction peak as well as at the peak

itself, the USAXS data typically begins 2 to 6 decades

below the peak intensity of the transmitted beam and

often extends over 8 decades of intensity.

In USAXS imaging, the analyzer crystal pair is

rotated to a specific angle and the angle-filtered x-rays

form an image of the sample. Since the image contrast

does not change during sample rotations about the

scattering vector (vertical axis in the lab), we produce

stereo USAXS images by combining images from two

such rotations. In addition, we have measured 3D

rotation series in preparation for full tomographic

reconstruction.

USAXS imaging and USAXS scans were made of

human ankle cartilage mounted in a wet cell to forestall

dehydration. The images that were taken with the

scattering vector parallel to the surface of the cartilage

showed few structures while images taken with the

scattering vector perpendicular to the surface showed

copious structures both near the surface (where the

collagen fibers are thought to be parallel to the surface)

and on the opposite side near the bone (where the

collagen fibers are expected to be perpendicular to the

bone). The middle of the sample (where the collagen

is “disordered”) showed few distinct structures.
5

Technical Highlights

Figure 2 shows USAXS images of a slow-cooled

tissue scaffold at q = 0 Å–1 and q = 0.0005 Å–1. The

upper panel shows the overall pore structure with

absorption and phase both contributing to the contrast.

Since the scattering at q = 0.0005 Å–1 is dominated by

the crystallites, the image in the lower panel highlights

their distribution within the sample. Comparison and

superposition of the two images allows us to determine

the locations of the crystallites relative to the pore

surfaces. Analysis of the scattering curve enables us

to extract the crystallite size distribution. The only

potential problem in extracting the size distribution

is uncertainty over whether double-Bragg diffraction

is contaminating the scattering curve. Rotating the

sample at q = 0.0005 Å–1 about the scattering

vector shows that the crystallites do not fluctuate

in intensity. This proves that the scattering curve is

not contaminated by double-Bragg diffraction, and

a size-distribution analysis can be made.

For More Information on this Topic

G. Long (Ceramics Division, NIST); C. Muehleman,

J. Li (Rush Medical College); T. Irving (Illinois Institute

of Technology); J. Dunkers (Polymers Division, NIST)

Figure 1: USAXS data and analysis of the surface region

of the cartilage.

USAXS data and analysis of the surface region, for

the scattering vector perpendicular to the surface, are

shown in Figure 1. The data were fitted by a broad

distribution of spheroids of aspect ratio equal to 5.

We find a distribution of sizes starting from the

smallest, with few structures above 1000 Å in size.

Analysis of the USAXS scans from the middle

region of the cartilage indicated the presence of a

bimodal size distribution with the 2nd peak around

1200 Å. In addition, there was evidence of a low-angle

diffraction peak. Data from the near-bone edge

contained a prominent low-angle diffraction peak at

the same position indicating the presence of 650 Å

spacings. Interestingly, the microstructures derived

from the sample with the scattering vector parallel to

the surface, and that from the middle region of the

sample perpendicular to the scattering vector were

very similar. This supports the model of “disorder”

in the middle region.

Polymer-based tissue engineering scaffolds were

produced from blended, co-extruded binary polymers

of polycaprolactone (PCL) and polyethylene oxide

(PEO). After annealing, the PEO was dissolved in

water, leaving a porous structure of biocompatible PCL

with connected pores approximately 100 μm across.

This type of structure is ideal for growing tissues, but

the degree of crystallinity on the pore surfaces can

strongly affect the cell growth. To explore this effect,

an additional annealing/cooling step was added to alter

the degree of crystallinity. USAXS scans from the

tissue scaffolds contained a pronounced peak near

q = 0.035 Å–1 (180 Å) produced by the lamellar

structure of the polymer. The density difference

between the amorphous phases leads to enhanced

scattering from the crystalline regions.

Figure 2: USAXS images from a slow-cooled tissue

engineered scaffold acquired with q = 0 Å–1 (upper panel) and

q = 5 × 10–4 A–1 (lower panel).
Technical Highlights

Data Evaluation Theory and Practice

The rapid pace of technological innovation and

the sometimes alarming rate of consumption of

natural resources create unprecedented demands

to use materials more wisely, more effectively, and

more strategically. The availability of reliable

data plays a fundamental role in attaining these

goals. Ascertaining the credibility of data is the

function of data evaluation.

Ronald G. Munro

Credible data form the cornerstone of materials

technology. Yet there are relatively few dedicated

and sustained efforts to compile and disseminate fully

evaluated materials property data. The scope of such

an undertaking usually is too broad for commercial

enterprises and too diffuse for national programs.

Consequently, there is a timely and persistent need

for guidance on how to assess the reliability of data.

Based on more than a decade of research at NIST,

the Recommended Practice Guide, Data Evaluation

Theory and Practice for Materials Properties,

SP 960-11 (NIST, 2003), establishes a scientific

foundation for data evaluation and provides an extensive

range of real-world examples. The Guide examines

keys to assessing data, pitfalls in applying certain types

of property data, and criteria for consistency among

related property values.

Data evaluation is the process by which

collections of data are assessed with respect to

reliability, completeness, and consistency. As such,

data evaluation may be regarded both as a tool and

as a formal discipline that plays an intrinsic and an

increasingly significant role in advanced technology.

Both of these aspects of data evaluation are explored

thoroughly in the new NIST Recommended

Practice Guide.

Figure 1: Data evaluation must account for the complexity of

polycrystalline materials and the resulting dependence of material

properties on chemical composition, physical microstructure,

and environmental conditions.

Figure 2: Formal materials metrology encompasses both the

measurable quantities of conventional metrology and a formally

new class of quantities known as procedural material properties.

All design and analytical applications of property

data are predicated on the existence of significant

collections of property values. Designers need to

have values that pertain to the materials that will be

used in their products. Materials scientists need values

that can be used to distinguish the roles of underlying

independent variables and, further, to deduce relations

and correlations among properties. Moreover, the

development of measurement standards requires data

of the highest attainable reliability.

Figure 3: Measurement results for procedural quantities depend

intimately on the measurement details, such as the load applied to

the indentor in a hardness test.

6
Technical Highlights

The Guide, therefore, is directed towards the

vast segment of technology whose scientists and

engineers must use materials property data, at least on

occasion, without the benefit of direct measurement

or other assessment experience. The intent is to

provide a thoughtful and systematic approach towards

establishing confidence in assessing and using collections

of numeric materials property data.

To attain this goal, we must first recognize that

metrology, like all scientific endeavors, is a paradigm

built upon a foundation of concise definitions of basic

terms and rational relations. This Guide takes the

further view that solutions to common issues that

may be encountered with diverse data sources derive

from a small number of underlying principles that may

be developed generically and applied systematically.

Consequently, two chapters of the Guide are

devoted to formal considerations: one on materials

metrology in general, and one on data evaluation

per se. Two additional chapters are used to develop

and illustrate the practical implementation of the

formal principles.

The discussions on the theoretical foundations of

data evaluation are followed by an extensive collection

of examples. All the examples in the Guide are taken

from actual exercises in data evaluation, and they are

individually selected for the purpose of examining, in

succession, the issues of accessibility, reproducibility,

consistency, and predictability. Distinctions are made

among definitive relations, correlations, derived and

semi-empirical relations, heuristic theories, and value

estimates. Subtopics 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.

For More Information on this Topic

R.G. Munro (Ceramics Division, NIST)

NIST Recommended Practice Guide, Data

Evaluation Theory and Practice for Materials

Properties, SP 960-11 (NIST, 2003).

However, it must be recognized that not all useful

applications of property data require values of the

highest quality. There are relatively primitive, but highly

legitimate and abundant, applications of property data

that need little more than a rough estimate of a property

value. Between the extremes of primitive applications,

needing only rough estimates, and advanced designs,

relying on fully refined uncertainty analyses, lie a

wealth of intermediate requirements that are suitable

for diverse purposes. The formal attributes of data

evaluation provide the essential means of distinguishing

the suitability of data for a given purpose and can do

so in the context of the intended application of the data.

Figure 4: Empirical correlations often are the first step towards

developing physical models or to assessing the limits of validity of

proposed mechanisms.

Figure 5: Models are essential tools in data evaluation helping to

identify and understand underlying variables and the roles they

play in controlling material behavior.

7
8

Technical Highlights

Inorganic Crystal Structure Database:

Accessibility in Support of Materials Research and Design

Access to reliable information on the 3-dimensional

structure of crystalline materials helps researchers

concentrate experimental work in areas that

optimize the discovery process. Researchers and

instrument manufacturers have a critical need

for evaluated data and also domain specific

tools capable of identifying quality structures

and compatible data. In cooperation with our

partners in the FIZ-Karlsruhe, Germany, NIST

has redefined the Inorganic Crystal Structure

Database (ICSD) infrastructure, provided expert

evaluation of the data, and developed scientific

software tools and products. The status and

future development are outlined herein.

Vicky Lynn Karen and Alec Belsky

Access to crystal structure data can be a key step

 in solving research and applications problems

involving materials, as in the chemical (catalytic

materials), petroleum (zeolites), and electronics

(semiconductors) industries. These data are of interest

to analysts in areas such as materials design, property

prediction, and compound identification. To support

these efforts, the ICSD contains three-dimensional

crystal structure information for inorganic compounds

including ceramics and minerals.

Recent efforts have focused on modernizing and

evaluating the ICSD. This has included a complete

redesign of the ICSD database structure, conversion

and loading of the data into a relational database

management system, designing graphical user

interfaces to access the data, and creating scientific

application modules to analyze the results of a database

search. The database system and software design

philosophy, Figure 1, used for the ICSD is, in principle,

the same for all materials databases. At the core is

a distributed database containing both archival and

derived data items. The ICSD graphical user interface

represents the intermediate, domain-specific layer,

where research and scientific expertise are important.

Finally, there is an outer problem-solving layer that

cuts across disciplines and links various property

databases and theory.

Figure 1: The idealized model for a distributed database system

in materials research and design is composed of 3 layers.

Figure 2: The latest release of the Inorganic Crystal Structure

Database on CDROM.

The ICSD currently contains more than 65,000

entries. In order to be included in the database, the

structure must be fully characterized, the atomic

coordinates determined, and the composition fully

specified. A typical entry includes the chemical name,

formula, unit cell parameters, space group, complete

atomic coordinate parameters, site occupation, title,

authors, journal or source citation, and other numeric

data or metadata, as needed. In addition to the

published data, many items are added through expert

evaluation and generated by computer programs,

such as Wyckoff sequence, molecular formula and

molar mass (a.k.a., molecular weight), ANX formula,

mineral groups, etc.

 Prior to their inclusion in the ICSD, data are

examined for completeness and various consistency

checks are performed. Several types of evaluation are

performed, including examination of individual data for

consistency within a complete entry, and determination

of the relationship of an individual entry to the entire

database.

The first release of the Windows-based product

for the Inorganic Crystal Structure Database and

a demonstration CDROM was presented at the
9

Technical Highlights

XIX Congress and General Assembly of the

International Union of Crystallography (Figure 2).

Since then, there have been two product updates,

adding about 3000 entries and revising the software in

response to customer input. The software product is

tabular in design and allows for searching in five

general categories: Chemistry, Crystal Data, Reduced

Cell, Symmetry, and Reference Data. The software

includes enhanced features for the characterization of

materials based on lattice search and chemistry search

modules, and it provides three-dimensional visualization

and powder pattern simulation for inorganic structures

(Figure 3). The ICSD can be searched in a hierarchy

or Boolean mode using NOT, AND, OR logic, and

multiple results sets can be generated. The different

results sets can be combined and individual entries

selected by the user to customize the results for

this specific problem. We have provided extensive

flexibility for exporting the results into user-defined

and standard formats for compatibility with outside

applications.

minerals. Ultimately, our goal (Figure 4) is to combine

these data sets with the inorganic data to form a single,

comprehensive non-organic crystal database. All entries

in the database include three-dimensional structural

information with about half having experimentally

refined coordinates. It is easy to assume that, because

the databases are all crystallographic databases, the

process for transforming the Metals and Inorganic data

(Figure 4) would be the same. However, this is not the

case as widely varying conventions, standards, and

formats have been employed throughout all three data

sets. For example, expert evaluation is required in

order to define and transform even the most critical

fields such as chemistry, positions of the atoms,

notations for multiple site occupancies, unit cells,

and space groups.

In addition to offering one comprehensive source

for all non-organic crystalline materials, inorganics,

and metals, the interoperability of the ICSD with other

data sources is becoming increasingly important for

future development. It is our aim that the development

strategies and implementations described herein for the

ICSD will be compatible with future demands from

the materials communities. Planning for this future

technology is currently underway.

For More Information on this Topic

V.L. Karen (Ceramics Division, NIST)

NIST Standard Reference Database 84, FIZ/NIST

Inorganic Crystal Structure Database (ICSD),

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

Figure 3: The new PC graphical user interface for the ICSD is

based on a relational database structure.

The ICSD is directly licensed to private industry,

universities, and individual scientists; in addition, there

are numerous indirect applications through instrument

manufacturers, software vendors, and third party

distributors.

In a parallel effort, NIST has two separate data

sources containing crystallographic and atomic

positional information for metallic crystalline

substances, including alloys, intermetallics, and

Figure 4: The development strategy for the ICSD is to establish

one comprehensive source of 3-dimensional structure data for

all non-organic crystalline materials.
10

Crystal Chemistry of Novel Wireless Dielectrics:

Bi-Zn-Nb-O Pyrochlores

Bi1.5Zn0.92Nb1.5O6.92 ceramics exhibit a

low-temperature dielectric relaxation, which has been

attributed to a dipolar glass-like mechanism, while

no such behavior is observed for Bi2Zn2/3Nb4/3O7

in the same temperature range.

Figure 1: Dielectric response of pyrochlore-type

Bi1.5Zn0.92Nb1.5O6.92 . (Courtesy of C. Randall and J. Nino, PSU.)

Figure 2: Illustrations of the pyrochlore structure. Pyrochlores

are often described by the formula B2O6•A2O ́, which emphasizes

that the structure is built of two interpenetrating networks: [BO6]

octahedra sharing vertices form a three-dimensional network

based on a diamond net (left), which results in large cavities

occupied by the O ́ and A atoms, themselves forming a second

cuprite-like A2O ́ tetrahedral net (right).

The primary technology drivers for wireless

consumer devices include miniaturization,

reduction of component part count, and increased

functionality. Multilayer ceramic integrated circuits

manufactured using low-temperature co-fired

ceramic technology provide a viable solution to

this challenge. Recently, bismuth-based pyrochlores

have been recognized as attractive candidates for

capacitor and high-frequency filter applications in

multilayer structures co-fired with metal electrodes.

However, understanding of the dielectric behavior

of these materials has been impeded by the absence

of detailed structural information. In the present

study, we conducted a detailed analysis of the cubic

pyrochlore-type compound Bi1.5Zn0.92Nb1.5O6.92

to establish the details of its crystal chemistry

and the structural origin of its dielectric response.

Igor Levin

Ternary oxides in the Bi2O3-ZnO-Nb2O5 (BZN)

system exhibit (Figure 1) high dielectric

constants (ε), relatively low dielectric losses, and

compositionally tunable temperature coefficients of

capacitance (τc). Such properties, combined with

sintering temperatures of less than 950 °C, render these

materials as attractive candidates for capacitor and filter

applications in multilayer structures co-fired with silver

electrodes. This system features two structurally

distinct ternary compounds, Bi1.5Zn0.92Nb1.5O6.92

(ε ≈ 145, τc ≈ –400 × 10–6/°C) and Bi2Zn2/3Nb4/3O7

(ε ≈ 80, τc ≈ +200 × 10–6/°C), exhibiting very dissimilar

dielectric properties. Since the two compounds

exhibit opposite signs of τc, their mixture yields

temperature-compensated ceramics.

Despite growing technological interest in these

ceramics, their crystal chemistry and the origin of

their dielectric behavior have remained uncertain.

The compound Bi1.5Zn0.92Nb1.5O6.92 was reported

to exhibit a cubic pyrochlore structure (Figure 2),

A2B2O7, implying that the Zn ions occupy both

A- and B-sites. However, in the absence of detailed

structural/compositional data, the presence of rather

small Zn ions on the eight-fold coordinated A-sites

remained highly controversial because the ionic radius

of Zn falls outside the known limits of structural

stability for pyrochlores. The other compound,

Bi2Zn2/3Nb4/3O7, according to our recent work,

was found to adopt a monoclinic zirconolite-like

arrangement. The zirconolite structure, which, like

pyrochlore, can be described as an anion-deficient

fluorite-derivative, features a distinctly different type

of cation arrangement on the metal sites. In the present

work, we conducted a detailed structural analysis of

the cubic pyrochlore Bi1.5Zn0.92Nb1.5O6.92 to elucidate

its crystal chemistry and the origin of the dielectric

relaxation.

Electron diffraction patterns from single grains

of Bi1.5Zn0.92Nb1.5O6.92 were consistent with both

a pyrochlore-type unit cell and symmetry. However,

several reflections (e.g., 442) observed in the

experimental electron, x-ray, and neutron powder

diffraction patterns, although accountable by the

Technical Highlights
11

Fd3m symmetry, violated special reflection conditions

for the 8b, 16c, 16d, and 48f sites occupied in the

ideal arrangement; these observations suggested that

some of the atoms are displaced to lower symmetry

positions. Indeed, Rietveld refinements using neutron

data confirmed appreciable distortion of the A-site

environment that occurs to accommodate the

bonding requirements of the A-cations (Figure 3).

This distortion is realized through (i) displacements

of both A-cations and O ́ anions from their ideal high

symmetry positions (16d-A, 8b-O ́), and (ii) local tilting

of [BO6] octahedra. A combination of the best fit and

most reasonable values of displacement parameters

were obtained by placing both A and O ́ ions on the

96g (x,x,z) positions. Similar positional parameters

were obtained at both 298 K and 12 K, suggesting that

the displacements are static in nature. In the disordered

model, each A cation is randomly distributed over six

sites, which are displaced from the ideal 16c positions

approximately along the three <112> directions

perpendicular to the corresponding O ́-A-O ́ link.

The displacements of the A-cations are confined to the

{111} layers and result in shortening of three-out-of-six

A-O bonds. The displacements of O ́ ions occur

along all six <110> directions, so that each O ́ ion is

statistically distributed over 12 sites.

Zn cations; in such configurations, the bonding

requirements of both Zn and Bi can be met. Electron

diffraction patterns (Figure 4) revealed weak, yet wellstructured, diffuse scattering which can be attributed to

such short-range ordering of Bi and Zn on the A-sites.

Figure 3: Nearest-neighbor environment indicated by the

refinement results for the A = (Bi/Zn) cations in the BZN

pyrochlore. Yellow and green spheres represent O and O ́ atoms,

respectively, while blue spheres correspond to the A-cations.

Left: View along <111> direction with six-randomly occupied

A-cation positions indicated by blue spheres. The O ́ atoms are

shown in the ideal positions for clarity. Right: View along the

direction nearly perpendicular to the <111>. The displaced

positions of both the A- and O ́ atoms are indicated.

The bond strain about the A-sites is minimized

when both O ́ ions in the O ́-A-O ́ link move toward

the corresponding {111} layer; these A-sites are

expected to be occupied by Zn. Three other O ́-A

bonds for the same O ́ ion will be stretched so that

those A-sites are likely to be occupied by Bi. Because

no superstructure reflections were observed, any such

structural correlation must be short-range in nature.

Crystal-chemical considerations suggest local ordering

in which each O ́ ion is bonded to three Bi and one

Figure 4: High-index zone axis electron diffraction pattern from the

pyrochlore Bi1.5Zn0.92Nb1.5O6.92 reveals well-structured diffuse

scattering likely associated with local ordering of Bi and Zn.

Studies of Bi1.5Zn0.92Nb1.5O6.92 using far-infrared

spectroscopy, conducted by S. Kamba at the Institute

of Physics in Prague, indicated that the lowest frequency

O ́-A-O ́ bending mode provides the strongest contribution

to the dielectric constant while the contribution of the

O-A-O bending is also significant. Both types of

bending resemble those produced by the presently

identified static displacements of the A, O ́ and O

atoms; therefore, these displacements are expected to

have a strong effect on the dielectric response of the

cubic pyrochlore-type compound. Thus, the displacive

disorder in the A2O ́ network most likely is the origin

of the “glass-like” dielectric behavior observed for

Bi1.5Zn0.92Nb1.5O6.92.

These studies of cubic pyrochlore-type

Bi1.5Zn0.92Nb1.5O6.92 have established a new crystal–

chemical mechanism for the accommodation of small

cations such as Zn on the A-sites of the pyrochlore.

This new principle has been applied to interpret the

structural behavior of other new pyrochlore compounds

in the Ca-Ti-Nb-O and Ca-Ti-Ta-O systems. These

phases were found to contain a mixture of Ca and Ti

on the A-sites, disordered displacements of Ti and O ́

atoms, and, also, dielectric relaxation similar to that

observed for the cubic Bi-Zn-Nb-O pyrochlore.

For More Information on this Topic

Igor Levin (Ceramics Division, NIST)

I. Levin, T.J. Amos, J.C. Nino, T.A. Vanderah,

C.A. Randall, and M.E. Lanagan. “Structural Study of

an Unusual Cubic Pyrochlore Bi1.5Zn0.92Nb1.5O6.92.”

J. Solid State Chem., 168 [1], 69–75 (2002).

I. Levin, T.J. Amos, J.C. Nino, T.A. Vanderah,

C.A. Randall, M.E. Lanagan, and I.M. Reaney.

“Crystal Structure of Compound Bi2Zn2/3Nb4/3O3.”

J. Mater. Res., 17 (6), 1406–1411 (2002).

Technical Highlights
12

Biaxial Stress Dependence of Raman and Photoluminescence

Lines in AlxGa1–xAs

Device manufacturers in the optoelectronics and

microelectronics industries have expressed the

need for a measurement technique to evaluate

local residual stresses in thin film systems. In

response, this project seeks to calibrate biaxial

stress-induced peak shifts in the first order Raman

and photoluminescence (PL) lines of AlxGa1–xAs

as functions of both stress and composition (x)

to provide a set of tools that can simultaneously

determine composition and biaxial stress state.

While the calibrations are specific to AlxGa1–xAs,

the approach is expected to be generally

applicable to other semiconductor systems.

Grady S. White and Albert J. Paul

Layered structures of ternary semiconductor

compounds, e.g., AlxGa1–xAs, are routinely used

in optoelectronics as light sources and detectors.

The wavelengths at which these devices perform,

as well as their mechanical and electronic stability,

are functions of the stress (strain) under which they

operate. Similar semiconductor ternary compounds are

used in the microelectronics industry and are subject to

the same stress-driven effects. The stresses, generated

during processing, are inherent in the devices and are

normally predicted by design models. However, there

is currently no way for the accuracy of the models to

be confirmed experimentally. The goal of this project

is to develop a suite of tools, consistent with those

used in industry, that can measure local stresses for

model verification.

Photoluminescence (PL) is widely used in the

U.S. optoelectronic and microelectronic industries to

monitor thin film composition in multilayer devices.

Because the same instrumentation can be used for

both PL and Raman measurements and because

Raman peak positions are known to be stress sensitive,

these two techniques were chosen as developmental

probes for simultaneously monitoring film stress

and composition. The critical question addressed

is whether a combination of the two techniques

allows separation of stress-induced peak shifts from

composition-induced peak shifts, thereby allowing

simultaneous evaluation of both stress and composition.

For this study, AlxGa1–xAs films with x = 0.2, 0.5,

0.8, and 0.9 were deposited by molecular beam epitaxy

on commercial 655 μm thick, 75 μm diameter undoped

GaAs substrates. The deposition temperature was

600 ± 5 oC and the film thickness, in each case, was

nominally 3 μm. Bulk x = 0 specimens were cleaved

from a polished, undoped, GaAs substrate, 500 μm

in thickness and 50 mm in diameter. All specimens

were oriented with the (100) direction normal to the

plane formed by the specimen surface. Squares

11 mm x 11 mm were cleaved from the wafers and

placed into a biaxial loading rig in the optical path of

a commercial micro-Raman system.

Figure 1: Unstressed Raman peak positions of GaAs-like (lower)

and AlAs-like (upper) peaks as function of x. Triangles and

“+” symbols represent two sets of specimens.

First order Raman spectra of AlxGa1–xAs (0 < x < 1)

consist of both a GaAs-like line and an AlAs-like line.

Figure 1 shows the peak position as a function of

x for both of these lines in the absence of stress.

The GaAs-like line is linear across the entire

composition range, whereas the AlAs-like line is

clearly nonlinear and is well described by a quadratic

expression (R2 > 0.99).

Data in Figure 2 were obtained from the GaAs-like

line of two x = 0.5 specimens. The behavior shown in

Figure 2 is typical of the behavior at all compositions

for both the GaAs-like and the AlAs-like peaks. Peak

shifts are linear with stress, and the peak position

decreases with increasing stress. Error bars in all of

the figures represent the 95 % Confidence Level.

Technical Highlights
13

Figure 2: Peak shift of GaAs-like peak; x = 0.5. The upward

and downward triangles represent data taken from two different

specimens.

Figure 3: Slopes (i.e., peak position/stress) of Raman lines as

a function of composition: GaAs-like peak (top) and AlAs-like

peak (bottom).

Figure 3 shows the change in peak position/stress

for both Raman lines as a function of composition.

Within the precision of the Raman measurements, the

stress sensitivity of both lines is independent of x.

However, the AlAs-like line shifts almost 50 % more

for a given stress than the GaAs-like line. Figures 2

and 3 show that while the phonon energy of both the

GaAs-like and the AlAs-like peaks depend strongly

upon the relative amounts of Ga and Al in the unit cells,

the change in energy with the application of stress

is essentially independent of the Ga/Al ratio.

of the multiple peaks composing the PL at those

compositions. However, none of the individual peaks

deviates substantially from the average values shown in

Figure 4. At x = 0.5, the PL is also indirect. However,

at that composition, the PL spectrum consists of

several peaks that are essentially independent of stress

(upper point in Figure 4) and one peak that is stress

dependent (lower point in Figure 4).

Figure 4: Slopes (i.e., peak position/stress) of PL lines as a

function of composition. In the left side of the figure, PL results

from direct transition; in the right side, PL results from indirect

transition.

In contrast to the Raman lines, the PL peak shift

with stress (Figure 4) shows strong composition

dependence for the direct electron transition (x < 0.5).

For x = 0.8 and 0.9, the PL spectra are more

complicated and result from indirect transitions.

The peak positions in this region, while still dependent

on x, are essentially independent of stress. The values

shown in Figure 4 for x = 0.8 and 0.9 are averages

Because both the Raman and PL spectra are

functions of stress and composition, the combination

of measurements can be used to solve for composition

and biaxial stress state simultaneously. Even for

x > 0.5, where the PL is independent of stress, the

measured composition dependence of the PL lines

coupled with the stress and composition dependence

of the Raman lines permits both composition and stress

to be determined. Because both the GaAs-like and the

AlAs-like Raman line positions have been calibrated

for both stress and composition, there are three, rather

than two, peaks that provide information regarding

stress and composition. The existence of the third

peak provides a tool for self-consistency checks

on the values obtained.

A manuscript, Biaxial Stress Dependence of the

GaAs-Like and AlAs-Like Raman Lines in AlxGa1–xAs,

by G.S. White, A.J. Paul, K.A. Bertness, and A. Roshko

that describes the Raman measurements in detail, has

been submitted for publication.

For More Information on this Topic

G.S. White, A.J. Paul (Ceramics Division, NIST);

K.A. Bertness, A. Roshko (Optoelectronics Division,

NIST)

Technical Highlights
14

Nanoscale Measurement of the Amount of Complex

Hydrocarbon Molecules on Magnetic Hard Disks

The requirement for protection in the head-disk

interface is rising. In order to reach 1 Terabit/in2

areal density and double the data transfer rate,

the spacing between the head and disk is shrinking

to 3.5 nm at a flying speed approaching 40 m/s.

Occasional contacts will test the shear strength

of the molecular layer on top of the carbon

overcoat. Current lubricant molecules are alcoholfunctionalized perfluoropolyether which are inert

and oxidatively resistant but lack solubility and

surface bonding strength. Alternative molecules

such as multiply alkylated cyclopentanes are being

considered to improve protection. In order for

any alternate molecules to be used, the average

molecular thickness on a hard disk surface needs

to be measured accurately at 10Å ± 1Å. We have

developed a unique master calibration technique

that, for the first time, is able to accurately determine

the average molecular thickness of a complex

hydrocarbon mixture on magnetic hard disks.

Richard Gates, Charles Ying, and Stephen Hsu

The Information Storage Industry Consortium

(INSIC) has set a goal of reaching 1Tbit/in2 areal

density by 2006 with a concurrent increase in data

transfer rate approaching 100 Gbit/s. This translates

to an extraordinarily ambitious technical goal of a

10-fold increase in capacity in four years. To reach

that goal, the flight height and the carbon overcoat

thickness need to be reduced to 3.5 nm and 1 nm

respectively. Since the disk is protected by the

thickness of the carbon overcoat and 10Å of lubricant

molecules, alternative carbons and lubricant molecules

are needed to provide the same degree of protection

with one-fifth the amount of lubricant and overcoat.

Under the proposed new design, head-disk interface

contacts are inevitable due to reduced flight height,

waviness of the disk, and rotational wobble. One of

the key characteristics that has been identified for

protective molecules is the adhesive strength to resist

high shearing action. A typical solution in this case

would be to add strongly surface-bonding molecules to

the lubricant as additives. The current disk lubricant, a

functionalized perfluoroalkyl ether, has limited solubility.

Therefore, hydrocarbon molecules with extremely low

volatility characteristics are needed. Multiply alkylated

cyclopentane is one such molecule.

Current industrial practice of measuring the thickness

of perfluoroalkyl ether on a hard disk surface (tip to valley

distance from 15 Å to 25 Å) relies on a cross calibration

between fourier transform infrared spectroscopy (FTIR)

and x-ray photoelectron spectroscopy (XPS) on CF2

bonds which is symmetrical and sharp. For complex

hydrocarbons, there are multiple peaks interrelated at

different frequencies, and there is no established technique

for such measurement.

The measurement of “average film thickness” needs

to be defined. The lubricant molecules are a complex

mixture of isomers with different molecular weights.

The surface is atomically rough, and the coverage is

below the full “monolayer” level. Nano- and microscale

aggregations undoubtedly take place, and the distribution

of molecules across the surface hills and valleys is not

known. Recent data from UC Davis tend to support

this observation. High-frequency modulation atomic

force microscopy (AFM) was used to image the

surface, and from these data, elasticity information can

be extracted. Figure 1 relates the topographic image

with elasticity of a hydrocarbon covered hard disk

surface. The bottoms of the valleys show higher

hardness suggesting that the hydrocarbon molecules

do not reside at the bottom of the valleys.

Figure 1: AFM topographic images and elasticity data.

Detection and measurement of a one nanometer

thick complex molecular layer on a rough surface taxes

the detection limits of analytical instrumentation. We first

used FTIR and a modified XPS technique. The modified

XPS technique scanned the surface twice: once without

lubricant coverage and once with lubricant coverage.

The decrease of x-ray photoelectron signal intensity

from the molecule coverage was used to estimate

film thickness. Unfortunately, the carbon overcoat

thickness was found to vary along the radial direction

of the disk. Depending on the specific batch of disks

tested, the variation could be as much as 5 % –10 % from

the inside radius to the outer edge of the disk. Hence,

this measurement technique is insufficient to measure

the “molecular thickness” as required by industry to

control the process.

Technical Highlights
15

We tried various techniques such as AFM

scratching, ellipsometry, and x-ray reflectivity (XRR).

The latter technique has difficulty with surface

roughness and the fact that the average film thickness

is below the peak-to-valley distance. For AFM, the

molecules wet the tip. Ellipsometry data at this range

have large scatter. So the conclusion is there is no

acceptable technique to measure such “film thickness”

of a complex hydrocarbon molecular mixture to the

industrial specification of 10 Å ± 1 Å.

To develop a solution to this industrially important

issue, we created a master calibration sample approach.

Basically we deposit a known (gravimetrically) solution

on a disk with a barrier film surrounding a known area

and allow the solvent to evaporate under controlled

conditions. The resulting “film thickness” can then be

used to calibrate various instruments. The challenges

are uniform distribution of molecules across the area,

containment of fluid, meniscus forces, and evaporation

rate control.

Figure 2: Confined lubricant solution on a hard disk.

Figure 3: Calibration curve relating FTIR signal to known

hydrocarbon film thickness determined gravimetrically. Error

bars are one standard deviation.

Figure 4: XPS signal calibration for known hydrocarbon film

thickness. Error bars are one standard deviation.

A calibration method for nanometer-scale complex

hydrocarbon films on an engineering surface has been

developed. The method is based on gravimetric solution

preparations and utilizes a novel freeze-evaporation

technique to extract the carrier solvent while leaving a

uniform film of complex hydrocarbon on the surface.

The method can be applied to a variety of surfaces

and offers the potential for calibrating many different

analytical techniques for their ability to measure

thickness of complex hydrocarbons.

For More Information on this Topic

S. Hsu (Ceramics Division, NIST)

Initially, this approach was attempted with liquid–phase

samples; however, under these conditions, evaporation

and meniscus forces lead to uncontrolled lubricant film

uniformity. This was solved by evaporating the solvent

from the mixture while it is in the solid state. The solution

is placed within the barrier (Figure 2) and rapidly frozen

using liquid nitrogen. Then the solvent is slowly removed

by evaporation into an inert gas at –10 °C.

By controlled slow evaporation of solvent directly

from a solid frozen state, we avoid the meniscus and

surface tension forces which tend to create non-uniformity

of the liquid mass. A pseudo “sublimation” process is

created. In this way, uniform signal detection by FTIR

confirms that the distribution of molecules across the area

is less than 5 % at less than full monolayer coverage.

Using this new technique, a series of “film thickness

calibration standards” was created (see Figure 3).

A series of three master calibration samples

was prepared and submitted for XPS photoelectron

attenuation analysis. The very small variation of XPS

intensity across the disk surface indicated that film

uniformity was quite good, varying by less than 5 %.

A correlation plot of XPS estimated thickness versus

master calibration target thickness (Figure 4) yielded a

straight line, but the slope was not 1.0 (referenced in

red). This indicates that the XPS attenuation technique

has an inherent bias due to inaccurate assumptions in

the model used in the analysis. The observation that the

slope of the XPS versus target thickness correlation is

0.6 indicates that the initial XPS attenuation technique

was underestimating the hydrocarbon film thickness

by about 40 %. The effect has been attributed to the

difference in density between the hydrocarbon and

carbon overcoat. Utilizing this information, the model

was refined to accommodate this effect.

Technical Highlights
16

Combinatorial Methods

and online at www.nist.gov/combi. Within the

Materials Science and Engineering Laboratory (MSEL),

novel methods for combinatorial library preparation are

designed to encompass variations of diverse physical

and chemical properties, such as composition, film

thickness, processing temperature, surface energy,

chemical functionality, UV-exposure, and topographic

patterning of organic and inorganic materials ranging

from polymers to nanocomposites to ceramics to

metals. New instrumentation and techniques have

been developed that enable the high-throughput

measurements of adhesion, mechanical properties,

failure mechanisms, film thicknesses, and refractive

index, among others. The combinatorial effort

extends to multiphase, electronic, optoelectronic,

and magnetic materials, including biomaterials

assays. On-line data analysis tools, process control

methodology, and data archival methods are also

being developed as part of the Program’s

informatics effort.

The extensive outreach activity in the Combinatorial

Methods Program is designed to facilitate technology

transfer with institutions interested in acquiring

combinatorial capabilities. The centerpiece of this effort

is the NIST Combinatorial Methods Center (NCMC),

an industry–university–government consortium organized

by MSEL that became operational on January 23, 2002

via a kick-off meeting in San Diego. The recognized

importance of NCMC activities is readily apparent, as

15 industrial partners, the Air Force Research Lab, and

the University of Southern Mississippi are participating

in the NCMC membership program. The membership

continues to grow and 80 % of the members from last

fiscal year have already renewed for this fiscal year.

The NCMC facilitates direct interaction between NIST

staff and these industrial partners, and it provides a

conduit by which Combinatorial Methods Program

research products, best practices and protocols,

instrument schematics and specifications, and other

combinatorial-related information can be effectively

disseminated. This outreach is mediated in large

part by a series of semi-annual workshops for

NCMC members. Indeed, since its inception,

four NCMC workshops have been held at NIST.

Further information on the NCMC can be found

on the website at www.nist.gov/combi.

Contact: Peter K. Schenck

The Combinatorial Methods Program develops

novel high-throughput measurement techniques and

combinatorial experimental strategies specifically

geared towards materials research. These tools

enable the industrial and research communities to

rapidly acquire and analyze physical and chemical data,

thereby accelerating the pace of materials discovery

and knowledge generation. By providing measurement

infrastructure, standards, and protocols, and by

expanding existing capabilities relevant to combinatorial

approaches, the Combinatorial Methods Program

lowers barriers to the widespread industrial

implementation of this new R&D paradigm.

The Combinatorial Methods Program has adopted a

two-pronged strategy for accelerating the development

and implementation of combinatorial approaches:

an active intramural R&D program and an ambitious

outreach activity. The intramural R&D program is

designed to better tailor combinatorial methods for the

materials sciences and extend the state-of-the-art in

combinatorial techniques. Measurement tools and

techniques are developed to prepare and characterize

combinatorial materials libraries, often by utilizing

miniaturization, parallel experimentation, and a high

degree of automation. A key concern in this effort is

the validation of these new approaches with respect

to traditional “one at a time” experimental strategies.

Accordingly, demonstrations of the applicability of

combinatorial methods to materials research problems

provide the scientific credibility needed to engender

wider acceptance of these techniques in the industrial

and academic sectors. The successful adoption of the

combinatorial approach also requires a highly developed

“workflow” scheme. All aspects of combinatorial

research, from sample “library” design and library

preparation to high-throughput assay and analysis,

must be integrated through an informatics framework,

which enables iterative refinement of measurements and

experimental aims. Combinatorial Methods Program

research projects give illustrations of how combinatorial

methodology is implemented effectively in a research

setting.

NIST-wide research collaborations, facilitated by

the Combinatorial Methods Program, have produced

a wide range of new proficiencies in combinatorial

techniques, which are detailed in a brochure,

“Combinatorial Methods at NIST” (NISTIR 6730),

Program Overview
17

Combinatorial Methods

Combinatorial Tools for Materials Science

Combinatorial methods are increasingly used

by industry for the discovery and optimization

of materials for use in electronic, optical, and

magnetic applications as well as for designing

chemical and biological sensors and for creating

molecular patterns. We have developed tools

for the fabrication of thin film libraries and

characterization of thickness and optical

properties. We introduce combinatorial near

edge x-ray absorption fine structure as a new

tool for the rapid, non-destructive determination

of the chemistry (including bond concentration)

and molecular orientation of chemically

heterogeneous surfaces.

Peter K. Schenck and Daniel A. Fischer

We have developed combinatorial tools that can be

applied to a broad range of materials: a pulsed

laser deposition (PLD) system for thin film library

fabrication; a rapid throughput, spatially-resolved

spectroscopic reflectometer for mapping thickness

and refractive index; and a combinatorial near edge

x-ray absorption fine structure (NEXAFS) tool.

PLD is a versatile, rapid method for growing thin

films that has the following advantages: complex target

compositions are possible; congruent vaporization

leads to stoichiometric material transfer; high energy

process; low substrate temperatures; and high deposition

rates. Our deposition chamber utilizes a dual-beam,

dual-target configuration designed for the fabrication

of compositionally graded films. Thickness and optical

Combinatorial NEXAFS is used to simultaneously

determine molecular orientation and bond chemistry

of planar, chemically heterogeneous surfaces.

Information on the chemistry and molecular

organization of chemical groups on surfaces is

needed, for example, to shed light on the behavior of

monomolecular templates and surface modifiers and

to characterize new classes of catalysts. We illustrate

the power of the combinatorial NEXAFS method by

simultaneously probing the concentration and molecular

orientation of semifluorinated F(CF2)8(CH2)2SiCl3

(F8H2) molecules in self-assembled monolayer (SAM)

gradients on flat silica substrates as shown in Figure 2.

Notable Outputs: Invited paper in Chemistry in

Britain, May 2003 (pgs. 45–47), “Blazing a Trail.”

Cover of Applied Physics Letters, January 13, 2003

(pgs. 266–268) and press release, January 17, 2003,

Brookhaven National Laboratory, “Scientists Develop

Technique to Determine Molecular Structure of

Heterogeneous Surfaces.”

Contributors and Collaborators

M. Vaudin, J. Kim, J. Blendell (Ceramics Division,

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

E. Bretschneider (Uniroyal Optoelectronics); J. Genzer,

K. Efimenko (North Carolina State University)

Figure 1: Reflectivity (450–500 nm, relative to sapphire) of

Ni-Au interconnects on GaN after heating to 400 oC.

Figure 2: Fraction of F8H2 in the SAM (fF8H2) (closed circles)

and the molecular orientation (open circles).

property assays are performed on the film libraries using

a semi-automated spectroscopic reflectometry apparatus.

BaTiO3-SrTiO3, Au-Ni, and Au-NiO film libraries have

been deposited and characterized using these tools. In

addition, combinatorial library films of Ni-Au interconnects

(88 compositions) on GaN have been characterized before

and after annealing (as shown in Figure 1).
18

Program Overview

Data and Data Delivery

The economic importance of technical data has

grown steadily over the past three decades. NBS/NIST

took an important lead early in the effort to emphasize

the pervasive use and increase the impact of reliable

materials property data. As early as 1985, former NBS

Director E. Ambler noted that the need for property

data had become a “national priority,” while the

National Research Council repeatedly observed that

there is a persistent “critical national need” for

materials property data.

The NIST Materials Science and Engineering

Laboratory (MSEL) has been a prominent leader in

responding to this national need. By design, the scope

of the MSEL effort is evolutionary and responds to the

ever-increasing advances in technology. Currently,

MSEL has six project areas in the Data and Data

Delivery program.

■ Crystallographic and Phase Equilibria Databases

[Project Leader — V. Karen]: This project

encompasses the two most venerable efforts in

MSEL, each of which recently has had a major new

release. In collaboration with Fachinformationszentrum

Karlsruhe (FIZ, Germany), a CDROM version of

the FIZ/NIST Inorganic Crystal Structure Database

(ICSD) has been released providing the full structural

data, i.e., lattice parameters and atomic coordinates,

for approximately 60,000 compounds. The

long-standing collaboration between NIST and the

American Ceramic Society (ACerS) has continued

with the completion of a new topical volume in the

NIST/ACerS Phase Equilibria Diagrams series, the

first of two planned volumes on electronic ceramics.

■ Phase Equilibria and Properties of Dielectric

Ceramics [Project Leader — T. Vanderah]:

An integrated theoretical and experimental effort is

underway to predict and measure phase equilibria

and electronic behavior in dielectric oxide systems.

This work includes relaxor ferroelectrics, dielectrics

for cellular infrastructure and hand-held devices, and

dielectrics for low temperature co-fired ceramics for

applications in multilayer ceramic integrated circuit

technology. The impact of this work was evident in

Dr. Vanderah’s invited perspective article, “Talking

Ceramics,” which appeared in the journal Science.

The timeliness of this work was emphasized further

by its subsequent feature in the science section of

the New York Times.

■ Phase Relationships in High Temperature

Superconductors [Project Leader — W. Wong-Ng]:

MSEL’s meticulous effort to provide phase information

critical to the development of practical superconductors

is currently directed towards two important systems:

Ba2RCu3O7–x, where R is yttrium or a lanthanide,

and MgB2. For Ba2RCu3O7–x, work has focused on

the phase relations in BaF2-BaO-Y2O3-CuOx-H2O and

the interactions of Ba2RCu3O6+x with buffer layers,

both of which are important for advances in the

“BaF2 ex situ” process and the “liquid-phase-epitaxy”

process. For MgB2, the enthalpy of formation,

vapor pressure, and sources of variability have

been determined.

■ Reaction Path Analysis in Multicomponent Systems

[Project Leader — C. Campbell]: Many industrial

processes rely on multicomponent diffusion to

control the formation and dissolution of precipitate

phases. MSEL is developing a multicomponent

diffusion mobility database for Ni-base superalloys

that will be used, for example, to predict the

formation of the γ′ (ordered FCC) phase during the

solidification of superalloys. A workshop, “High

Throughput Analysis of Multicomponent Multiphase

Diffusion Data,” was held in March 2003 to focus

on the development of methods to extract diffusion

data from multicomponent diffusion couples. 

■ Evaluated Materials Property Data [Project

Leader — R. Munro]: Engineering designs utilizing

advanced materials require reliable data. Elasticity,

strength, toughness, hardness, creep, thermal

expansion, conductivity, diffusivity, and durability

are prominent among the data categories needed and

desired for materials applications and development.

This project is directed both towards the development

of evaluated databases of these properties for

structural and superconducting ceramics and towards

the establishment of the evaluation methodologies that

form the foundation of reliable materials property

data systems. A significant achievement in this

effort is “Data Evaluation Theory and Practice for

Materials Properties,” SP960-11, the eleventh NIST

Recommended Practice Guide produced by MSEL.

■ Informatics and Visualization in Materials

Data Delivery [Project Leader — C. Beauchamp]:

The internet, and the World Wide Web in particular,

has become a dominant resource medium for

technical information. MSEL has undertaken a

major commitment to make its extensive data

collections available via this medium. New efforts,

now underway, will provide web access to the MSEL

lead-free solder materials property database and

the diffusion data archive that is important for the

processing of metal alloys. Additionally, the internet

will be used increasingly as a means of disseminating

MSEL’s prodigious technical publications in the form

of electronic manuscripts.

Contact: Ronald G. Munro
19

Crystallographic and Phase Equilibria Databases

Crystallographic data models are used on a

daily basis to visualize, explain and predict the

behavior of chemicals and materials, as well

as to establish the identity of unknown phases in

crystalline materials. Phase diagrams are used

throughout the ceramics industry to understand

and control the complex phenomena which

increasingly underlie advanced industrial

material production and materials performance.

Literally tens of thousands of structures and

phase diagrams have been reported in the

literature, all with varying degrees of reliability

and completeness. This project develops,

maintains, and disseminates comprehensive,

critically-evaluated data in printed and modern

computerized formats, along with scientific

software to exploit the content of these databases.

Vicky Lynn Karen, Terrell A. Vanderah,

and Peter K. Schenck

The Inorganic Crystal Structure Database (ICSD) is

a comprehensive collection of crystal structures

covering the literature from 1915. The ICSD database

system now includes chemical and 3-dimensional

structure information for more than 65 000 inorganic

materials. The data and scientific software are licensed

to instrument manufacturers, software vendors, and

other third-party distributors as well as to individual

researchers in industry and academia. Additional

information about the ICSD can be found in the

Technical Highlights section of this report.

To service the need for reliable phase diagram

data, the NIST Phase Equilibria Data Center and the

American Ceramic Society (ACerS) jointly publish

a series of critically evaluated collections of phase

diagrams. The series “Phase Equilibria Diagrams,”

originally published under the title “Phase Diagrams

for Ceramists” (1964–1992), provides current,

evaluated data on the phase equilibria of ceramics

and related materials. These publications also provide

bibliographic data, graphical representations, and

analytical capabilities so that researchers have access to

reliable, up-to-date data for use in designing, applying,

analyzing, and selecting materials. The published

portion of the database includes about 16 000 entries

with 26 000 phase diagrams contained in nineteen

books and a CD-ROM — over 53 000 units have been

sold world-wide. Approximately 1000 new entries are

collected from the primary literature each year.

Currently underway is a complete modernization to

replace the outdated 1980’s system with an integrated

production facility using a relational structure that will

facilitate electronic publishing in a variety of formats,

including a web-based version. Much of this year’s

effort has involved assisting and working with on-site

ACerS staff to design and build the new system, which

must incorporate all of the scientific data relationships

embodied in the original database.

The latest database products completed this year

include the topical volume, Phase Diagrams for

Electronic Ceramics I: Dielectric Ti, Nb, and Ta

Oxide Systems, edited by R.S. Roth (see Figure 1).

This is the first volume of a new collection of phase

diagrams focused on the increasingly important field

of electronic ceramics. More than 1100 diagrams

are presented along with commentaries written by

knowledgeable associate editors. Also completed

this year was an updated Cumulative Index 2003

which provides comprehensive indexing of published

equilibria data sorted by chemical system and author.

In preparation is “Volume XIV — Oxides” (2004)

which will contain a wide variety of metal, non-metal,

and semi-metal oxide systems — more than 900 entries

with 1300 diagrams are already available for inclusion.

Contributors and Collaborators

R.S. Roth, H. Ondik, M.A. Harne (Ceramics Division,

NIST); H.F. McMurdie, C. Cedeno, J. You, X. Wang,

N. Swanson, E. Farabaugh, M. Mecklenborg (The

American Ceramic Society); Fachinformationszentrum

Karlsruhe, Germany; D. Watson (Cambridge

Crystallographic Data Centre, UK); A. Belsky,

S. Young (Measurement Services Division, NIST)

Figure 1: The latest volume in the series “Phase Equilibria

Diagrams” features systems of major interest to the fields of

dielectric, ferroelectric, and piezoelectric ceramics.

Data and Data Delivery
20

Evaluated Materials Property Data

Reliable data form the cornerstone of materials

research and advanced engineering designs.

Capturing and assessing materials property data

from multiple sources is a key effort in responding

to this critical national priority.

Ronald G. Munro

The concurrence of two rapidly advancing

technologies, materials science and internet

communications, has created the potential for a

crisis in the reliability of available materials property

information. Once, researchers and designers relied

on handbooks and data compilations that were carefully

and thoughtfully produced through dedicated and

deliberately organized efforts. The magnitude of the

effort, the expense, and the time consumed from design

to production combined to form an effective quality

filter on the results. Efforts not undertaken with a

serious and sober intent were strongly deterred by

the inevitable costs and commitments.

Now, researchers and designers increasingly turn to

the internet for instant access to whatever information

is required. The ready accessibility of the internet,

however, is as much a weakness as it is a strength.

The internet provides a broad open forum where ideas

and results can be exchanged and disseminated with

remarkable ease, relatively little financial burden, and

scarcely any delay between the realization of an idea

or result and its expression. Unfortunately, the facility

with which information can be conveyed on the internet

lacks the inherent process filter that once served as a

useful safeguard on the quality of the information

content.

The success of the internet in allowing more

individuals to communicate more directly and effectively

ironically may also cause older information sources to

become relatively inaccessible. The materials information

populating the internet’s information forums represent

current efforts. Older information sources, such as

handbooks, that have not been adapted to the internet

may soon be overlooked or abandoned.

NIST is responding to the full range of challenges

presented by these circumstances. The key to reliable

data, whether in handbooks or on the internet, is data

evaluation. NIST has accepted the responsibility of

providing evaluated data on the internet and has taken

the lead in educating data users about the methods and

significance of data evaluation. Most notably, more

than a decade of development and experience in

evaluation methodology has been summarized in a

new NIST Recommended Practice Guide, SP960-11.

(For more information about this Guide, see Data

Evaluation Theory and Practice in the Technical

Highlights section of this report.)

Efforts in the Ceramics Division to provide

evaluated data on the internet are focused on the

sustained development of the Ceramics WebBook.

Currently, three data systems are maintained:

Standard Reference Database Number 30, the

Structural Ceramics Database (SCD); Standard

Reference Database Number 62, High Temperature

Superconductors (HTS); and a collection of topical

compilations called Property Data Summaries (PDS).

Figure 1: The elastic (Young’s) modulus at room temperature

for polycrystalline specimens of the high temperature

superconductor Y:123.

In FY 2003, two additions were made to the

Ceramics WebBook. The compilation, Elastic Moduli

Data for Polycrystalline Ceramics, NISTIR 6853,

consisting of approximately 4000 data points, was

added to the PDS collection. This collection exhibits

the dependence of the elastic moduli (E, G, B, ν) on

temperature and porosity for approximately 50 ceramic

compositions (e.g., Figure 1). A data update was

also completed for the Structural Ceramics Database.

This update increased the number of citations in the

SCD by 100, bringing the total to 834 citations and

approximately 38000 data points.

Contributors and Collaborators

C. Sturrock, J. Harris (Ceramics Division, NIST)

Data and Data Delivery
21

Phase Equilibria and Properties of Dielectric Ceramics

Ceramic compounds with exploitable dielectric

properties are widely used in technical applications

such as actuators, transducers, capacitors, and

resonators or filters for microwave communications.

The commercial competitiveness of next-generation

devices depends on new ceramics with improved

properties and/or reduced processing costs. Phase

equilibria determination integrated with systematic

experimental/theoretical chemistry–structure–

property studies contributes toward the fundamental

understanding and rational design of these

technologically important materials.

Experimental studies of microwave ceramics include

structural analyses (by x-ray and neutron powder

diffraction) combined with dielectric property correlations

of the technically important Ba3M2+M5+

2O9 (M2+ = Mg,

Zn, Ni; M5+ = Nb, Ta) systems. In these systems, the

M5+ cations tend to undergo a second-order Jahn–Teller

distortion and hence shift from the centers of the [MO6]

octahedra — this effect occurs simultaneously with 2:1

B-site cation ordering. Both phenomena influence dielectric

response. Modeling of the crystal structures using bond

valence methods is in progress to understand the interplay

between the distortion and dielectric behavior.

Figure 1: Subsolidus phase relations in the La2O3–MgO–TiO2

system (air, ≈ 1450 °C), sign of the temperature coefficient of

resonant frequency (τf; in parentheses), and approximate

locations of two regions of temperature-stable (τf = 0) equilibrium

mixtures (dotted lines).

Subsolidus phase equilibria, crystal chemistry, and

dielectric behavior were studied for the La2O3–MgO–

TiO2 system and for the ternary sections LaMg1/2Ti1/2

O3–CaTiO3–La2O3 and LaMg1/2Ti1/2O3–CaTiO3–La2/3

TiO3. Six phases form in the La2O3–MgO–TiO2 system,

and extensive perovskite-type solid solutions form in both

ternary sections (see Figure 1). By mapping dielectric

properties (relative permittivity and temperature coefficient

of resonant frequency, τf ; 5–10 GHz) onto the phase

diagrams, the compositions of temperature-stable

(τf = 0) compounds and mixtures were predicted.

From these studies, it was determined that the quaternary

La2O3–CaO–MgO–TiO2 system contains an extensive

single-phase, perovskite-type volume through which

passes a surface of temperature-stable compositions

with relative permittivities in the range of 40 to 50.

Contributors and Collaborators

W. Wong-Ng, R.S. Roth (Ceramics Division, NIST);

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

R. Geyer (Radio Frequency Technology Division, NIST);

S. Bell (TRAK Ceramics, Inc.); K. Leung (Sandia);

L. Bellaiche (University of Arkansas); U. Waghmare

(JNCASR, India); S. Prosandeev (Rostov State University)

Data and Data Delivery

Benjamin Burton, Eric Cockayne, Lawrence Cook,

Igor Levin, Michael Lufaso, and Terrell Vanderah

Next-generation ceramic packaging requires

fabrication of multilayered structures that include

embedded functional dielectric ceramics. Technical

challenges include understanding and control of

deleterious reactions at interfaces during firing.

A detailed study of the system Ag-Bi2O3-Nb2O5-O2

is in progress to develop a model of interfacial

interactions applicable to other co-fired metal–ceramic

systems. A partial phase diagram of the system has

been determined, and includes a new compound,

Bi5AgNb4O18, which is also observed as a product in

Ag/BiNb5O15 reaction couples. Surface diffusion was

found to dominate mass transport of Ag at the reaction

interface — this phenomenon could be important

for co-firing metals with porous ceramics. Further

modelling will incorporate kinetic aspects of interfacial

reactions using equilibrium thermodynamics as a basis.

Important transducer/actuator materials include

Pb-containing perovskite-type relaxor ferroelectrics.

First-principles (FP) methods were successfully used

to calculate the phonon frequencies for the prototype

relaxor PbMg1/3Nb2/3O3. In FP studies of PbTiO3,

the dipole moment generated by a nearest-neighbor Pb-O

vacancy pair was calculated; the results demonstrate

that local electric fields generated by defects strongly

affect physical properties. Calculations were also

performed for a Pb-free relaxor, K1–xLixTaO3. For

small x, Li ions are displaced from centrosymmetric

positions. The dominant mechanisms for Li hopping

between off-centered positions and the resulting effects

on the dielectric response were determined.

First-principles methods were also applied to the

microwave dielectric system (1–x)CaAl1/2Nb1/2O3–

xCaTiO3. The resulting model yields a dielectric

constant that increases with increasing disorder, and

increases nonlinearly with increasing x, in agreement

with experiment.
22

Phase Relationships in High Temperature Superconductors

Phase diagrams serve as “blue prints” for

improved processing of high Tc superconductor

materials. Of current interest are the

Ba2RCu3O6+x (R = lanthanides and yttrium)

superconductors. The construction of phase

diagrams of these systems and the role of phase

equilibria and kinetics in the formation of the

Ba2YCu3O6+x phase using barium fluoride

amorphous precursor films are important for

rapid advancement of the RABiTS/IBAD coated

conductor technology. By providing the phase

equilibria data for optimal processing, high Tc

technology will be advanced through reductions

in cost and improvements in performance.

Winnie Wong-Ng, Lawrence P. Cook, and

Igor Levin

I

n 2003, NIST materials research has continued

 to provide critical information pertinent to the

development of practical superconductors. This project

is an integral part of the Department of Energy intensive

research program focused on high Tc wires and cables

for high-impact commercial applications. Our effort

included two principal groups of superconductors:

(1) Ba2RCu3O7 (Y-213 and R-213, R = lanthanide)

coated conductors produced by rolling assisted biaxially

textured substrate/ion beam assisted deposition

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

Part of our effort has been focused on the

dependence of BaO-R2O3-CuOx phase relations (under

carbonate-free conditions to match the processing

conditions of RABiTS/IBAD conductors) on both

oxygen pressure, pO2, and choice of lanthanides. This

year, we have completed the study of three systems,

with R = Gd, Eu and Ho. The trends of phase formation

and tie-line relationships with respect to lanthanide size

that were found previously for R = Nd, Sm, Eu, Gd, Ho,

Y, and Er, were observed in the present work. Near the

BaO-rich region, phase formation was very different

from what was found previously for samples prepared

in the presence of carbonate.

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 of the extent of solid solution

formation with respect to the size of R was observed

in Ba2–x(Nd1+x–yR′y)Cu3O6+z (R′ = Gd, Y and Yb) and

in Ba2–x(R1+x–yYy)Cu3Oz (R = Eu and Gd). There is

considerable improvement of critical current density,

Jc(H), for samples with partial Y-substitution at high

fields at 77 K as compared with that of Nd-213 and

Y-213. This improvement is likely due to the increased

flux pinning as a result of doping of Nd3+ in the

Ba2+ site.

The “BaF2 ex-situ” process is a promising

method for producing long-length, high-quality

Y-213 superconducting tapes. Previously, using a

controlled-atmosphere differential thermal analysis

system, we detected the presence of low temperature

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

system, which can be modeled in compositional

space as a trigonal prism. This year, we initiated

a study to understand the details of complex phase

relations in selected Ba-Y-Cu//O,F subsystems:

BaO-Y2O3-CuOx-BaF2, BaF2-YF3-CuF2-CuOx,

BaF2-Y2O3-CuOx-YF3, BaF2-CuO, and BaF2-Cu2O.

Our results explained the presence of low temperature

melts, and confirmed the importance of pO2 in

oxyfluoride melting reactions.

To control film properties, it is important to

understand the details of Y-213 phase evolution

from amorphous “BaF2” films. High temperature

x-ray diffraction has been successfully applied to

a number of films deposited on SrTiO3 model

substrates (provided by Oak Ridge National Laboratory,

ORNL). The phase formation sequences in the binary

(BaF2-Y2O3, BaF2-CuOx and Y2O3-CuOx) and ternary

(BaF2-Y2O3-CuOx) systems have been determined.

Further studies of phase evolution of these films on

both SrTiO3 and RABiTS substrates will be conducted.

Understanding the interfacial reactions of Y-213 with

buffer layers in RABiTS/IBAD films is critical to the

development of coated conductor tapes. Since phase

diagrams can provide information on how to avoid or

control the formation of second phases, we have

initiated a study of the BaO-Y2O3-CeO2-CuOx system

(interaction of Y-213 with the CeO2 buffer layer).

Efforts have continued on the measurement of

enthalpy of formation and vapor pressure of MgB2.

Sources of the variability in these properties have also

been determined.

Contributors and Collaborators

M. Vaudin (Ceramics Division, NIST); Q. Huang

(NIST Center for Neutron Research); R. Shull

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

Division, NIST); R. Feenstra (ORNL); T. Holesinger

(Los Alamos National Laboratory); M. Rupich

(American Superconductor Corp.); J. Kaduk (BP-Amoco);

T. Haugan (U.S. Air Force); P. Canfield (Iowa State)

Data and Data Delivery
23

Materials for Micro- and Opto-Electronics

U.S. microelectronics and related industries

are in fierce international competition to design and

produce smaller, lighter, faster, more functional,

and more reliable electronics products more quickly and

economically than ever before. At the same time, there

has been a revolution in recent years in new materials

used in all aspects of microelectronics fabrication.

Since 1994, the NIST Materials Science and

Engineering Laboratory (MSEL) has worked closely

with the U.S. semiconductor, component, packaging,

and assembly industries. These efforts led to the

development of an interdivisional MSEL program

committed to addressing industry’s most pressing

materials measurement and standards issues central

to the development and utilization of advanced

materials and material processes. The vision that

accompanies this program — to be the key resource

within the Federal Government for materials metrology

development for commercial microelectronics

manufacturing — may be realized through the

following objectives:

■ Develop and deliver standard measurements and data;

■ Develop and apply in situ measurements on materials

and material assemblies having micrometer- and

submicrometer-scale dimensions;

■ Quantify and document the divergence of material

properties from their bulk values as dimensions

are reduced and interfaces contribute strongly

to properties;

■ Develop models of small, complex structures to

substitute for or provide guidance for experimental

measurement techniques; and

■ Develop fundamental understanding of materials

needed in future micro- and opto-electronics.

With these objectives in mind, the program

presently consists of projects led by the Metallurgy,

Polymers, Materials Reliability, and Ceramics

Divisions that examine and inform industry on key

materials-related issues. These projects are conducted

in concert with partners from industrial consortia,

individual companies, academia, and other government

agencies. The program is strongly coupled with

other microelectronics programs within government

and industry, including the National Semiconductor

Metrology Program (NSMP) at NIST. Materials

metrology needs are also identified through industry

groups and roadmaps, including 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) roadmaps, and the National

[Magnetic Data] Storage Industry Consortium (NSIC).

Although there is increasing integration

within various branches of microelectronics and

optoelectronics, the field can be considered in three

main areas. The first, microelectronics, includes

needs ranging from integrated circuit fabrication to

component packaging to final assembly. MSEL

programs address materials metrology needs in

each of these areas, including lithographic polymers

and electrodeposition of interconnects, electrical,

mechanical, and physical property measurement

of dielectrics (interlevel, packaging, and wireless

applications), and packaging and assembly processes

(lead-free solders, solder interconnect design, thermal

stress analysis, and co-fired ceramics).

The second major area is optoelectronics, which

includes work which often crosses over into electronic

and wireless applications. Projects currently address

residual stress measurement in optoelectronic films,

optical and structural characterization of wide bandgap

semiconductors, and standards development for

III–V compound semiconductors. Cross-laboratory

collaborations with EEEL figure prominently in

this work.

The third area is magnetic data storage, where

the market potential is vast and growing and the

technical challenges extreme. NSIC plans to

demonstrate a recording density of 1 terabit per

square inch — 40 times today’s level — by 2006.

To reach these goals, new materials are needed that

have smaller grain structures, can be produced as thin

films, and can be deposited uniformly and economically.

New lubricants are needed to prevent wear as spacing

between the disk and head becomes smaller than the

mean free path of air molecules. Some measurements

require calibration of magnetometers using certified

magnetic standards in several different shapes and

magnetic strengths, and with a wide range in magnetic

character. MSEL is working with the magnetic

recording industry to develop measurement tools,

modeling software, and standards to help achieve

these goals, with MSEL, the Electronics and Electrical

Engineering Laboratory, the Physics Laboratory,

the Information Technology Laboratory, and the

Manufacturing Engineering Laboratory working as

partners in this effort.

Contact: Grady White

Program Overview
24

Nano- and Micro-Electronic Materials Characterization

As the scale of electronic devices is reduced,

tools for characterizing materials properties

and behavior at the nano- and micro-scale are

required. We are developing and characterizing

techniques to measure local properties, e.g.,

texture, strain, chemical homogeneity, and

phase evolution, in materials used in nanoand micro-electronic systems.

John E. Blendell and Mark D. Vaudin

The characterization of nano- and micro-electronic

 materials requires different techniques than those

used for bulk electronic materials. For example,

optimizing the properties of multilayer systems

requires knowledge of the structure and composition

of interfaces at nearly atomic resolution. In ferroelectric

thin films for ferroelectric random access memory

(FRAM), local texture is known to have a significant

effect on fatigue and imprint. The origin of strains

at phase interfaces that cause microcracking can be

determined from the structure of the surface near

the crack. Examples of our research addressing

these issues are highlighted below.

order of 0.05°. The width of the strain field varied

from 2 μm to 15 μm in different specimens.

The presence of impurities or an intergranular liquid

phase can significantly alter properties by affecting the

motion of grain boundaries and transport or conductivity

between grains. We have studied the influence of boundary

misorientation and chemistry on the velocity of interfaces

in SrTiO3 single crystals of varying orientations. Crystals

were bonded to dense textured polycrystalline SrTiO3

ceramics; upon heating, the interface migrates into the

ceramic. This experiment allows the isolation of key

variables including crystallographic misorientation,

impurity content, curvature, and boundary energy, leading

to control over the nature of the grain boundaries, and

the potential for improved properties.

Piezo-force microscopy (PFM) is used for

characterizing individual domain orientations and the

piezoelectric coefficient of ferroelectric thin films.

Interpretation of results is complicated by highly

localized, short-range interactions acting at the tip, as

well as long-range interactions acting along the lever.

The resulting distributed loads change the load applied

at the tip by a factor of ≈ 3/8. Of greater importance

is the impact of distributed loading on the angle along

the lever. PFM measurements of piezoactuation can

differ substantially from the true piezoactuation under

conditions that have been modeled. Model calculations

are supported by AFM measurements performed

with interferometric lever detection and by PFM

measurements on lead zirconate titanate thin films

and triglycine sulfate crystals.

Silicon oxide-nitride-oxide multilayers are potential

materials for charge storage structures in non-volatile

memory devices; individual layers are 5 nm to 10 nm

thick. Thorough microscopic examination of

multilayers using electron energy loss spectroscopy,

secondary ion mass spectrometry, and x-ray absorption

spectroscopy revealed numerous details of the interface

structure as a function of processing. There is a

broadening of the nitrogen distribution across the

nitride/oxide interfaces and reduction of the hydrogen

content with increasing thermal budget in processing

the top oxide. Also, radial-distribution functions are

similar for differently processed silicon oxide layers.

Contributors and Collaborators

I. Levin, B. Huey, A. Scotch, D. Yoder (Ceramics

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

NIST); R. Leapman (National Institutes of Health, NIH);

M. Kovler (Tower Semiconductor, Ltd.); W. Dawson,

E. Sabolsky (NexTech Materials, Ltd.)

Figure 1: Average tilt angle of lattice planes of AlxGa1–xN thin

films versus distance from a crack.

A road block in the application of AlxGa1–xN as

light sources and detectors is the development of

cracks during deposition of the films. Electron

back-scatter diffraction (EBSD) was used to

characterize the misorientation around individual

cracks in 0.25 μm – 1.2 μm thick AlGaN films on (111)

silicon substrates. EBSD showed that the orientation

of the AlGaN in the vicinity of each crack changed so

that lattice planes in the film tilted away from the crack

causing uplift of the specimen surface, which was also

seen by atomic force microscopy (AFM). The basal

plane orientation change across the cracks was typically

0.6° (Figure 1) with a measurement accuracy of the

Materials for Micro- and Opto-Electronics
25

Wide Band Gap/Optoelectronic Materials

The Optoelectronics Industry Development

Association roadmaps cite the need for standard

reference materials (SRMs) and measurement

methods to calibrate deposition processes and

evaluate material properties. This project

addresses those needs in the following areas:

photoluminescence measurements of AlxGa1–xAs

films for SRMs; photoreflectance measurements

of band gap in InGaAsN; cathodoluminescence

measurements to assess film quality in AlGaN;

and Raman and photoluminescence measurements

to evaluate stress and composition in AlxGa1–xAs.

Albert Paul, Lawrence Robins, and Grady White

The NIST program to produce AlxGa1–xAs standard

reference materials (SRMs) for the optoelectronics

industry is nearing completion. Photoluminescence

(PL) determined compositions of AlxGa1–xAs/Ge films

and AlGaAs lift-off films have been compared with

results of inductively-coupled-plasma optical-emission

spectroscopy (ICP–OES) measurements made in the

Analytical Chemistry Division at NIST. Although Ge

substrates eliminated biasing the ICP–OES results with

Ga or As from GaAs substrates, there was concern

that the Ge substrates would alter the AlxGa1–xAs

band gaps. However, PL measurements confirmed

that band gap energies for AlGaAs/Ge agreed with

AlGaAs/GaAs. Al.20Ga.80As SRMs are to be released

in September 2003.

A paper, “Refractive Index Study of AlxGa1–xN

Films Grown on Sapphire Substrates,” has been

accepted by the Journal of Applied Physics.

Raman and PL spectra of AlxGa1–xAs have been

calibrated in terms of stress and composition. Details are

given in the Technical Highlights section of this report.

Contributors and Collaborators

Y.-S. Kang, M.D. Vaudin (Ceramics Division, NIST);

T.A. Butler, G.C. Turk (Analytical Chemistry Division,

NIST); A.V. Davydov, W.J. Boettinger, A.J. Shapiro

(Metallurgy Division, NIST); K.A. Bertness, T.E. Harvey,

N.A. Sanford (Optoelectronics Division, NIST);

A.G. Birdwell (Semiconductor Electronics, NIST);

D. Bryson, M. Fahmi, S.N. Mohammad (Howard

University); S. Keller, U.K. Mishra, S.P. DenBaars

(University of California, Santa Barbara); D.V. Tsvetkov,

V.A. Soukoveev, A.V. Dmitriev (Technologies and

Devices International, Inc.)

Figure 1: PR of InGaAs films.

Figure 2: CL of AlGaN films

Photoreflectance (PR) is a useful probe of the

electronic structure of InGaAsN films, a new class of

infrared optoelectronic materials. Figure 1 shows PR

spectra of films with 8 % In, 0.4 % N, and varying

silicon dopant and free carrier (“n”) concentrations.

The lines broaden and critical point energies shift

upward with increasing “n”. Arrows indicate the fitted

band gap (lowest direct transition) energies. Higher-lying

transitions (not labeled) are ascribed to splitting of

both the valence and conduction bands in these alloys.

As part of a study of compositional, structural,

and optical properties of AlGaN films, grown by either

metalorganic chemical vapor deposition (MOCVD)

or hydride vapor phase epitaxy (HVPE) on (0001)

sapphire, the near-band-edge optical properties of the

samples were probed by cathodoluminescence (CL)

spectroscopy. Figure 2 compares low-temperature CL

of films produced by different deposition processes.

The near-band-edge CL lineshape is sensitive to

compositional fluctuations and defect levels. The

results suggest that recent HVPE grown films have

improved homogeneity and crystalline quality.

Materials for Micro- and Opto-Electronics
26

Materials Property Measurements

This program responds both to the Materials

Science and Engineering Laboratory (MSEL) customer

requests and to the Department of Commerce 2005

Strategic Goal of “providing the information and

framework to enable the economy to operate efficiently

and equitably.” For example, manufacturers and their

suppliers need to agree on how material properties

should be measured. Equally important, engineering

design depends on accurate property data for the

materials that are used.

The MSEL Materials Property Measurement

Program works toward solutions to measurement

problems on scales ranging from the macro to

the nano, in four of the Laboratory’s Divisions

(Ceramics, Materials Reliability, Metallurgy, and

Polymers). The scope of its activities ranges from

the development and innovative use of state-of-the-art

measurement systems, to leadership in the development

of standardized test procedures and traceability

protocols, to the development and certification of

Standard Reference Materials (SRMs). A wide range

of materials is being studied, including polymers,

ceramics, metals, and thin films (whose physical

and mechanical properties differ widely from the

handbook values for their bulk properties).

Projects are directed toward innovative new

measurement techniques. These include:

■ Measurement of the elastic, electric, magnetic, and

thermal properties of thin films and nanostructures

(Materials Reliability Division); and

■ Alternative strength test methods for ceramics,

including cylindrical flexure strength and diametral

compression (Ceramics Division).

The MSEL Materials Property Measurement

Program is also contributing to the development of

test method standards through committee leadership

roles in standards development organizations such as

the American Society for Testing of Materials (ASTM)

and the International Standards Organization (ISO).

In many cases, industry also depends on measurements

that can be traced to NIST Standard Reference Materials

(SRMs). This program generates the following SRMs

for several quite different types of measurements:

■ Charpy impact machine verification (Materials

Reliability Division);

■ Hardness standardization of metallic materials

(Metallurgy Division); and

■ Hardness standardization and fracture toughness

of ceramic materials (Ceramics Division).

Supporting the Materials Property Measurements

Program is a modeling and simulation effort to connect

microstructure with properties. The Object-Oriented

Finite-Element (OOF) software developed at NIST is

being used widely in diverse communities for material

microstructural design and property analysis at the

microstructural level.

In addition to the activities above, all four

divisions provide assistance to various government

agencies on homeland security and infrastructure

issues. Projects include assessing the performance

of structural steels as part of the NIST World

Trade Center Investigation, advising the Bureau of

Reclamation on metallurgical issues involving pipelines

and dams, advising the Department of the Interior

on the structural integrity of the U.S.S. Arizona

Memorial, advising the U.S. Customs Service on

materials specifications for ceramics, and advising

the Architect of the Capitol on repair procedures for

cracks in the outer skin of the Capitol Dome.

Contact: George Quinn

Program Overview
27

Mechanics of Materials

The reliability of brittle materials may be

improved through study of their microstructure,

mechanical properties, and failure mechanisms.

Fractography, computational modeling tools, and

transmission electron microscopy are being used

to study the effects of structure, particularly the

role of flaws and defects, on the strength and

reliability of ceramic components.

George Quinn, Edwin Fuller, Jr., and

Bernard Hockey

Ceramic materials, by virtue of their light weight,

good, high-temperature performance, and

broad-ranging electronic and optical properties,

offer many highly desirable qualities to the designers

of devices and components. However, problems

can arise when high-fracture toughness or accurate

lifetime prediction are required because of the inherent

brittleness of most ceramics and their propensity to

fail from small flaws or defects. We study the effects

of microstructure on the mechanical properties of

brittle materials, including microstructural features

that result from such manufacturing processes as

coating deposition or surface grinding or machining.

The strength of a brittle material is very often

determined by the size of the largest flaw in a test

specimen; large flaws concentrate stress and lower

strength. In the case of ceramic parts that are brought

to their final shape by an abrasive grinding process,

the largest flaws can be those created at the surface by

the machining process. Sometimes small changes in

that process can have a dramatic effect on the strength

of the part. An intensive study of damage in ground

ceramic surfaces has been completed and important

trends documented in NIST Special Publication 996.

The telltale signs of machining cracks were identified,

and schematic illustrations and simple techniques to

detect these features were added as a major revision

to the fractography standard ASTM C 1322. The size

and severity of cracks were correlated to grinding

conditions. Wheel grit size and grinding direction were

reconfirmed to be dominant factors, and the effect was

quantified for the first time. Grinding damage maps

for silicon nitride were determined; an example is

shown in Figure 1.

Another area of work concerns the structure

and mechanical properties of alumina and zirconia

thermal barrier coatings (TBCs). Transmission electron

microscopy examination of plasma spray coatings made

with submicron-sized powders revealed that the coating

microstructures were very non-uniform and showed

improved hardness and wear resistance relative to

conventional plasma sprayed coatings. Controlled

indentation flaws were also used to characterize

interfacial fracture toughness in TBC systems.

Microstructure-based finite-element simulations,

based on the NIST object oriented finite element (OOF)

code, were used to elucidate crack–microstructure

interactions. Experimental studies and corroborative

OOF simulations on particulate-reinforced ceramic

matrix composites showed strong crack path variations

with changes in the loading/unloading rate and

microstructure. OOF simulations were used to

elucidate the influence of grain orientation texture on

bulk physical properties (e.g., coefficients of thermal

expansion) and on physical behavior (e.g., residual

stresses and microcracking propensity). Misorientation

distribution functions were shown to have a profound

influence on the residual stress networks that were

observed in both real and simulated microstructures.

Contributors and Collaborators

D. Saylor, L. Ives (Ceramics Division, NIST);

W. Luecke (Metallurgy Division, NIST); M. Bartsch,

B. Baufeld (German Aerospace Research Laboratory,

Germany); S. Wu, B. Palted (University of Alabama);

A. Wereszczak, M. Ferber (Oak Ridge National Lab);

S. Lee (Sun Moon University, Korea)

Figure 1: Grinding damage map for silicon nitride.

Materials Property Measurements
28

Materials Structure Characterization

Fundamental to the field of materials science and

engineering is the study of the relationships between

processing, structure, properties, and performance

of materials. Therefore, tools and techniques for

the characterization of materials structure is a

cornerstone of the field. The NIST Materials Science

and Engineering Laboratory (MSEL) has a long tradition

of supporting and developing measurement methods

and facilities for materials structure characterization.

Facilities within MSEL include optical and electron

microscopy, optical and electron scattering and

diffraction, a state-of-the-art x-ray diffractometer, the

NIST Center for Neutron Research, and experimental

stations at the National Synchrotron Light Source

(NSLS) at Brookhaven Laboratory and at the Advanced

Photon Source (APS) at Argonne National Laboratory.

At the NSLS, NIST operates a soft x-ray station in

partnership with Dow and Brookhaven National

Laboratory. At the APS, NIST is a partner with the

University of Illinois at Urbana/Champaign, Oak Ridge

National Laboratory, and UOP in a collaboration called

UNICAT. At both facilities, NIST scientists and

researchers from industry, universities, and government

laboratories perform state-of-the-art measurements on

a wide range of advanced materials. NIST scientists

have consistently advanced the limits of these facilities

in order to improve spatial resolution and sensitivity

needed, for example, to interrogate the microstructure

of both highly anisotropic and/or gradient materials

such as advanced thermal coatings and fuel cell

systems. Studies currently underway at these facilities

include: in situ measurements of nanoparticle

production; structure and dispersion of carbon

nanotubes; three-dimensional imaging of natural and

artificial tissues; surface and subsurface damage in

UV lithography optics; strain-induced ferroelectric

transitions in thin films; and determination of molecular

orientation and bond concentration on chemically

heterogeneous surfaces.

The materials characterization program has

a strong emphasis on electron microscopy. The MSEL

Electron Microscopy Facility provides structure and

compositional characterization of a wide range of

materials. The facility consists of two transmission

electron microscopes (TEMs), three scanning electron

microscopes (SEMs), a specimen preparation laboratory,

and an image analysis/computational laboratory.

The JEM3010 TEM resolves the atomic structure and

employs an energy selecting imaging filter and x-ray

detector (EDS) for analytical characterization of thin

foil specimens. The JSM6400 SEM employs electron

backscattered diffraction/phase identification and EDS

systems to characterize the texture and composition

of materials. Highlights from the facility for FY2003

include: the computer domain is now active, providing

streamlined user access and network file storage;

a research collaboration with the NIST Semiconductor

Electronics Division is underway to characterize

quantum effects in confined Si devices; the size and

shape of III–V quantum dots are characterized with

the NIST Optoelectronics Division; and composition

maps of electrodeposited nanowires with tunable

magnetic properties are generated in collaboration

with Johns Hopkins University.

This MSEL program also incorporates standards

activities. A state-of-the-art x-ray diffractometer has

been developed to study the metrology of powder

diffraction in order to develop the next generation of

diffraction standard reference materials. A variety of

standard reference materials (SRMs) needed by the

U.S. polymers industry, research laboratories, and

other federal agencies have recently been developed:

polyethylene of narrow mass distribution; nonlinear

fluids for rheological measurements; melt flow

standards; and the first reference biomaterial, an

orthopedic grade ultra-high molecular weight

polyethylene.

Recent program activities utilize matrix-assisted laser

desorption/ionization time-of-flight mass spectrometry

(MS) to address the need for improved characterization

of the molecular structure of polyolefins, a dominant

commercial polymer. This work has extended the

upper mass limit detectable by MS to 15,000 g/mol

and, by observing individual oligomeric species by

mass, has revealed details of the molecular structure.

A major cross-cutting activity within this program

is the multi-scale, multi-modal imaging and visualization

project. The goal of this project is to combine disparate

sets of 3-D imaging data that contain complementary

information on overlapping length scales to produce

an interactive visualization scheme for multivariate

data sets. This year focused on further improvements

and additions to the suite of imaging tools for tissue

engineering metrology. Osteoblasts cultured in a

poly (ε-caprolactone) scaffold have been imaged,

demonstrating the advantages of optical coherence

and confocal fluorescence microscopies over

conventional laser scanning confocal microscopy.

This instrument was upgraded by completely rebuilding

the image acquisition software, hardware, and optical

train. These improvements enabled an increase in

image acquisition speed (2X) and accuracy

(from 5 μm to 360 nm).

Contact: David R. Black

Program Overview
29

Diffraction Metrology and Standards

Both powder and high-resolution diffraction can

provide a wealth of information with a relatively

simple scan. However, the data are beset by a

complex error function. It is the characterization

of this function, critical to the accuracy of the

technique, that is one of the prime functions of

NIST diffraction Standard Reference Materials

(SRMs). In order to be traceable to Systeme

Internationale (SI) based units, certification

measurements must be performed on equipment

that features goniometers that are self-calibrating,

i.e., equipped with stable, high-resolution

encoders that have been calibrated using the

circle closure method.

James P. Cline and Donald A. Windover

This project establishes the traceability of NIST

diffraction SRMs certified with respect to lattice

parameter or layer spacing. From Bragg’s Law,

λ = 2d sinθ, we see that traceability in spacing, d,

requires both traceabilty in wavelength, λ, and angle, θ.

The linkage of wavelength to the SI has been developed,

and follows the first four levels in the traceability

diagram shown in Figure 1. Here we devise a rigorous

approach for the calibration of the goniometers in

the Ceramics Division parallel beam diffractometer,

establishing the traceabilty of angle measurement in

future SRM certification.

We utilize a goniometer assembly with two axes of

interest and a third stage for rotation of optical faces.

This approach provides a matrix of encoder errors.

Matrix inversion yields the calibration curves, shown

in Figure 2, for the ω and 2θ goniometers.

Contributors and Collaborators

Figure 1: Measurement chain of NIST certified diffraction SRMs. Albert Henins (Ceramics Division, NIST)

Figure 2: Encoder error corrections from circle closure.

To be useful in a metrological context, a goniometer

must have a stable, accurate and precise optical encoder.

However, the encoder will exhibit an error function that

must be characterized. The term “self-calibrating” refers

to the ability of the goniometer to measure angles in a

metrologically credible manner without relying on an

external artifact and is realizable through the method of

circle closure. A caveat to the method is that encoder

errors must only be long range in nature, i.e., caused by

mounting misalignment, eccentricity, etc. In order to

realize a conceptual understanding of the circle closure

method, assume the goniometer of interest is equipped

with a second, coaxially mounted rotation stage. This

second stage rotates two optical faces, mounted parallel

to the rotation axis and exhibiting a 30° dihedral angle.

A scanning autocollimator is used to generate a feature

associated with the angle of each face. The fitting of

this feature results in a measurement precision of the

angle between the faces that is much greater than that

offered by the encoder itself. After each measurement,

the second stage is rotated 30°, and the process repeated

to yield a series of data points through 360°. Circle closure

asserts that the sum of the angle measurements for one

complete axis rotation must be 360°, and therefore, all

errors sum to zero. Thus, the average of the measured

dihedral angles provides the true angle, and deviations

from this angle map the encoder correction curve.

Materials Structure Characterization
30

Small-Angle Scattering and Imaging

Microstructure (or nanostructure) control is the

key to property and performance optimization

for many materials that provide critical functions

in advanced technological systems. Achieving

this control requires quantitative characterization

of microstructure over a contiguous size range

from the nanoscale to the mesoscale. This project

addresses this need by combining small-angle

x-ray and neutron scattering methods with x-ray

imaging capabilities to provide a microstructurecharacterization-based metrology that links

materials processing to performance.

Andrew Allen, Jan Ilavsky, and Gabrielle Long

New technological materials, such as those for

 fuel cells or thermal barrier coatings, present

increasingly difficult microstructure characterization

challenges. At the Advanced Photon Source (APS),

as part of UNICAT (university/national laboratory/

industry collaborative access team), we have made

significant advances in the development of x-ray

micro-tomography (XMT) and in the application of

small-angle x-ray scattering (SAXS) to meet these

challenges. The unique capability of the NIST

ultra-SAXS (USAXS) instrument to measure absolute

intensity now makes it a reference for several SAXS

instruments at the APS and positions us for possible

development of a SAXS standard reference material.

In a continuing effort to more rapidly develop and to

expand our suite of synchrotron-radiation-based x-ray

characterization tools, we have developed a partnership

with the X-ray Operations and Research (XOR)

Division at the APS. The XMT capability at XOR

serves as a proving ground for the development of

nanoscale resolution XMT at UNICAT, and their

capability for high-energy SAXS (HESAXS) provides

increased sample penetration and spatial resolution

that complement the NIST USAXS capability. Several

examples of our research efforts are highlighted below.

A multi-component anisotropic-void model for

USAXS analyses was used to quantify the complex

microstructure of electron beam physical vapor

deposited (EBPVD) thermal barrier coatings. These

coatings are used in advanced gas turbine engines

and are of particular interest to companies such as

GE and Siemens–Westinghouse. Measurements of

coatings before and after heat treatment reveal that,

due to thermal expansion mismatch, a 2 % by volume

population of cracks oriented normal to the substrate

forms. When combined with thermal and mechanical

property measurements performed by collaborators at

SUNY Stony Brook, new insight has been gained into

coating failure modes.

Electron-beam directed vapor deposited (EB-DVD)

coatings are proposed as an alternative to conventional

electron beam physical vapor-deposited coatings

for high temperature thermal barrier applications.

In collaboration with the University of Virginia,

HESAXS has been combined with wide-angle x-ray

diffraction to study EB-DVD coatings. The same

sample volume was measured with both techniques at

a spatial resolution of 20 μm. The measurements show

that preferred crystallographic growth axes dominate

near the top of the coating while void anisotropy,

which plays a key role in coating durability and

performance, varies throughout the thickness.

In collaboration with the University of Utah, the

structure of solid oxide fuel cell (SOFC) materials has

been investigated. Measurements of pore structure

and phase content have been made within each layer

using USAXS, HESAXS (at 5 μm spatial resolution)

and XMT. At a spatial resolution of 1.35 μm, XMT

shows in 3D, for the first time, both the pore and

segregated-phase size and interconnectivity actually

present in the membrane layers (see Figure 1).

Use of different x-ray energies allows the image

contrast for different features to be optimized.

This research supports current efforts to join major

Department of Energy initiatives in fuel cell research.

Contributors and Collaborators

T.A. Dobbins, D.R. Black (Ceramics Division,

NIST); C. Rau (Purdue University); P.R. Jemian

(University of Illinois); A. Kulkarni, H. Herman (SUNY

Stony Brook); C.A. Johnson (GE); D. Hass, H. Wadley

(University of Virginia); A. Virkar (University of Utah);

J. Almer, F. De Carlo (Argonne National Laboratory)

Figure 1: XMT single-slice images through a SOFC anode layer

at (a) 17 keV and (b) 27 keV x-ray energy. The 27 keV image

exhibits a strong contrast between the Ni and yttria-stabilized

zirconia components.

Materials Structure Characterization
31

Synchrotron Beam Line Operation and Development

The synchrotron radiation project is focused on

the operation and continued development of unique

experimental facilities at the Advanced Photon

Source (APS) at Argonne National Laboratory

and at the National Synchrotron Light Source

(NSLS) at Brookhaven National Laboratory

(BNL). The emphasis is on the development and

application of microstructural characterization

tools and techniques that allow researchers from

industry, universities and government laboratories

to perform leading edge measurements on

technologically advanced materials.

David R. Black

At the APS, the Ceramics Division, through UNICAT

 (a NIST/University of Illinois/Oak Ridge National

Laboratory/UOP collaboration), supports activities in

ultra-small-angle x-ray scattering (USAXS) and USAXS

imaging on the insertion device line and x-ray absorption

fine structure (XAFS) and diffraction topography on

the bending magnet line. A hard x-ray microscope is

under development. As in previous years, the USAXS

instrument received the highest demand of any UNICAT

instrument, with nearly 50 % of the available beam time

being used for USAXS experiments. The USAXS

instrument has been upgraded with an overconstrained

weak-link rotational stage, which has significantly

improved stability and reproducibility. The software for

data reduction has been completed and the first version

of software for data analysis is available on the Web.

Examples of research supported by this facility include:

in-situ production of nanoparticles in a flame; fuel cell

microstructure; fillers for human medical implant glues;

and imaging of human and artificial tissues.

Research from this facility was featured on

the cover of the January 13, 2003 issue of Applied

Physics Letters, as shown in Figure 2, “Combinatorial

near-edge x-ray absorption fine structure: simultaneous

determination of molecular orientation and bond

concentration on chemically heterogeneous surfaces.”

This year, a larger and more versatile main experimental

chamber was commissioned, enabling all of our unique

fluorescence and electron detection capabilities to be

installed simultaneously.

Contributors and Collaborators

A.J. Allen, H.E. Burdette, D.A. Fischer, G.G. Long,

J.C. Woicik, D. Yoder (Ceramics Division, NIST);

L.E. Levine (Metallurgy Division, NIST); S. Sambasivan

(University of Delaware); J. Genzer, K. Efimenko

(North Carolina State University); J. Ilavsky, C. Rau

(Purdue University); P. Jemian, P. Zschack, H. Hong,

J. Karapetrova (University of Illinois)

On the bending magnet beamline, NIST researchers

have used XAFS and diffraction to study SrTiO3

single-crystals and thin films grown on Si (100)

surfaces. Figure 1 shows the Ti-K near-edge XAFS

for a series of thin films of differing thickness.

The increase in the intensity of the pre-edge peak for

films thinner than about 80 Å indicates hybridization

of the Ti 3d and 4p states. This hybridization occurs

because inversion symmetry is broken due to strain

from the substrate. This “clamping effect” leads to a

local ferroelectric transition in the films.

At the NSLS, the NIST/Dow beamline (U7A) is

recognized as a leading materials science experimental

facility on the UV ring. For the last reporting period from

the NSLS, beamline U7A accounted for over 1/3 of the

total number of publications reported for the UV ring.

Figure 1: XAFS data for SrTiO3 thin films.

Figure 2: Cover of

Applied Physics Letters.

Materials Structure Characterization
32

Program Overview

Nanocharacterization

The emphasis on nanotechnology around the world

and the successful implementation of the National

Nanotechnology Initiative in the U.S. are accelerating

the development of science and technology at the

nanoscale. Nanotechnology is expected to play a key

role within the next 10 years in a wide spectrum of

industry sectors including manufacturing, information

technology, electronics, and healthcare. Novel devices

at the micro- and nanoscale will become increasingly

important in all of these industries. The ability to

measure dimensions, characterize materials, and

elucidate structures of new and novel materials at

the nanoscale will be critical to the advancement of

nanotechnology. In addition, one of the exciting

prospects of nanotechnology lies in the ability of

molecules or particles, under specific conditions, to

self-assemble to form new materials with unusual

properties. Successful development of these new

materials will require the ability to monitor such

processes at the nanoscale in real time. Metrology,

the science of measurement, is therefore the foundation

of nanotechnology. Standards and reference materials

will also provide essential infrastructural support to

this emerging technology.

The objective of the program in the NIST Materials

Science and Engineering Laboratory (MSEL) is to

develop basic measurement metrology at the nanoscale

for the determination of bulk and surface material

properties and for process monitoring. Measurement

methods are being developed for use in conjunction

with new instrumentation and calibration artifacts.

The scope of the program encompasses metals,

ceramics, and polymers in various forms — particles,

thin films, nanotubes, and self-assembled structures

— and also includes studies of nanocomposites

and liquid-state properties for microfluidics-based

fabrication and measurement techniques. Physical

properties such as mechanical strength, elastic moduli,

friction, stiction, adhesion, and fatigue strength

are measured, as well as the size of nanoparticles

and the structure and dispersion behavior of

nanoparticulate systems. Other properties such

as electrical conductivity, thermal conductivity,

magnetic properties, electronic properties, and

optical properties are also examined. While the

program focuses on developing measurement

techniques at the nanoscale, proper data interpretation

requires fundamental studies in nanomechanics,

scaling laws, and imaging techniques.

There are currently ten projects under the program:

■ Bridging Length Scales in Theory and Modeling;

■ Electrochemical Processing of Nanoscale Materials;

■ Metrology for Nanoscale Properties;

■ Nanofiller Processing;

■ Nanoindentation;

■ Nanomechanics and Standards;

■ Nanoscale Manufacturing;

■ Nanotribology and Surface Properties;

■ Particle Metrology and Standards; and

■ Physical Properties of Thin Films and Nanostructures.

In many of these individual projects, objectives

are directed toward the study of a particular class of

materials or material properties, but the underlying

theme of the program as a whole is to develop

reliable, accurate measurement techniques for a

broad range of materials and material properties at the

nanoscale. As just one example, four methods for the

determination of the elastic properties of thin films —

atomic force acoustic microscopy, surface acoustic

wave spectroscopy, Brillouin light scattering, and

nanoindentation — are being compared using common

sets of specimens. This study will lead to a better

understanding of the complementary nature of these

techniques for measuring nanostructured materials

and their combined use to determine supplementary

properties such as film thickness or density. Standard

reference materials are being developed in collaboration

with other National Measurement Institutes around the

world for use in the verification of the performance

of these instruments.

Contact: Stephen M. Hsu
33

Nanocharacterization

Nanomechanics and Standards

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 IIT machine verification. This effort involves

the comparison of IIT results to measurements done in

the Materials Reliability Division using surface acoustic

wave spectroscopy. Results on SiO2 and TiO2 coatings

show the techniques to be in good agreement.

Other intercomparisons of thin-film mechanical

test methods are underway in Technical Working

Area (TWA) 22 of VAMAS (Versailles Project on

Advanced Materials and Standards, www.vamas.org).

Here, international round robin testing for hardness,

elastic properties, and adhesion is being conducted to

determine the reproducibility of the results between

different laboratories using different commercial

testing equipment.

In electronic and optoelectronic multilayer

structures, delamination driven by residual stress can

lead to device failure. In collaboration with the NIST

Optoelectronics Division, we characterize composition

and structure in III–V optoelectronic materials and are

developing Raman and photoluminescence techniques

for measuring residual stress in films as thin as 30 nm.

Three-dimensional finite-element simulations are being

used to elucidate the influence of film properties and

geometry on the residual stress tensor.

In many mechanical test methods, 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 because the Standard International (SI)

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

The Microforce Competence Program at NIST is

developing a primary realization of force, traceable to

electronic and length SI units, for force calibration in

the range 1 mN to 1 nN. 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.

Contributors and Collaborators

B. Hockey, D. Saylor, G. White, G. Quinn, E. Fuller,

S. Hsu (Ceramics Division, NIST); D. Hurley (Materials

Reliability Division, NIST); B. Lawn (MSEL, NIST);

K. Bertness (Optoelectronics Division, NIST);

J. Pratt (Manufacturing Metrology Division, NIST);

U. Beck (BAM, Germany); N. Jennett (National Physical

Laboratory, U.K.); O. Takai (Nagoya University, Japan)

Although much of the focus in nanotechnology

is on the electronic and magnetic properties of

nanoscale devices, there are many applications

where device performance depends on the

mechanical properties of the materials used.

Stress and interfacial adhesion affect the

reliability of multilayer electronic structures.

Devices with micro- and nano-scale moving

parts, such as cantilevers, gears and micro-mirror

arrays, suffer mechanical fatigue and premature

failure for reasons that are often not well

understood. We develop test methods and

standards for measuring mechanical properties

at the nanoscale.

Douglas T. Smith

I

n the world of macroscopic mechanical testing,

 many well-characterized, standardized test methods

are available to measure elastic modulus, hardness,

strength, fracture toughness, adhesion, residual stress

and a host of other properties critical to the successful

design of reliable macroscopic structures. Often,

knowledge of these same properties is just as critical to

the design of micro- and nano-scale devices, but in this

realm, accurate, reliable test methods for determining

mechanical properties are rare. We are working on

developing and evaluating techniques for mechanical

property measurement, helping to draft standard test

methods and developing Standard Reference Materials

(SRMs) and force calibration methodology for

low-force (mN down to nN) mechanical testing.

One of the most commonly used techniques for

determining hardness and elastic modulus of small

volumes of materials is instrumented indentation testing

(IIT), often referred to as nanoindentation, in which a

diamond indenter is pushed into a specimen surface and

the force on, and displacement into, the surface are

recorded, and those data are analyzed. The technique

is capable of providing information on the elastic and

plastic deformation of a specimen for indentations as

shallow as 10 nm to 20 nm, and it is routinely used

to measure the mechanical properties of thin films.

However, until now there have been no accepted test

methods that would allow IIT to be used as part of a

thin-film or coating product specification. We are

working with both the American Society for Testing

of Materials, ASTM (E28.06.11), and the International

Standards Organization, ISO (TC 164/SC 3), on draft

standards for IIT; an ISO document for the technique

is now at the level of Final Draft International Standard

(FDIS 14577). In addition, the Ceramics and Materials
34

Nanotribology and Surface Properties

Accurate adhesion/friction measurements at the

nanoscale are needed in microelectromechanical

systems (MEMS) and nanoelectromechanical

systems (NEMS) devices. Lubrication by

molecular assemblies at nanometer dimension

is required to control the surface properties

of device components and ensure durability.

The magnetic storage industry also needs control

of friction via lubrication in the push towards

1 Terabit/in2 areal density and a fast data

transfer rate. The head-disk interface space is

shrinking to 3.5 nm, with a head speed of 40 m/s.

Occasional contacts between the head and

disk will test the strength and robustness of the

carbon overcoat and lubricant layers which

are continuously being reduced in thickness.

Stephen Hsu

Significant progress has been achieved in two areas:

 measurements for adhesion, friction, and lubrication

at the nanoscale and establishing test methods relevant

to magnetic hard disk performance (with input from

the National Storage Industry Consortium.)

The nanofriction measurement activity aims

to develop a constitutive equation for nanofriction

to include surface force components and material

characteristics. We set up a novel, multiscale friction

apparatus, developed jointly with Hysitron, allowing

friction measurements across nm to mm scales.

Figure 1 shows friction data from a diamond tip sliding

on silica for different tip sizes (tip radius). The coefficient

of friction values show significant dependence on tip size.

Future work in nanofriction comparing results among

different scales will provide an understanding of how

the scale affects frictional forces.

We continue to work with our external academic

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

the NIST Nanotechnology Extramural Initiative. This

collaboration focuses on the development of friction

measurement by three approaches: MEMS devices,

AFM-based methods, and a novel ultra-high vacuum

method. Results thus far have revealed that meniscus

forces and electrostatic forces exert a significant effect

on nanofriction. We are now quantifying these effects.

Significant progress has been made in establishing

test methods for assessing the performance of the

carbon overcoat and lubricant layers in magnetic head/

disk interfaces. A high speed impact test was developed

to simulate the occasional high-speed impacts that

occur between the head and the disk media under the

ramp-load and unload operating conditions. As the

magnetic spacing continues to shrink, this type of

contact could lead to data loss. In our test, a 1000 nm

ridge is artificially created on a disk, and a ruby ball is

used to collide with the ridge at 20 m/s. The impact

force and the deformation are measured using an

acoustic sensor. Recent improvements in the impact

height control were achieved by installing capacitance

probes to control the location and positioning of the

ruby ball in the z direction. Crater imaging was also

improved by using a new dual white light interferometer

microscope. (See Figure 2.) Results show that the

performance ranking of lubricants and overcoats agrees

with field experience.

Figure 1: Effect of tip sizes on friction.

Figure 2: Microscopic image of impact craters.

A finite element model was developed last year

to describe the stress distribution in the carbon

overcoat/lubricant multilayer films. Recently, the

model was improved by incorporating brittle fracture

criteria for the carbon overcoat. This refinement

allows the determination of the threshold stress level

where data loss may occur.

Contributors and Collaborators

C. Ying, R. Gates, J. Chuang, D. Fischer

(Ceramics Division, NIST); B. Bhushan (Ohio State);

K. Komoupoulas (UC Berkeley); G. Liu (UC Davis);

Y.T. Hsia (Seagate); J. Sengers (University of Maryland)

Nanocharacterization
35

Particle Metrology and Standards

As technology migrates toward smaller physical

dimensions, new analytical approaches are

required to characterize material properties

and to investigate scientifically important issues.

In particle technology, these needs become

critical in the nanosize regime. Industrial

processes involving nanoparticle technology

include advanced device manufacture and

the development and production of functional

materials for microelectronic, pharmaceutical,

and biotechnology applications. Our goal

is to improve existing metrology and develop

new methods and standards for measuring the

physical and interfacial properties of nanosize

and nanostructured particle systems.

Vincent A. Hackley and James Kelly

Standard reference materials (SRMs) are critical

 for calibrating instruments used for nanoparticle

characterization. Primary customers for nanoparticle

SRMs are quality control laboratories in the ceramic and

pharmaceutical industries. This year, we have initiated

the production of a 100 nm to 500 nm particle size

distribution (PSD) SRM, the first of its kind (inorganic

material system with a broad size distribution), to fulfill

a pressing need in the sub-micrometer size range.

Interest in this TiO2-based standard has been

expressed from a wide range of industries. The SRM

will be certified for PSD using electron microscopy

and by X-ray disc centrifuge methods. Additionally,

certification of SRM 1021 was completed. This

SRM is intended for the evaluation and calibration of

equipment used to measure PSDs in the 2 μm to 12 μm

diameter range. The size range of this SRM follows

that of the coarser beads of existing SRM 1003c.

Another activity involves ultra-small angle x-ray

scattering (USAXS) of nanoparticle suspensions and

partially-gelled systems. Objectives are to develop

sensitive metrological techniques for characterizing

metastable and unstable nanoparticle suspensions and

to gain new insights into mechanisms influencing their

agglomeration and stabilization. Systems of interest

include SiO2, TiO2, and ZrO2, studied after stabilization

at pH values representing states close to and far from

the isoelectric point. For example, Figure 1 shows

discrete particle doublets (right-hand peak) in SiO2

suspensions that form only at the isoelectric pH.

USAXS allows such phenomena to be quantified to

an unprecedented level. A flow cell for in situ,

real-time USAXS studies of unstable suspensions

is under development.

This year, a new activity was initiated on interfacial

property measurements of nanostructured particulates.

The goal is to develop the measurement methodology

to obtain reliable data to establish a clear relationship

between charge development and particle size,

crystallinity and interparticle structure. Metal oxides

exposed to an aqueous phase develop charge via

protonation of surface hydroxyl sites. Surface charge

and surface site reactivity play key roles in dissolution,

precipitation and growth, corrosion, aggregation, and

sorption processes. As particle size shrinks into the

low nano-regime (< 10 nm), charge development

and reactivity are predicted to exhibit size dependent

behavior. Preliminary results indicate some potentially

important findings.

■ A systematic decrease in the isoelectric point of

TiO2 with decreasing crystallite size was observed;

data will be incorporated into modeling efforts by

NSF-funded researchers to account for proton-induced

charge formation as a function of crystal size.

■ Zeta potential measurements indicate that adducts

formed between nanocrystalline MgO and molecular

halogen species are more stable in an aqueous medium

than had been previously predicted; this has important

implications for their use as microbial biocides.

■ Small-angle neutron scattering experiments suggest

MgO may be capable of localized expansion around

individual crystallites in response to an aqueous

intrusion, without fully disrupting the assembly

structure; this would represent a unique attribute

not typically associated with inorganic particles.

Contributors and Collaborators

A. Allen, A. Jillavenkatesa, L. Lum (Ceramics

Division, NIST); L. Sung, C. Ferraris (Materials &

Construction Research Division, NIST); D. Ho (Center

for Neutron Research, NIST); K. Klabunde (Kansas State

University); U. Paik (Hanyang University); M. Ridley

(Texas Tech University); M. Machesky (Illinois State

Figure 1: Volume fraction PSD for SiO Water Survey); P. Jemian (University of Illinois) 2 at the isoelectric point.

Nanocharacterization
36
37

Ceramics Division Databases and Standards

Ceramics Division Databases and Standards

Databases:

NIST Standard Reference Database 15:

NIST/Sandia/International Centre for Diffraction

Data (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. (NIST

Contact: V.L. Karen.) Available for purchase at

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

NIST Standard Reference Database 30:

Structural Ceramics Database. Physical, mechanical,

and thermal properties; more than 38,000 numeric

values. (NIST contact: R.G. Munro.) Available online

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

NIST Standard Reference Database 31:

NIST/ACerS Phase Equilibria Diagrams. Produced

jointly by NIST and the American Ceramic Society;

thirteen regular book volumes, five topical volumes,

and a computerized database on CD ROM; more than

53,000 units have been sold; the current CD contains

approximately 26,000 critically evaluated diagrams

and 15,000 expert commentaries. (NIST Contact:

T.A. Vanderah.) Available for purchase at

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

NIST Standard Reference Database 62:

High Temperature Superconductors. Physical,

mechanical, thermal, and superconducting

properties; more than 30,000 numeric values.

(NIST contact: R.G. Munro.) Available online at

http://www.ceramics.nist.gov/srd/hts/htsquery.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. (NIST Contact: V.L. Karen.) Available for

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

NIST Standard Reference Database 84:

FIZ/NIST Inorganic Crystal Structure Database,

Release 2003/1 (August 2003); produced cooperatively

by the Fachinformationszentrum Karlsruhe (FIZ)

and NIST; a comprehensive collection of full

structural crystal data of inorganic compounds;

contains more than 60,000 entries. (NIST contact:

V.L. Karen.) Available for purchase at

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

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. (NIST contact: R.G. Munro.)

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 Materials:

Available for purchase at http://ts.nist.gov/ts/

htdocs/230/232/232.htm:

Standard Reference Material 1021: Glass Beads

– Particle Size Distribution, a particle size standard for

size range 2 μm to 12 μm. (NIST contact: J. Kelly.)

Standard Reference Material 1003c: Glass Beads

– Particle Size Distribution, a particle size standard for

size range 20 μm to 50 μm. (NIST contact: J. Kelly.)

Standard Reference Material 1018b: Glass Beads

– Particle Size Distribution, a particle size standard

for size range 220 μm to 750 μm. (NIST contact:

J. Kelly.)

Standard Reference Material 1019b: Glass Beads

– Particle Size Distribution, a particle size standard

for size range 750 μm to 2450 μm. (NIST contact:

J. Kelly.)

Standard Reference Material 659: Particle Size

Distribution for Sedigraph Calibration, a particle size

standard for size range 0.2 μm to 10 μm. (NIST

contact: J. Kelly.)
38

Standard Reference Material 8010: Sand for

Sieve Analysis. (NIST contact: J. Kelly.)

Standard Reference Material 1982: Zirconia

Thermal Spray Powder – Particle Size Distribution, a

particle size standard for size range 10 μm to 150 μm.

(NIST contact: J. Kelly.)

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. (NIST contact: J. Kelly.)

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. (NIST contact:

J. Kelly.)

Standard Reference Material 2831: Vickers

Hardness of Ceramics and Metals, a tungsten carbide

Vickers hardness block with nominal Vickers Hardness

of 15.0 GPa (1530 kgf /mm2) for use at a testing force

of 9.8 N (1.0 kgf). (NIST contact: G. Quinn.)

Measurement Standards:

ASTM C 1161, (2002): Standard Test Method for

Flexural Strength of Advanced Ceramics at Ambient

Temperature. (NIST contact: G. Quinn.)

ASTM C 1322, (2002): Standard Practice for

Fractography and Characterization of Fracture Origins

in Advanced Ceramics. (NIST contact: G. Quinn.)

ASTM F 2094, (2001): Standard Specification for

Silicon Nitride Bearing Balls. (NIST contact: G. Quinn.)

ASTM C 1211, (2002): Standard Test Method for

Flexural Strength of Advanced Ceramics at Ambient

Temperature. (NIST contact: G. Quinn.)

ISO Standard 17565, (2001): Fine Ceramics

(Advanced Ceramics, Advanced Technical Ceramics) —

Test Method for Flexural Strength of Monolithic Ceramics

at Elevated Temperature. (NIST contact: G. Quinn.)

ISO 18756, (2002): 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. (NIST contact: G. Quinn.)

Ceramics Division Databases and Standards
39

Ceramics Division FY03 Annual Report Publication List

Ceramics Division FY03 Annual Report Publication List

Allen, A.J. “Neutron Methods Link Microstructure

to Processing and Performance for Thermal Barrier

Coatings.” News Brief, J. Res. Nat. Inst. Stand.

Technol., 107, 134 (2002).

Allen, A.J., N.F. Berk, J. Ilavsky, and G.G. Long.

“Multiple Small-Angle Neutron Scattering Studies of

Anisotropic Materials.” Appl. Phys. A, Mater. Sci.

Process., Part 2 Suppl., 74, S937–S939 (2002).

Balasubramanian, M., H.S. Lee, X. Sun, X.Q. Yang,

A.R. Moodenbaugh, J. McBreen, D.A. Fischer, and

Z. Fu. “Formation of Solid Electrolyte Interface on

Cycled Lithium-Ion Battery Cathodes: Soft X-ray

Ab-sorption Study.” Electrochemical and Solid-State

Letters, 5, A22–A25 (2002).

Bartsch, M., B. Baufeld, and E.R. Fuller, Jr.

“Elucidating Thermo-Mechanical Spallation of Thermal

Barrier Coating-Systems Using Controlled Indentation

Flaws.” Ceram. Eng. Sci. Proc., 24 [3–4] (2003).

Bartsch, M., U. Schulz, J.-M. Dorvaux, O. Lavigne,

E.R. Fuller, Jr., and S.A. Langer. “Simulating Thermal

Response of EB-PVD Thermal Barrier Coating

Microstructures.” Ceram. Eng. Sci. Proc., 24 [3–4]

(2003).

Begley, E.F., and C.P. Sturrock. “The Background

and Development of MatML, a Markup Language for

Materials Property Data.” Proceedings of the 18th

International CODATA Conference, Toronto, Ontario,

Canada, September 30–October 4, 2002, ICSU

Committee on Data for Science and Technology,

Paris, France (2002).

Belsky, A.J., M. Hellenbrandt, V.L. Karen, and

P. Lucksch. “New Developments in the Inorganic

Crystal Structure Database (ICSD): Accessibility in

Support of Materials Research and Design.” Acta

Crystallographica Section B, Structural Science, B58,

364–369 (2002).

Blendell, J.E., M.R. Locatelli, J.S. Wallace and

B.J. Hockey. “Modeling of Anisotropic Shrinkage

During Sintering of Low Temperature Co-fired Ceramic

Tapes.” IMAPS Advanced Technology Workshop on

Ceramic Applications for Microwave and Photonic

Packaging Report, Providence, RI (2002).

Blendell, J.E., and J.S. Wallace, “Grain Growth in

Relaxor Ferroelectrics.” AFOSR Joint Contractors

Meeting Report, Bar Harbor, ME (August 2002).

Boettinger, W.J., M.D. Vaudin, M.E. Williams,

L.A. Bendersky, and W.R. Wagner. “Electron

Backscattered Diffraction and Energy Dispersive X-ray

Specroscopy Study of the Phase NiSn4.” Journal of

Electronic Materials, 32 (6), 511–515 (2003).

Boukari, H., A.J. Allen, G.G. Long, J. Ilavsky,

J.S. Wallace, C.C. Berndt, and H. Herman. “Small-Angle

Neutron Scattering Study of the Role of Feedstock

Particle Size on the Microstructural Behavior of

Plasma-Sprayed Yttria-Stabilized Zirconia Deposits.”

J. Mater. Res., 18, 624–634 (2003).

Burton, B.P., and A. Van de Walle. “First Principles

Based Calculations of the CaCO3-MgCO3 Subsolidus

Phase Diagrams.” Physics and Chemistry of Minerals,

30, 88–97 (2003).

Cedeno, C.L., and M.A. Harne. Phase Equilibria

Diagrams 2003 Cumulative Index. Westerville, OH:

The American Ceramic Society (2003).

Chawla, N., B.V. Patel, M. Koopman, K.K. Chawla,

R. Saha, B.R. Patterson, E.R. Fuller, Jr., and

S.A. Langer. “Microstructure-Based Simulation of

Thermomechanical Behavior of Composite Materials by

Object Oriented Finite (OOF) Element Analysis.”

Mater. Charac., 49, 395–407 (2003).

Chen, C.I., and S.M. Hsu. “A Chemical Kinetic

Model to Predict Lubricant Performance in a Diesel

Engine. Part I: Simulation Methodology.” Tribology

Letters, 14, No. 2, 83–90 (2003).

Ching, W.Y., Y.N. Xu, L. Ouyang, and

W. Wong-Ng. “Comparative Study of the Electronic

Structure of Ternary Superconductors MoRuP and

ZrRuP in the Orthorhombic and Hexagonal Phases.”

J. Appl Phys., 93 (10), 8209-8211 (2003).

Choi, J.H., D.K. Kim, S.M. Wiederhorn,

J.E. Blendell, B.J. Hockey, and C.A. Handwerker.

“The Equilibrium Shape of Internal Cavities in Ruby

and the Effect of Surface Energy Anisotropy on the

Equilibrium Shape.” J. Am. Ceram. Soc., 85 [7],

1841–44 (2002).

Chuang, T.-J., and E.R. Fuller, Jr. “Analysis of

Residual Stress State in Thermal Barrier Coatings.”

Fracture Mechanics of Ceramics, 13, 169–178 (2003).

Chuang, T.-J., S. Jahanmir, and H.C. Tang.

“Finite Element Simulation of Straight Plunge Grinding

for Advanced Ceramics.” J. Europ. Ceram. Soc., 23,

1723–1733 (2003).
40

Ceramics Division FY03 Annual Report Publication List

Cook, L.P., W. Wong-Ng, P. Schenck, M. Vaudin,

and J. Suh. “A Model System for Interfacial

Reactions in LTCC Materials.” Proceedings of

IMAPS International Microelectronics and Packaging

Society (IMAPS) Conference on Ceramic Interconnect

Technology, April 7–9, 2003, Denver, CO, International

Microelectronics and Packaging Society, pp. 177–182

(2003).

Dieng, L.M., A.Y. Ignatov, T.A. Tyson, M. Croft,

F. Dogan, C.-Y. Kim, J.C. Woicik, and J. Grow.

“Observation of Changes in the Atomic and Electronic

Structure of Single-Crystal YBa2Cu3O6.6 Accompanying

Bromination.” Phys. Rev. B, 66, Art. No. 14508

(2002).

Evans, C.E., A.C. Smith, D.J. Burnett, A.L. Marsh,

D.A. Fischer, and J.L. Gland. “Polymer Conversion

Measurement of Diacetylene-Containing Thin-Films

and Monolayers using Soft X-ray Fluorescence

Spectroscopy.” J. Phys. Chem. B, 106, 9036–9043

(2002).

Farber, L., I. Levin, A. Borisevich, I.E. Gray,

R.S. Roth, and P.K. Davies. “Structural Study of

Li1+x-y Nb1-x-3yTix+4yO3 Solid Solutions.” J. Solid

State Chem., 166 (1), 81–90 (2002).

Ferraris, C.F., V.A. Hackley, A.I. Avilés, and

C.E. Buchanan. “Analysis of the ASTM Round-Robin

Test on Particle Size Distribution of Portland Cement:

Phase II.” NISTIR 6931, National Institute of

Standards and Technology, Technology Administration,

USDOC, Gaithersburg, MD (2002).

Gallagher, D.T., C. Stover, D. Charlton,

L. Arnowitz, and D.R. Black. “X-ray Topography

of Microgravity-Grown Rnase S Crystals.” J. Crystal

Growth, 255/3–4, 403–413 (2003).

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

“Molecular Orientation and Grafting Density in

Semifluorinated Self-Assembled Monolayers of

Mono-, Di- and Trichloro Silanes on Silica Substrates.”

Langmuir, 18, 9307–9311 (2002).

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

“Combinatorial Near-Edge X-Ray Absorption Fine

Structure: Simultaneous Determination of Molecular

Orientation and Bond Concentration on Chemically

Heterogeneous Surfaces.” Applied Physics Letters, 82,

266–268 (2003).

Genzer, J., E.J. Kramer, and D.A. Fischer.

“Accounting for Auger Yield Energy Loss for Improved

Molecular Orientation Using Soft X-Ray Absorption.”

J. Applied Physics, 92, 7070–7079 (2002).

Goyal, A., W. Wong-Ng, M. Murakami, and

J. Driscoll, eds. “High Temperature Superconductor

Processing.” Electronics Division Focus Session

at the ACerS Annual Meeting, St. Louis, MO,

April 29–May 1, 2002. Ceramics Transaction, Vol. 140.

Columbus, OH: The American Ceramic Society (2003).

Hackley, V.A., M. Naito, and R. Wäsche.

“Measuring the Isoelectric Point of Ceramic

Powder Suspensions: A Pre-Standardization Study.”

Ed. M. Matsui, S. Jahanmir, H. Mostagaci, M. Naito,

K. Uematsu, R. Waesche, and R. Morrell. Improved

Ceramics Through New Measurements, Processing,

and Standards, Ceramic Transactions, 133, 15–24,

Maui, Hawaii, Nov. 4–8, 2001. Westerville, OH:

The American Ceramic Society (2002).

Haugan, T.J., W. Wong-Ng, L.P. Cook, M.D. Vaudin,

L. Swartzendruber, and P. Barnes. “Partial Melt

Processing of Solid–Solution Bi2SrCaCu2O8+x Thick

Film Conductors with Nanophase Al2O3 Additions.”

J. Mater Res. Soc., 18 [5], 1054–1066 (2003).

Haugan, T.J., M.E. Fowler, J.C. Tolliver,

P.N. Barnes, W. Wong-Ng, and L.P. Cook.

“Flux Pinning and Properties of Solid-Solution

(Y,Nd)1+xBa2-xCu3O7-z Superconductors.” Electronics

Division Focus Session at the ACerS Annual Meeting,

St. Louis, MO, April 29–May 1, 2002. Ed. A. Goyal,

W. Wong-Ng, M. Murakami, and J. Driscoll. High

Temperature Superconductor Processing, Ceramics

Transaction, 140, 299–308. Columbus, OH: The

American Ceramic Society (2003).

Hockey, B.J., S.M. Wiederhorn, J.E. Blendell,

J.-S. Lee, and M.-K. Kang. “Structure of Sapphire

Bicrystal Boundaries Produced by Liquid-Phase

Sintering.” J. Am. Ceram. Soc., 86 [4], 612–22 (2003).

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

Proceedings of the Second Asian International

Conference on Tribology, Jeju, Korea, Oct. 21–23,

2002, KSTLE, Seoul, Korea, pp. 49–50 (2002).

Hsu, S.M., J. Zhang, and Z.F. Yin. “The Nature

and Origin of Tribochemistry.” Tribology Letters,

13, 2, 131–139 (2002).

Hsu, S.M., R.G. Munro, and M.C. Shen.

“Wear in Boundary Lubrication.” J. Engineering

Tribology, 216, 427– 441 (2002).

Hsu, S.M. “Nanotribology: the Link to

Macrotribology.” Ed. G.W. Stachowiak. Proceedings

of the 6th International Tribology Conference,

Austrib’02: Frontiers in Tribology, Perth, Australia,

Dec. 2– 5, 2002, pp. 9–16 (2002).
41

Ceramics Division FY03 Annual Report Publication List

Hsu, S.M., and Z.C. Ying, eds. Nanotribology:

Critical Assessment and Research Directions. New

York: Kluwer Academic Press (2002).

Hsu, S.M. “Nano-Lubrication: Principle and

Design.” Ed. S.M. Hsu and Z.C. Ying. Nanotribology:

Critical Assessment and Research Directions, Chap. 23,

pp. 327–346. New York: Kluwer Academic Press (2002).

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

Proceedings of the First U.S.–China Joint Conference

on Tribology, Beijing, China, Oct. 16–18, 2002,

Tsinghua University, Beijing, China (2003).

 Hsu, S.M., R.S. Gates, and D.E. Deckman.

“Ceramics Lubrication.” Proceedings of 10th

CIMTEC International Ceramics Congress (2003).

Hsu, S.M., and C.I. Chen. “A Chemical Kinetic

Model to Predict Diesel Engine Performance. Part II.

Bench Test Procedures.” Tribology Letters, 14, No. 2,

91–97 (2003).

Hsueh, C.H., S. Lee, and T.-J. Chuang.

“An Alternative Method of Solving Multilayer Bending

Problems.” J. Appl. Mech., 70, 151–154 (2003).

Huang, Q.Z., V.L. Karen, A. Santoro, A., Kjekshus,

J. Linden, T. Pietari, and P. Karen. “Substitution of

Co3+ in YBa2Fe3O8.” J. Solid State Chem., 172, 73–80

(2003).

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

“Effective Pinhole-Collimated Ultrasmall-Angle X-ray

Scattering Instrument for Measuring Anisotropic

Microstructures.” Rev. of Sci. Instrum., 73, Part 2,

1660–1662 (2002).

Jeffrey, G.A., and V.L. Karen. “Crystallography.”

Ed. E.R. Cohen, D.R. Lide, and G.L. Trigg.

AIP Physics Desk Reference, 3rd edition, Chap. 9,

pp. 306–348. New York: Springer–Verlag (2002).

Kalin, M., S. Jahanmir, and B.J. Hockey. “Wear

of Hydroxyapatite Sliding Against Glass-Infiltrated

Alumina. J. Mater. Res., 18 [1], 27–36 (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. Released 2002/1 (August 2002),

2002/2 (February 2003), and 2003/1 (August 2003).

Karen, P., A. Kjekshus, Q. Huang, V.L. Karen,

J.W. Lynn, N. Rosov, I. Natali Sora, and A. Santoro.

“Neutron Powder Diffraction Study of Nuclear

and Magnetic Structures of Oxidized and Reduced

YBa2 Fe3 O8+w.” J. Solid State Chem., 174, 87–95

(2003).

Keller, T., W. Wagner, A.J. Allen, J. Ilavsky,

N. Margadant, S. Siegmann, and G. Kostorz.

“Characterisation of Thermally-Sprayed Metallic

NiCrAlY Deposits by Multiple Small-Angle Scattering.”

Appl. Phys. A, Mater. Sci. Process., Part 2 Suppl., 74,

S975–S977 (2002).

Kim, C.-Y., M.J. Bedzyk, E.J. Nelson, J.C. Woicik,

and L.E. Berman. “Site-Specific Valence Band

Photoemission Study of alpha-Fe2O3.” Phys. Rev. B.,

66, Art. No. 085115 (2002).

Klein, R., L.P. Cook, and W. Wong-Ng.

“Enthalpies of Formation of the Strontium Plumbates

SrPbO3 and Sr2PbO4 from Solution Calorimetry and

Knudsen Effusion Thermogravimetry.” J. Chemical

Thermodynamics, 34, 2083–2092 (2002).

Kulkarni, A., Z. Wang, T. Nakamura, S. Sampath,

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

G.G. Long, J. Frahm, and R.W. Steinbrech.

“Comprehensive Microstructural Characterization

and Predictive Property Modeling of Plasma-Sprayed

Zirconia Coatings.” Acta Mater., 51, 2457–2475

(2003).

Lenhart, J.L., R.L. Jones, E.K. Lin, C.L. Soles,

W.L. Wu, D.A. Fischer, S. Sambasivan, D.L. Goldfarb,

and M. Angelopolous. “Probing Surface and Bulk

Chemistry in Resist Films Using NEXAPS.” J. Vac.

Sci. and Technol. B, 20, 2920–2926 (2002).

Lenhart, J.L., R.L. Jones, E.K. Lin, C.L. Soles,

W.L. Wu, D.A. Fischer, S. Sambasivan, D.L. Goldfarb,

and M. Angelopolous. “Probing Surface and Bulk Deprotection in Resist Films Using NEXAFS.” Proc. ACS

Div. Poly. Mat. Sci. and Eng., 87, 417 (2002).

Leung, K., E. Cockayne, and A.F. Wright.

“Effective Hamiltonian Study of PbZr0.95Ti0.05O3.”

Physical Review B, 65, 214111–24 (2002).

Levin, I., T.A. Vanderah, R. Coutts, and S.M. Bell.

“Phase Equilibria and Dielectric Properties in

Perovskite-Like (1-x)LaCa0.5Zr0.5O3–xATiO3

(A = Ca, Sr) Ceramics.” J. Mater. Res., 17 [7],

1729–1734 (2002).

Levin, I., T.J. Amos, J.C. Nino, T.A. Vanderah,

C.A. Randall, M.E. Lanagan, and I.M. Reaney.

“Crystal Structure of Compound Bi2Zn2/3Nb4/3O3.”

J. Mater. Res., 17 [6], 1406–1411 (2002).

Levin, I., J.Y. Chan, J.H. Scott, L. Farber,

T.A. Vanderah, and J.E. Maslar. “Complex Polymorphic

Behavior and Dielectric Properties of Perovskite-Related

Sr(Sr1/3Nb2/3)O3.” J. Solid State Chem., 166 [1],

24– 41 (2002).
42

Levin, I., T.G. Amos, J. Nino, T.A. Vanderah,

I.M. Reaney, C.A. Randall, and M.T. Lanagan.

“Crystal Structure of the Compound Bi2Zn2/3Nb4/3O7.”

J. Materials Res., 17 [6], 1406–1411 (2002).

Levin, I., T.G. Amos, J.C. Nino, T.A. Vanderah,

C.A. Randall, and M.T. Lanagan. “Crystal Structure of

an Unusual Cubic Pyrochlore Bi1.5Zn0.92Nb1.5O6.92.”

J. Solid State Chem., 168, 69–75 (2002).

Li, X., L. Andruzzi, E. Chiellini, G. Galli,

C.K. Ober, A. Hexemer, E.J. Kramer, and D.A. Fischer.

“Semifluorinated Aromatic Side-Group Macromolecules

Polystyrene-Based Block Copolymers: Bulk Structure

and Surface Orientation Studies.” Macromolecules, 35,

8078–8087 (2002).

Lin, Y.-S., R. Puthenkovilakam, J.P. Chang,

C. Bouldin, I. Levin, N.V. Nguyen, Y. Sun, P. Pianetta,

T. Conard, W. Vandervost, V. Venturo, and S. Selbrede.

“Interfacial Properties of ZrO2 on Silicon.” J. Appl.

Phys., 93 [10], 5945–5952 (2003).

Liu, C.Y., S. Lee, and T.-J. Chuang. “GrainBoundary Crack Growth in Interconnects with an

Electric Current.” Materials Science and Engineering,

B86, 101–108 (2003).

Lofaj, F., S.M. Wiederhorn, G.G. Long, B.J. Hockey,

P.R. Jemian, L. Browder, J. Andreason, and U. Taffner.

“Non-Cavitational Tensile Creep in Silicon Nitride with

Lu-Based Additives.” J. Eur. Ceram. Soc., 22 [14–15],

2479–2487 (2002).

Lofaj, F., D.T. Smith, G.V. Blessing, W.E. Luecke,

and S.M.Wiederhorn. “Instrumented Indentation and

Ultrasonic Velocity Techniques for the Evaluation of

Creep Cavitation in Silicon Nitride.” J. Mater. Sci., 38,

1403–1412 (2003).

Mighell, A.D. “Conventional Cells: Monoclinic

I- and C-centered Cells.” Acta Crystallographica,

B59 [2], 300–302 (2003).

Mighell, A.D. “Lattice Matching (LM) — Prevention

of Inadvertent Duplicate Publications of Crystal

Structures.” J. Res. Natl. Inst. Stand. Technol., 107,

425–429 (2002).

Mighell, A.D. “Conventional Cells — The Last Step

Toward General Acceptance of Standard Conventional

Cells for the Reporting of Crystallographic Data.”

J. Res. Natl. Inst. Stand. Technol., 107, 373–377

(2002).

Munro, R.G. “Titanium Diboride (TiB2).” NIST

Property Data Summaries, Ceramics WebBook, http://

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

(2002).

Munro, R.G. Data Evaluation Theory and Practice

for Materials Properties. NIST Recommended Practice

Guide, SP 960-11, Gaithersburg, Maryland (2003).

Munro, R.G., and C.P. Sturrock. “Structural

Ceramics Database Update (April 2003).”

NISTIR 7022 and Ceramics WebBook, http://

www.ceramics.nist.gov/srd/scd/scdquery.htm,

Gaithersburg, Maryland (2003).

Nelson, E.J., J.C. Woicik, P. Pianetta,

I.A. Vartanyants, and J.W. Cooper. “Quadrapole

Effects in Core- and Valence-Photoelectron Emission

from Crystalline Germanium Measured via a Spatially

Modulated X-ray Interference Field.” Phys. Rev. B,

65, Art. No. 165219 (2002).

Newell, D.B., J.A. Kramar, J.R. Pratt, D.T. Smith,

and E.R. Williams. “The NIST Microforce Realization

and Measurement Project.” IEEE Transactions on

Instrumentation and Measurement, 53 [2], 508–511

(2003).

Paik, U., J.-G. Yeo, M.-H. Lee, V.A. Hackley, and

Y.-G. Jung. “Dissolution and Reprecipitation of Barium

at the Particulate BaTiO3-Aqueous Solution Interface.”

Mater. Res. Bull., 37, 1623–1631 (2002).

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

of Poly(acrylic acid) and Poly(vinyl alcohol) on the

Solubility of Colloidal BaTiO3 in an Aqueous Medium.”

J. Mater. Res., 18 [5], 1266–1274 (2003).

Park, D.-S., T.-W. Roh, B.J. Hockey, Y. Takigawa,

B.-D. Han, H.-D. Kim, and Y. Yasutomi. “Two Cores

in One Grain in the Microstructure of Silicon Nitride

Prepared with Aligned Whisker Seeds.” J. Eur. Ceram.

Soc., 23, 555–560 (2003).

Park, C.-W., D.-Y. Yoon, J.E. Blendell, and

C.A. Handwerker. “Singular Grain Boundaries In

Alumina and Their Roughening Transition.” J. Amer.

Ceram. Soc., 86 [4], 603–11 (2003).

Park, J.-K., D.-Y. Kim, H.-Y. Lee, J.E. Blendell,

and C.A. Handwerker. “Crystallographic Orientation

Dependent Dissolution Behavior of Sapphire in Anorthite

Liquid Containing Cr2O3.” J. Amer. Ceram. Soc.,

86 [6], 1014–1018 (2003).

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

“First Principles Studies of KNbO3, KTaO3,

and LiTaO3 Solid Solutions.” Ed. R.E. Cohen.

Fundamental Physics of Ferroelectrics 2002. AIP

Conference Proceedings, 626, 64–73. Woodbury, NY:

American Institute of Physics (2002).

Ceramics Division FY03 Annual Report Publication List

42
43

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

V. Trepakov, S. Kapphan, M. Savinov, and L. Jastrabik.

“Properties of K1–xLixTaO3 Solid Solutions;

First-Principles Computations and Comparison

with Experiments.” Japanese Journal of Applied

Physics, Part 1, 41, 7179–7180 (2002).

Qiang, L., L. Wu, Y. Zhu, A.R. Moodenbaugh,

G.D. Gu, M. Suenaga, Z.X. Ye, and D.A. Fischer.

“Comparative Studies of MgB2/Mg Nano-Composites

and Press-Sintered MgB2 Pellets.” IEEE Trans. on

Applied Superconductivity, 13, 3051–3055 (2003).

Quinn, G.D., P.J. Patel, and I. Lloyd. “Effect

of Loading Rate Upon Conventional Ceramic

Microindentation Hardness.” J. Res. Natl. Inst. Stand.

Technol., 107 [3], 299–306 (2002).

Quinn, G.D., P. Green, and K. Xu. “Cracking and

the Indentation Size Effect for Knoop Hardness of

Glasses.” J. Amer. Ceram. Soc., 86 [3], 441– 448

(2003).

Quinn, G.D., J.J. Swab, and M.J. Motyka.

“Fracture Toughness of a Toughened Silicon Nitride

by ASTM C 1421.” J. Am. Ceram. Soc., 86 [6],

1043–1045 (2003).

Quinn, G.D. “Weibull Strength Scaling for

Standardized Rectangular Flexure Specimens.”

J. Am. Ceram. Soc., 86 [3], 508–510 (2003).

Quinn, G.D. “Weibull Effective Volumes and

Surfaces for Cylindrical Rods Loaded in Flexure.”

J. Am. Ceram. Soc., 86 [3], 475–478 (2003).

Quinn, G.D., L.K. Ives, and S. Jahanmir.

“On the Fractographic Analysis of Machining Cracks

in Ground Ceramics: A Case Study on Silicon Nitride.”

Special Publication SP 996, NIST, Gaithersburg, MD

(May 2003).

Quinn, G.D., L.K. Ives, and S. Jahanmir.

“Fractography Reveals Machining Cracks.” Bull. Amer.

Ceram. Soc., 82 [7], 11 (2003).

Quinn, G.D., and J.J. Swab. “Standard Practice

for Fractography and Characterization of Fracture

Origins in Advanced Ceramics.” Annual Book of

Standards, ASTM C 1322-02a, Vol. 15.01, ASTM.

West Conshohocken, PA (2003).

Quinn, G.D. “Standard Test Method for

Flexural Strength of Advanced Ceramics at Ambient

Temperature.” Annual Book of Standards, ASTM

C 1161-02, Vol. 15.01, ASTM. West Conshohocken,

PA (2003).

Robins, L.H., J.T. Armstrong, R.B. Marinenko,

A.J. Paul, J.G. Pellegrino, and K.A. Bertness.

“High-Accuracy Determination of the Dependence

of the Photoluminescence Emission Energy on Alloy

Composition in AlxGa1–xAs Films.” Journal of Applied

Physics, 93, 3747–3759 (2003).

Robins, L.H., B. Steiner, N.A. Sanford, and

C. Menoni. “Low-Electron-Energy Cathodoluminescence

Study of Polishing and Etching Effects on the Optical

Properties of Bulk Single-Crystal Gallium Nitride.”

Eds. E.T. Yu, C.M. Wetzel, J.S. Speck, A. Rizzi, and

Y. Arakawa. Materials Research Society Symposium

Proceedings, Pittsburgh, PA, GaN and Related Alloys

2002, 743, 213–218 (2003).

Roth, R.S., ed. Phase Diagrams for Electronic

Ceramics I: Dielectric Ti, Nb, and Ta Oxide Systems.

Westerville, OH: The American Ceramic Society (2003).

Sahiner, M.A., S.W. Novak, J.C. Woicik,

Y. Takamura, P.B. Griffin, and J.D. Plummer.

“The Local Structure of Antimony in High Dose

Antimony Implants in Silicon by XAFS and SIMS.”

MRS 2002 Spring Meeting, San Francisco, CA,

April 1–5, 2002, Mat. Res. Soc. Symp. Proc., 717,

Art. No. C3.6 (2002).

Schenck, P.K., and D.L. Kaiser. “Blazing a Trail.”

Chemistry in Britain, 39, 45–47 (2003).

Siegrist, T., T.A.Vanderah, Ch. Svensson, and

R.S. Roth. “Crystal Structure of Ba27Fe16Ti33O117.”

Solid State Sciences, 4, 911–916 (2002).

Sturrock, C.P., and E.F. Begley. “MatML: A New

Language for the Exchange of Materials Property Data

over the World Wide Web.” AMPTIAC Quarterly, 6,

No. 3, 7–9. Rome, NY: IIT Research Institute (2002).

Vanderah, D.J., R.S. Gates, V. Silin, D.N. Zeiger,

J.T. Woodward, C.W. Meuse, G. Valincius, and

B. Nickel. “Isostructural Self-Assembled Monolayers.

1. Octadecyl 1-Thiaoligo(ethylene oxides).” Langmuir,

19, 2612–2620 (2003).

Vanderah, D.J., J. Arsenault, H. La,

R.S. Gates, V. Silin, C.W. Meuse, and G. Valincius.

“Structural Variations and Ordering Conditions for the

Self-Assembled Monolayers of HS(CH2CH2O3-6CH3.”

Langmuir, 19, 3752–3756 (2003).

Vanderah, T.A., T.R. Collins, W. Wong-Ng, I. Levin,

R.S. Roth, and L. Farber. “Phase Equilibria and Crystal

Chemistry in the BaO-Al2O3-Nb2O5 and BaO-Nb2O5

Systems.” J. Alloys Cmpds., 346 (1–2), 116–128

(2002).

Ceramics Division FY03 Annual Report Publication List
44

Vanderah, T.A. “Talking Ceramics.” Science, 298,

1182–1184 (2002).

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

J.M. Loezos, and W. Wong-Ng. “Subsolidus Phase

Equilibria and Crystal Chemistry in the System

BaO-TiO2-Ta2O5.” Solid State Sciences, 5, 49–164

(2003).

Vaudin, M.D., G.R. Fox, and G.R. Kowach.

“Accuracy and Reproducibility of X-ray Texture

Measurements on Thin Films.” Magnetic and

Electronic Films-Microstructure, Texture and

Applications to Data Storage, Mater. Res. Soc. Proc.,

721, 17–23. Pittsburgh, PA (2002).

Vertanessian, A., A.J. Allen, and M.J. Mayo.

“Agglomerate Formation During Drying.” J. Mater

Res., 18, 495–506 (2003).

Wallace, J.S., J.-M. Huh, J.E. Blendell, and

C.A. Handwerker. “Grain Growth and Twin Formation

in 0.74 PMN – 0.26 PT.” J. Amer. Ceram. Soc., 85 [6],

1581–1584 (2002).

Wallace, W.E., and D.A. Fischer. “Soft X-Ray

Pho-tofragmentation of Propane.” J. Electron

Spectroscopy and Related Phenomena, 130, 1–6 (2003).

Wang, Z., J.E. Blendell, G.S. White, and Q. Jiang.

“Atomic Force Microscope Observations of Domains in

Fine-Grained Bulk Lead Zirconate Titanate Ceramics.”

Smart Materials and Structures, 12, 217–222 (2003).

Wang, W.L., S. Lee, and T.-J. Chuang.

“Steady-state Crack Growth along a Grain Boundary

in Interconnects with a High Electric Field Intensity.”

Phil. Mag. A82, 955–970 (2002).

Weiss, T., S. Siegesmund, and E.R. Fuller, Jr.

“Thermal Stresses and Microcracking in Calcite and

Dolomite Marbles via Finite Element Modelling.”

Eds. S. Siegesmund, A. Vollbrecht, and T. Weiss.

“Natural Stone, Weathering Phenomena, Conservation

Strategies and Case Studies,” Special Publication,

No. 205, pp. 81–94. London: Geological Society

(2002).

Weiss, T., S. Siegesmund, and E.R. Fuller, Jr.

“Thermal Degradation of Marble: Indications From

Finite Element Modelling.” Building and Environment,

38, [9–10], 1251–1260 (2003).

White, G.S., E.R. Fuller, Jr., and S.W., Freiman.

“Mechanical Reliability and Life Prediction for Brittle

Materials.” Ed. Myer Kutz. Handbook of Materials

Selection, Chap. 28, pp. 809–828. New York: John

Wiley & Sons, Inc. (2002).

White, G., and T. Tsurumi, eds. Proceedings of the

13th IEEE International Symposium on Applications

of Ferroelectrics. Nara, Japan, May 28–June 1, 2002.

IPiscataway, NJ: EEE Service Center (2003).

Wiederhorn, S.M., and E.R. Fuller, Jr. “Structural

Behavior of Ceramics.” Eds. B. Karihaloo and

W.G. Knauss. Comprehensive Structural Integrity,

Volume 2: Fundamental Theories and Mechanisms of

Failure, Chap. 2.08, pp. 429–454. Oxford: Elsevier

Science (2003).

Woicik, J.C., E.J. Nelson, L. Kronik, M. Jain,

J.R. Chelikowsky, D. Heskett, L.E. Berman, and

G.S. Herman. “Hybridization and Bond-Orbital

Components in Site-Specific X-ray Photoelectron

Spectra of Rutile TiO2.” Phys. Rev. Lett., 89, Art. No.

077401 (2002).

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

Phase Relationships of the BaO-Y2O3-CuOx System

Under Carbonate-Free Conditions at pO2 = 100 Pa and

at pO2 = 21 kPa.” Physica C, 377, 107–113 (2002).

Wong-Ng, W., W.Y. Ching, X. Yong-Nian,

J.A. Kaduk, I. Shirotani, and L. Swartzendruber.

“The Structure and Electronic Properties of the

Orthorhombic MoRuP Superconductor Prepared at

High Pressure.” Phy. Rev., B14, 144523-1 to 144523-9

(2003).

Wong-Ng, W., J.A. Kaduk, and J. Dillingham.

“Crystal Structures and Reference Diffraction Patterns

of BaSrR4O8.” Powd. Diffr., 17 (No. 3), 202–205

(2002).

Wong-Ng, W. “The 2001 Material Research Society

(MRS) Fall Meeting.” Powd. Diffr., 17 (1), 61– 62

(2002).

Wong-Ng, W. “The 2002 Material Research Society

(MRS) Fall Meeting.” Powd. Diffr., 18 (1), 61–62

(2003).

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

Equilibria of the BaF2-CuOx System.” High Temperature

Superconductor Processing. Electronics Division Focus

Session at the ACerS Annual Meeting, St. Louis, MO,

April 29–May 1, 2002. Eds. A. Goyal, W. Wong-Ng,

M. Murakami, and J. Driscoll. Ceramics Transaction,

140, 385–397. Columbus, OH: The American Ceramic

Society (2003).

Xu, H.H.K., J.B. Quinn, D.T. Smith,

A.A. Giuseppetti, and F.C. Wichmiller. “Effects

of Different Whiskers on the Reinforcement of

Dental Resin Composites.” Dental Materials, 19,

359–367 (2003).

Ceramics Division FY03 Annual Report Publication List
45

Ceramics Division FY03 Annual Report Publication List

Zelezny, V., E. Cockayne, J. Petzelt, M.F. Limanov,

D. Usvyat, V.V. Lemanov, and A.A. Volkov. “Temperature

Dependence of Infrared-Active Phonons in CaTiO3:

A Combined Spectroscopic and First-Principles Study.”

Physical Rev. B, 66, Art. No. 224303 (2002).

Zhu, Y., A.R. Moodenbaugh, G. Schnieider,

J.W. Davenport, T. Vogt, Q. Li, G. Gu, D.A. Fischer,

and J. Tafto. “Unraveling the Symmetry of the Hole

States Near the Fermi Level in the MgB2 Superconductor.”

Phys. Rev. Letters, 88, Art. No. 247002 (2002).
46
47

Ceramics Division

Ceramics Division

Chief

Debra L. Kaiser

Phone: 301–975–6119

E-mail: debra.kaiser@nist.gov

Deputy Chief

David R. Black

Phone: 301–975–6119

E-mail: david.black@nist.gov

Group Leaders

Characterization Methods

David R. Black

Phone: 301–975–5976

E-mail: david.black@nist.gov

Data and Standards Technology

Ronald G. Munro

Phone: 301–975–6127

E-mail: ronald.munro@nist.gov

Electronic and Optoelectronic Materials

Grady S. White, Acting

Phone: 301–975–5752

E-mail: grady.white@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
48

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

Dobbins, Tabbetha

tabbetha.dobbins@nist.gov

Small-angle x-ray scattering

Small-angle neutron scattering

Ceramic microstructural analysis

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

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

Kaiser, Debra

debra.kaiser@nist.gov

Ferroelectric oxide thin films

Combinatorial material analysis
49

Research Staff

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

Long, Gabrielle

gabrielle.long@nist.gov

Small-angle x-ray and neutron scattering

Ceramic microstructure evolution

X-ray optics

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

Data evaluation and validation

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

White, Grady

grady.white@nist.gov

Residual stress measurements

Mechanical reliability

Raman spectroscopy

Windover, Donald

donald.windover@nist.gov

High-resolution x-ray diffraction

X-ray reflectometry

Standard reference materials
50

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

Guest Scientists and Graduate Students

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

Ilavsky, Jan

Purdue University

Jang, Mi-Hye

Yonsei University

Jemian, Peter

University of Illinois at Urbana/Champaign

Jillavenkatesa, Ajitkumar

Alfred 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

Liang, Yanang

Universided Oviedo, Spain

Research Staff

50
51

Luong, Mario

University of Maryland

McMurdie, Howard

Consultant

Mighell, Alan

Consultant

Ondik, Helen

Consultant

Ozmen, Yilmaz

Pamukkale University, Turkey

Pei, Patrick

Consultant

Peiris, Suhithi

Naval Research Laboratory

Piermarini, Gasper

University of Maryland

Prosandeev, Serguei

Rostov State University

Przedlacki, Marcin

Warshaw University of Technology

Purushotham, Kavuri

Swinbourn University

Rajagoopalan, 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, Changwon

Rensselaer Polytechnic Institute

Suh, Julia

Consultant

Swanson, Nils

American Ceramic Society

Texter, John

National Science Foundation

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
52
53

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

D.R. Black, Deputy

Materials Reliability

A.F. Clark, Chief

T.A. Siewert, Deputy

NIST Center for

Neutron Research

J.M. Rowe, 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