chemical vapor deposition of refractory metals and...

$: Chemical Vapor Deposition of Refractory Metals and Ceramicsassets.cambridge.org/97811074/10275/frontmatter/... · chemical vapor deposition of refractory metals and ceramics ... part$
Chemical Vapor Deposition ofRefractory Metals and Ceramics

www.cambridge.org© in this web service Cambridge University Press

Cambridge University Press978-1-107-41027-5 - Materials Research Society Symposium Proceedings: Volume 168:Chemical Vapor Deposition of Refractory Metals and CeramicsEditors: Theodore M. Besmann and Bernard M. GalloisFrontmatterMore information

http://www.cambridge.org/9781107410275

http://www.cambridge.org


MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS VOLUME 168

Chemical Vapor Deposition ofRefractory Metals and Ceramics

Symposium held November 29-December 1, 1989, Boston,Massachusetts, U.S.A.

EDITORS:

Theodore M. BesmannOak Ridge National Laboratory, Oak Ridge, Tennessee, U.S.A.

Bernard M. GalloisStevens Institute of Technology, Hoboken, New Jersey, U.S.A.

IMIR1S1 MATERIALS RESEARCH SOCIETYPittsburgh, Pennsylvania






cambridge university press Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore, São Paulo, Delhi, Mexico City

Cambridge University Press32 Avenue of the Americas, New York ny 10013-2473, USA

Published in the United States of America by Cambridge University Press, New York

www.cambridge.orgInformation on this title: www.cambridge.org/9781107410275

Materials Research Society506 Keystone Drive, Warrendale, pa 15086http://www.mrs.org

© Materials Research Society 1990

This publication is in copyright. Subject to statutory exceptionand to the provisions of relevant collective licensing agreements, no reproduction of any part may take place without the written permission of Cambridge University Press.

This publication has been registered with Copyright Clearance Center, Inc.For further information please contact the Copyright Clearance Center,Salem, Massachusetts.

First published 1990 First paperback edition 2012

Single article reprints from this publication are available throughUniversity Microfilms Inc., 300 North Zeeb Road, Ann Arbor, mi 48106

CODEN: MRSPDH

isbn 978-1-107-41027-5 Paperback

Cambridge University Press has no responsibility for the persistence oraccuracy of URLs for external or third-party internet websites referred to inthis publication, and does not guarantee that any content on such websites is,or will remain, accurate or appropriate.

This work was supported in part by the U.S. Army Research Office under Grant Number DAAL03-90-G-0014. The views, opinions, and/or findings contained in this report are those of the authors and should not be construed as an official Department of the Army position, policy, or decision unless so designated by other documentation.

This work was supported by the Air Force Office of Scientific Research, Air Force Systems Command, USAF, under Grant Number AFOSR 90-0081.






Contents

PREFACE xi

ACKNOWLEDGMENTS xi i i

MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS xv

PART I: FUNDAMENTALS/MODELING

•BENEFITS AND LIMITS OF THE THERMODYNAMIC APPROACH TOC.V.D. PROCESSES 3

C. Bernard and R. Madar

•PREDICTING THE CHEMISTRY IN CVD SYSTEMS 19Karl E. Spear and Ryan R. Dirkx

GAS PHASE REACTIONS RELEVANT TO CHEMICAL VAPORDEPOSITION: NUMERICAL MODELING 31

D. Burgess, Jr. and M.R. Zachariah

BOND GRAPHS FOR CVD PROCESSES 37Surya R. Kalidindi and Seshu B. Desu

CALCULATION OF TRANSPORT-SHIFTED-CVD PHASE DIAGRAMS 43Daniel E. Rosner and Joshua Collins

TRANSPORT PROPERTIES OF CVI PREFORMS AND COMPOSITES 49G.B. Freeman, T.L. Starr, and T.C. Elston

3-D MODELING OF FORCED-FLOW THERMAL-GRADIENT CVI FORCERAMIC COMPOSITE FABRICATION 55

Thomas L. Starr and Arlynn W. Smith

ANALYTICAL SIMULATION OF AN IMPROVED CVI PROCESS FORFORMING HIGHLY DENSIFIED CERAMIC COMPOSITES 61

Nyan-Hwa Tai and Tsu-Wei Chou

A MODEL FOR CHEMICAL VAPOR INFILTRATION OF FIBROUSSUBSTRATES 67

Rajesh R. Melkote and Klavs F. Jensen

MODELLING TRANSPORT, REACTION, AND PORE STRUCTUREEVOLUTION DURING DENSIFICATION OF CELLULAR OR FIBROUSSTRUCTURES 73

Stratis V. Sotirchos and Manolis M. Tomadakis

PART II: DIAGNOSTICS

BORAZINE ADSORPTION AND REACTION ON A Re(0001) SURFACE 81J.-W. He and D.W. Goodman

•Invited Paper






EARLY GROWTH IN THE CHEMICAL VAPOR DEPOSITION OF TiNAND TiC AND MONITORING BY LASER SCATTERING 93

Max Klein and Bernard Gallois

LIGHT-SCATTERING MEASUREMENTS OF CVD SILICON CARBIDE 9 9B.W. Sheldon and T.M. Besmann

IN SITU REFLECTOMETRY DURING LPCVD TUNGSTEN GROWTH 107Jisk Holleman, Albert Hasper, and Jan Middelhoek

INITIAL STAGES IN THE GROWTH OF OXIDE THIN FILMS BY CVD 113Lisa A. Tietz, Scott R. Summerfelt, Gerald R. English,and C. Barry Carter

GAS PHASE DECOMPOSITION OF AN ORGANOMETALLIC CHEMICALVAPOR DEPOSITION PRECURSOR TO A1N: [Al (CHO oNHJ 3 119

Carmela C. Amato, John B. Hudson, andLeonard V. Interrante

MECHANISTIC ASPECTS OF THE DEPOSITION OF THIN ALUMINAFILMS DEPOSITED BY MOCVD 125

R.W.J. Morssinkhof, T. Fransen, M.M.D. Heusinkveld,and P.J. Gellings

GAS PHASE CHARACTERIZATION IN LP CVD PROCESSES BY APERFORMANT RAMAN EQUIPMENT : GAS TEMPERATURE IN THEVICINITY OF THE SUBSTRATE 131

R. Gaufres, P. Huguet, D. Boya, and J. Lafforet

GAS PHASE REACTIONS RELEVANT TO CHEMICAL VAPORDEPOSITION: OPTICAL DIAGNOSTICS 137

D. Burgess, Jr.

PART III: PROCESS-MICROSTRUCTURE RELATIONSHIPS

•CORRELATION AMONG PROCESS ROUTES, MICROSTRUCTURES ANDPROPERTIES OF CHEMICALLY VAPOR DEPOSITED SILICON CARBIDE 145

Robert F. Davis

MICROSTRUCTURAL CHARACTERIZATION OF MULTIPHASE COATINGSPRODUCED BY CHEMICAL VAPOR DEPOSITION 159

R.A. Lowden, K.L. More, T.M. Besmann, and R.D. James

CHEMICAL VAPOR DEPOSITION OF SILICON BORIDES 167T. Goto, M. Mukaida, and T. Hirai

CHARACTERIZATION OF SILICIDE FORMATION OF LPCVD-W BYMEANS OF RUTHERFORD BACKSCATTERING SPECTROMETRY ANDX-RAY DIFFRACTOMETRY ^ 173

S.-L. Zhang, R. Buchta, and M. Ostling

SELECTIVE CHEMICAL VAPOUR DEPOSITION OF TUNGSTEN USING./WF6 CHEMISTRYC.A. van der Jeugd, A.H. Verb rug g<G.C.A.M. Janssen, and S. Radelaar

SiH-/WF6 CHEMISTRY 179C.A. van der Jeugd, A.H. Verbruggen, G.J. Leusink,

•Invited Paper






IDENTIFICATION OF W20O58 PHASE IN CVD TUNGSTEN FILMS 185M. Lawrence A. Dass, Siva Sivaram, and Bryan Tracy

INVESTIGATION OF CVD S-SiC SURFACES PRODUCED VIA A"NOVEL" SURFACE REPLICATION PROCESS 193

Aliki K. Collins, Joseph T. Keeley,Michael A. Pickering, and Raymond L. Taylor

INFLUENCE OF IMPURITIES AND MICROSTRUCTURE ON THERESISTIVITY OF LPCVD TITANIUM NITRIDE FILMS 199

M.J. Buiting and A.H, Reader

PART IV: MICROSTRUCTURE-MECHANICALPROPERTY RELATIONSHIPS

ADHESION OF DIAMOND FILMS ON VARIOUS SUBSTRATES 207Tyan-Ywan Yen, Cheng-Tzu Kuo, and S.E. Hsu

TUNGSTEN CARBIDE EROSION RESISTANT COATING FOR AEROSPACECOMPONENTS 213

D. Garg and P.N. Dyer

INTERNAL STRESSES IN AMORPHOUS MOCVD SiO2 FILMS 221Seshu B. Desu

INFLUENCE OF SUBSTRATE AND PROCESS PARAMETERS ON THEPROPERTIES OF CVD-SiC 227

A. Parretta, G. Giunta, E. Cappelli, V. Adoncecchi,and V. Vittori

EFFECTS OF DEPOSITION CONDITIONS ON THE MICROSTRUCTUREAND PROPERTIES OF CVD SiC 233

Eric Minford, Robert E. Stevens, Vincent L. Magnotta,Paul N. Dyer, Thomas R. Watkins, and David J. Green

INTERACTION OF TITANIUM WITH SiC COATED BORON FIBER 239Luchen Hwan, Beng Jit Tan, Steven L. Suib, andFrancis S. Galasso

OXIDATION RESISTANT COATINGS PRODUCED BY CHEMICAL VAPORDEPOSITION: IRIDIUM AND ALUMINUM OXYNITRIDE COATINGS 247

P. Netter and Ph. Campros

PART V: NOVEL/LARGE-SCALE TECHNOLOGIES

•APPLICATION OF AI CONTROL TO THE VLS SiC WHISKER PROCESS 255Peter D. Shalek and W.J. Parkinson

MORPHOLOGICAL EVOLUTION OF TITANIUM CARBIDE WHISKERS 267R. Mathur and B.M. Gallois

CHARACTERIZATION OF CERAMIC MATRIX COMPOSITES FABRICATEDBY CHEMICAL VAPOR INFILTRATION 273

D.P. Stinton, D.M. Hembree, Jr., K.L. More,B.W. Sheldon, and T.M. Besmann

•Invited Paper

vii






THE EMERGENCE OF PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION(PECVD) AS A VIABLE INDUSTRIAL COATING PROCESS 281

George Engle and James W. Warren

LASER CHEMICAL VAPOR DEPOSITION OF TiN FILMS 287B. Chen, N. Biunno, R.K. Singh, and J. Narayan

LASER INDUCED PHOTOCHEMICAL VAPOR DEPOSITION OF TUNGSTENON SILICON 293

A.J.P. van Maaren and W.C. Sinke

SILICON NITRIDE SYNTHESIS BY LASER PYROLYSIS OF ANAEROSOL-DISPERSED PRECURSOR 299

Tongsan D. Xiao, Peter R. Strutt, andKenneth E. Gonsalves

REACTIVE CHEMICAL VAPOR DEPOSITION (R.C.V.D.) AS AMETHOD FOR COATING CARBON FIBRE WITH CARBIDES 305

J. Bouix, C. Vincent, H. Vincent, and R. Favre

A LOW TEMPERATURE CVD PROCESS FOR TiN COATINGS 311A. Aguero, D. Little, and P. Lowden

PART VI: METAL-ORGANIC CHEMICAL VAPOR DEPOSITION

*LOW TEMPERATURE MOCVD ROUTES TO THIN FILMS FROMTRANSITION METAL PRECURSORS 319

Gregory S. Girolami and John E. Gozum

LOW TEMPERATURE MOCVD OF SILICON-BASED CERAMIC FILMS 331Honghua Du, Yongwoong Bae, Bernard Gallois,and Kenneth E. Gonsalves

CHARACTERIZATION OF MOCVD GROWN EPITAXIAL CERAMIC OXIDETHIN FILMS 337

J.C. Parker, H.L.M. Chang, J.J. Xu, and D.J. Lam

PREPARATION, STRUCTURE AND PROPERTIES OF VO AND TiO«THIN FILMS BY MOCVD X 343

H.L.M. Chang, J.C. Parker, H. You, J.J. Xu,and D.J. Lam

STRUCTURE, COMPOSITION, AND PROPERTIES OF MOCVD ZrO«THIN FILMS 349

Seshu B. Desu, Tian Shi, and Chi K. Kwok

TITANIUM NITRIDE THIN FILMS: PROPERTIES AND APCVDSYNTHESIS USING ORGANOMETALLIC PRECURSORS 357

Renaud M. Fix, Roy G. Gordon, and David M. Hoffman

CHEMICAL VAPOR DEPOSITION OF NIOBIUM CARBIDE USING ANOVEL ORGANOMETALLIC PRECURSOR 363

Paul D. Stupik, Linda K. Cheatham, John J. Graham,and Andrew R. Barron

•Invited Paper

viii






LOW-TEMPERATURE CHEMICAL VAPOR DEPOSITION OF RHODIUM ANDIRIDIUM THIN FILMS 3 69

David C. Smith, Steve G. Pattillo, Norman E. Elliott,Thomas G. Zocco, Carol J. Burns, Joseph R. Laia, andAlfred P. Sattelberger

ORGANOMETALLIC CHEMICAL VAPOR DEPOSITION OF STRONTIUMTITANATE THIN FILMS 375

W.A. Feil, B.W. Wessels, L.M. Tonge, and T.J. Marks

HIGHLY RESOLVED GRADIENT PATTERNS IN GLASS BY MEANS OFCHEMICAL VAPOR DEPOSITION 381

E. Wolkow, H.D. Gafney, E. Mendoza, P. Wong,and A.L. Hanson

THE EFFECT OF METAL IMPREGNATION ON THE MICROSTRUCTUREOF POROUS VYCOR GLASS 3 87

D. Sunil, J. Sokolov, M.H. Rafailovich, E. Mendoza,E. Wolkow, H.D. Gafney, G.G. Long, P. Jemian, andA.L. Hanson

AUTHOR INDEX 39 5

SUBJECT INDEX 397

MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS 4 01






Preface

The papers contained in this volume were originally presentedat the Symposium on the Chemical Vapor Deposition of RefractoryMetals and Ceramics held at the Fall Meeting of the MaterialsResearch Society in Boston, Massachusetts on November 29 -December lf 19 89. This symposium was sponsored by the Directorateof Electronic and Materials Sciences - Air Force Office ofScientific Research and the Army Research Office. The object ofthe symposium was to promote dialogue between scientists andengineers who are working in the field of chemical vapor deposi-tion of refractory materials. With this focus the symposium wasable to directly address issues which are often bypassed in othervapor deposition meetings that principally concentrate on low-temperature process for electronic materials.

The sessions in the symposium were designed to move smoothlyfrom fundamentals/model ing and diagnostics, emphasizing theunderstanding and monitoring of basic deposition processes,through process-microstructure and microstructural-mechanicalproperty relationships which deal with understanding and predict-ing deposit characteristics. Additional sessions dealt withnovel/large-scale technologies allowing some very innovative ideasto be presented, and metal-organic chemical vapor deposition,which is a blossoming area resulting in lower deposition tempera-tures and heretofore impossible to produce coatings.

The invited papers, presented by leaders in the field, laidthe groundwork for the various sessions of the symposium. Theinvited papers on fundamentals/modeling clearly demonstrated thehigh degree of sophistication that has just recently been obtainedin understanding and modeling chemical vapor deposition, andhighlighted the long way we still have to go. The invited paperson process-property relationships displayed the breadth of ourunderstanding, which is just beginning to depart from theempirical. The invited paper on metal-organic chemical vapordeposition clearly demonstrated the enormous versatility of thetechnique, as well as its certain pitfalls.

January 19, 19 90 T.M. BesmannB.M. Gallois






Acknowledgments

The symposium cochairs would like to thank the session chairswho did an excellent job of organizing and running the sessions.These very helpful individuals were:

E.A.L.C.W.J.N.A.P.N.F.S.

WhittakerHammondLackeyScovilleDyerGalasso

D. GaillardK. GonsalvesD.P. Stinton

The invited speakers, leaders in the field, expendedsignificant effort in contributing to this volume, and we wouldlike to acknowledge them:

C. BernardR. MadarK.E.R.F.P.D.W.J.G.S.J.E.

SpearDavisShalekParkinsonGirolamiGozum

We are also greatly indebted to C.A. Valentine who organized,kept track, revised, mailed, and did everything else necessary toprepare this book for publication by the MRS.

Finally, we sincerely appreciate the financial supportprovided by the Directorate of Electronic and Materials Sciences- Air Force Office of Scientific Research and Division of MaterialScience of the Army Research Office.

xiii






MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS

Recent Materials Research Society Symposium Proceedings

Volume 145—III-V Heterostructures for Electronic/Photonic Devices, C.W. Tu,V.D. Mattera, A.C. Gossard, 1989, ISBN: 1-55899-018-6

Volume 146—Rapid Thermal Annealing/Chemical Vapor Deposition and IntegratedProcessing, D. Hodul, J. Gelpey, M.L. Green, T.E. Seidel, 1989,ISBN: 1-55899-019-4

Volume 147—Ion Beam Processing of Advanced Electronic Materials, N.W. Cheung,A.D. Marwick, J.B. Roberto, 1989, ISBN: 1-55899-020-8

Volume 148—Chemistry and Defects in Semiconductor Heterostructures, M. Kawabe,T.D. Sands, E.R. Weber, R.S. Williams, 1989, ISBN: 1-55899-021-6

Volume 149—Amorphous Silicon Technology-1989, A. Madan, M.J. Thompson,P.C. Taylor, Y. Hamakawa, P.G. LeComber, 1989, ISBN: 1-55899-022-4

Volume 150—Materials for Magneto-Optic Data Storage, CJ. Robinson, T. Suzuki,CM. Falco, 1989, ISBN: 1-55899-023-2

Volume 151—Growth, Characterization and Properties of Ultrathin Magnetic Films andMultilayers, B.T. Jonker, J.P. Heremans, E.E. Marinero, 1989,ISBN: 1-55899-024-0

Volume 152—Optical Materials: Processing and Science, D.B. Poker, C. Ortiz, 1989,ISBN: 1-55899-025-9

Volume 153—Interfaces Between Polymers, Metals, and Ceramics, B.M. DeKoven,AJ. Gellman, R. Rosenberg, 1989, ISBN: 1-55899-026-7

Volume 154—Electronic Packaging Materials Science IV, R. Jaccodine, K.A. Jackson,E.D. Lillie, R.C. Sundahl,1989, ISBN: 1-55899-027-5

Volume 155—Processing Science of Advanced Ceramics, LA. Aksay, G.L. McVay,D.R. Ulrich, 1989, ISBN: 1-55899-028-3

Volume 156—High Temperature Superconductors: Relationships Between Properties,Structure, and Solid-State Chemistry, J.R. Jorgensen, K. Kitazawa,J.M. Tarascon, M.S. Thompson, J.B. Torrance, 1989, ISBN: 1-55899-029

Volume 157—Beam-Solid Interactions: Physical Phenomena, J.A. Knapp, P. Borgesen,R.A. Zuhr, 1989, ISBN 1-55899-045-3

Volume 158—In-Situ Patterning: Selective Area Deposition and Etching, R. Rosenberg,A.F. Bernhardt, J.G. Black, 1989, ISBN 1-55899-046-1

Volume 159—Atomic Scale Structure of Interfaces, R.D. Bringans, R.M. Feenstra,J.M. Gibson, 1989, ISBN 1-55899-047-X

Volume 160—Layered Structures: Heteroepitaxy, Superlattices, Strain, andMetastability, B.W. Dodson, L.J. Schowalter, J.E. Cunningham,F.H. Pollak, 1989, ISBN 1-55899-048-8

Volume 161—Properties of II-VI Semiconductors: Bulk Crystals, Epitaxial Films,Quantum Well Structures and Dilute Magnetic Systems, J.F. Schetzina,F.J. Bartoli, Jr., H.F. Schaake, 1989, ISBN 1-55899-049-6

Volume 162—Diamond, Boron Nitride, Silicon Carbide and Related Wide BandgapSemiconductors, J.T. Glass, R.F. Messier, N. Fujimori, 1989,ISBN 1-55899-050-X

Volume 163—Impurities, Defects and Diffusion in Semiconductors: Bulk and LayeredStructures, J. Bernholc, E.E. Haller, D.J. Wolford, 1989,ISBN 1-55899-051-8

Volume 164—Materials Issues in Microcrystalline Semiconductors,P.M. Fauchet, C.C. Tsai, K. Tanaka, 1989, ISBN 1-55899-052-6

Volume 165—Characterization of Plasma-Enhanced CVD Processes, G. Lucovsky,D.E. Ibbotson, D.W. Hess, 1989, ISBN 1-55899-053-4

Volume 166—Neutron Scattering for Materials Science, S.M. Shapiro, S.C. Moss,J.D. Jorgensen, 1989, ISBN 1-55899-054-2






MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS

Volume 167—Advanced Electronic Packaging Materials, A. Barfknecht, J. Partridge,C-Y. Li, CJ. Chen, 1989, ISBN 1-55899-055-0

Volume 168—Chemical Vapor Deposition of Refractory Metals and Ceramics,T.M. Besmann, B.M. Gallois, 1989, ISBN 1-55899-056-9

Volume 169—High Temperature Superconductors: Fundamental Properties and NovelMaterials Processing, J. Narayan, C.W. Chu, L.F. Schneemeyer,D.K. Christen, 1989, ISBN 1-55899-057-7

Volume 170—Tailored Interfaces in Composite Materials, C.G. Pantano, EJ.H. Chen,1989, ISBN 1-55899-058-5

Volume 171—Polymer Based Molecular Composites, D.W. Schaefer, J.E. Mark, 1989,ISBN 1-55899-059-3

Volume 172—Optical Fiber Materials and Processing, J.W. Fleming, G.H. Sigel,S. Takahashi, P.W. France, 1989, ISBN 1-55899-060-7

Volume 173—Electrical, Optical and Magnetic Properties of Organic Solid-StateMaterials, L.Y. Chiang, D.O. Cowan, P. Chaikin, 1989,ISBN 1-55899-061-5

Volume 174—Materials Synthesis Utilizing Biological Processes, M. Alper, P.D. Calvert,P.C. Rieke, 1989, ISBN 1-55899-062-3

Volume 175—Multi-Functional Materials, D.R. Ulrich, F.E. Karasz, AJ. Buckley,G. Gallagher-Daggitt, 1989, ISBN 1-55899-063-1

Volume 176—Scientific Basis for Nuclear Waste Management XIII, V.M. Oversby,P.W. Brown, 1989, ISBN 1-55899-064-X

Volume 177—Macromolecular Liquids, C.R. Safinya, S.A. Safran, P.A. Pincus, 1989,ISBN 1-55899-065-8

Volume 178—Fly Ash and Coal Conversion By-Products: Characterization, Utilizationand Disposal VI, F.P. Glasser, R.L. Day, 1989, ISBN 1-55899-066-6

Volume 179—Specialty Cements with Advanced Properties, H. Jennings, A.G. Landers,B.E. Scheetz, I. Odler, 1989, ISBN 1-55899-067-4

MATERIALS RESEARCH SOCIETY MONOGRAPH

Atom Probe Microanalysis: Principles and Applications to Materials Problems,M.K. Miller, G.D.W. Smith, 1989; ISBN 0-931837-99-5

Earlier Materials Research Society Symposium Proceedings listed in the back.






chemical vapor deposition of refractory metals and...

Documents