Handbook of Hard Coatings, R F Bunshah · HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by...

HANDBOOK OF HARD COATINGSDeposition Technologies, Properties and

Applications

Edited by

Rointan F. Bunshah

University of California, Los AngelesLos Angeles, California

NOYES PUBLICATIONSPark Ridge, New Jersey, U.S.A.

WILLIAM ANDREW PUBLISHING, LLCNorwich, New York, U.S.A.

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Copyright © 2001 by Noyes PublicationsNo part of this book may be reproduced orutilized in any form or by any means, electronicor mechanical, including photocopying, recordingor by any information storage and retrievalsystem, without permission in writing from thePublisher.

Library of Congress Catalog Card Number: 01-27318ISBN: 0-8155-1438-7Printed in the United States

Published in the United States of America byNoyes Publications / William Andrew Publishing, LLCNorwich, New York, U.S.A.

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Library of Congress Cataloging-in-Publication Data

Handbook of hard coatings / edited by Rointan F. Bunshahp. cm.

Includes bibliographical references.ISBN 0-8155-1438-71. Protective coatings. 2. Hard materials. 3. Coating processes.

4. Surface hardening. I. Bunshah. R. F. (Rointan Framroze)TA418.76.H363 2001667'.9--dc21 01-27318

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MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIESSeries Editors

Gary E. McGuire, Microelectronics Center of North CarolinaStephen M. Rossnagel, IBM Thomas J. Watson Research CenterRointan F. Bunshah, University of California, Los Angeles (1927-1999), founding editor

Electronic Materials and Process TechnologyCHARACTERIZATION OF SEMICONDUCTOR MATERIALS, Volume 1: edited by GaryE. McGuireCHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur ShermanCHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: byJohn E. J. SchmitzCHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A. VanderahCONTACTS TO SEMICONDUCTORS: edited by Leonard J. BrillsonDIAMOND CHEMICAL VAPOR DEPOSITION: by Huimin Liu and David S. DandyDIAMOND FILMS AND COATINGS: edited by Robert F. DavisDIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS:edited by Devendra Gupta and Paul S. HoELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by JohnMcHardy and Frank LudwigELECTRODEPOSITION: by Jack W. DiniHANDBOOK OF CARBON, GRAPHITE, DIAMONDS AND FULLERENES: by Hugh O. PiersonHANDBOOK OF CHEMICAL VAPOR DEPOSITION, Second Edition: by Hugh O. PiersonHANDBOOK OF COMPOUND SEMICONDUCTORS: edited by Paul H. Holloway andGary E. McGuireHANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited byDonald L. TolliverHANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS, Sec-ond Edition: edited by Rointan F. BunshahHANDBOOK OF HARD COATINGS: by Rointan F. BunshahHANDBOOK OF HYDROTHERMAL TECHNOLOGY: by K. Byrappa and MasahiroYoshimuraHANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J.Cuomo, Stephen M. Rossnagel, and Harold R. KaufmanHANDBOOK OF MAGNETO-OPTICAL DATA RECORDING: edited by Terry McDanieland Randall H. VictoraHANDBOOK OF MULTILEVEL METALLIZATION FOR INTEGRATED CIRCUITS: ed-ited by Syd R. Wilson, Clarence J. Tracy, and John L. Freeman, Jr.HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M.Rossnagel, Jerome J. Cuomo, and William D. WestwoodHANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, 2nd Edition: by JamesLicari and Laura A. HughesHANDBOOK OF REFRACTORY CARBIDES AND NITRIDES: by Hugh O. PiersonHANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C.O’Mara, Robert B. Herring, and Lee P. HuntHANDBOOK OF SEMICONDUCTOR WAFER CLEANING TECHNOLOGY: edited byWerner Kern



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HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa andShigeru HayakawaHANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited byKlaus K. SchuegrafHANDBOOK OF VACUUM ARC SCIENCE AND TECHNOLOGY: edited by Raymond L.Boxman, Philip J. Martin, and David M. SandersHANDBOOK OF VLSI MICROLITHOGRAPHY: edited by William B. Glendinning andJohn N. HelbertHIGH DENSITY PLASMA SOURCES: edited by Oleg A. PopovHYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK, Second Edition: by James J.Licari and Leonard R. EnlowIONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori TakagiMOLECULAR BEAM EPITAXY: edited by Robin F. C. FarrowSEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: editedby Gary E. McGuireULTRA-FINE PARTICLES: edited by Chikara Hayashi, R. Ueda and A. TasakiWIDE BANDGAP SEMICONDUCTORS: edited by Stephen J. Pearton

Ceramic and Other Materials—Processing and TechnologyADVANCED CERAMIC PROCESSING AND TECHNOLOGY, Volume 1: edited by Jon G.P. BinnerCEMENTED TUNGSTEN CARBIDES: by Gopal S. UpadhyayaCERAMIC CUTTING TOOLS: edited by E. Dow WhitneyCERAMIC FILMS AND COATINGS: edited by John B. Wachtman and Richard A. HaberCORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: editedby David E. Clark and Bruce K. ZoitosFIBER REINFORCED CERAMIC COMPOSITES: edited by K. S. MazdiyasniFRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J. BlauHANDBOOK OF CERAMIC GRINDING AND POLISHING: edited by Ioan D. Mavinescu,Hans K. Tonshoff, and Ichiro InasakiHANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C. Carnigliaand Gordon L. BarnaSHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E. MurrSOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICSAND SPECIALTY SHAPES: edited by Lisa C. KleinSOL-GEL SILICA: by Larry L. HenchSPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G. K. BhatSUPERCRITICAL FLUID CLEANING: edited by John McHardy and Samuel P. Sawan

— OTHER RELATED TITLES —HANDBOOK OF PHYSICAL VAPOR DEPOSITION (PVD) PROCESSING: by Donald M.MattoxHERMETICITY OF ELECTRONIC PACKAGES: by Hal GreenhouseSEMICONDUCTOR INDUSTRIAL HYGIENE HANDBOOK: by Michael E. Williams andDavid G. BaldwinSEMICONDUCTOR SAFETY HANDBOOK: edited by Richard A. Bolmen, Jr.



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It is with great sadness that we note the death of Professor Rointan (Ron) F.Bunshah. Ron passed away on October 24, 1999 after a long, gallant and quietbattle with leukemia. This book constitutes his final project and will stand as amemorial to his career and his many accomplishments over the years. This bookis also one of many dozens of books in the Materials Science and Process TechnologySeries, originally from Noyes Publications, and now William Andrew Publishing,that Ron helped originate and manage as Series Editor for many, many years.

Ron's career started over fifty years ago with his B.S. degree in 1948 fromthe Banares Hindu University in India. After moving to the United States, hereceived his M.S. and D.Sc. degrees in 1951 and 1952, respectively, from theCarnegie Institute of Technology in Pittsburgh. He remained at Carnegie until1954 as a research metallurgist and instructor. He then joined New York Univer-sity as an Adjunct Professor and Research Scientist. Six years later, he moved tothe Lawrence Radiation Laboratory in Livermore, CA as a Senior Metallurgist. Hislast appointment, in 1968, was to the University of California at Los Angeles, asa Professor in the Department of Materials Science which is in the School ofEngineering and Applied Science. He took “early” retirement from UCLA in 1991,but returned soon thereafter for another seven years, continuing to teach and leadactive research projects until the fall of 1998.

While at UCLA, Professor Bunshah was a distinguished senior facultymember who took an active part in the University. He was presented with the

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Professor Rointan F. (Ron) Bunshah1927 – 1999

IN MEMORIAM



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Stephen Rossnagel June, 2000Yorktown Heights, NY

Distinguished Teaching Award of the Engineering Graduate Student Associationin 1971, and directly supervised twenty-eight M.S. and ten Ph.D. students as wellas mentoring over twenty post-doctoral researchers. His laboratory and his workon vacuum metallurgy and thin films were internationally recognized as among thebest in the world.

Ron’s technical contributions covered a wide range, not only with metalsand alloys, but also in the realm of semiconductors, dielectrics, and diamondcoatings. His work covered the materials themselves as well as novel fabricationand deposition techniques and technologies. The most important of these tech-nologies is known as Activated Reactive Evaporation (ARE), which combinedevaporative deposition with a reactive plasma activation or modification of thedepositing films. This novel technology allowed researchers to alter the kineticsof an evaporative deposition in ways which had been impossible, and led to newdiscoveries in materials and processing. His research output was documented innearly three-hundred publications, a number of edited books, and innumerableinvited talks and presentations at conferences.

Professor Bunshah was also very generous in devoting a significant fractionof his professional time to his colleges outside of UCLA. Much of this focused onthe American Vacuum Society, of which he was President in the early 1960's. Hewas instrumental in two key accomplishments with the AVS: the formation of theVacuum Metallurgy Division in 1960, and the initiation of the InternationalConference on Metallurgical Coatings (ICMC) in 1973. He served as the firstChair of the Vacuum Metallurgy Division, and was Chair of the ICMC for at leastthe first ten years of its operation. In recognition of this founding role, the ICMCinitiated in 1983 an “R.F. Bunshah” award, which is given in his honor each yearfor the best paper at the Conference.

Ron received many honors during his career. From the AVS, he was awardedthe Gaede-Langmuir prize, AVS Fellow, and AVS Honorary Member. At theICMC Conference in 1998, I had the honor of presenting him with the Founder’sAward, recognizing his singular devotion to organizing and running the Confer-ence. Other honors included the First Life Member of the Indian Vacuum Society,Life Membership in the Indian Institute for Metals, the Distinguished AlumnusAward of the Benares Hindu University, and Fellowship in the American Societyfor Metals. He was on the editorial board of many journals, including AppliedSurface Science, Surface Technology, Coatings Science and Technology, ThinSolid Films, Research and Development, and International Research/Development.

His colleges within the ICMC community, the AVS, UCLA, and thenumerous students and collaborators, will now miss his leadership, his insight, andhis active drive to develop new deposition techniques and coatings, along with hisfriendship which, for many, goes back several decades. We extend our deepestsympathy to his wife, Zoreh, and his family.



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Contributors

Bharat BhushanOhio State UniversityColumbus, Ohio

Steve J. BullThe University of NewcastleNewcastle upon Tyne, England

Rointan F. BunshahUniversity of California, Los

AngelesLos Angeles, California, U.S.A.

J. Wesley CoxOrland Park, Illinois

Bal K. GuptaOhio State UniversityColumbus, Ohio

Lars HultmanLinkoping UniversityLinkoping, Sweden

Otto KnotekTechnische Hochschule AachenAachen, Germany

G. KrämerTechnische Hochschule AachenAachen, Germany

F. LöfflerTechnische Hochschule AachenAachen, Germany

David S. RickerbyHarwell LaboratoryUnited Kingdom Atomic Energy

AuthorityOxfordshire, England

Chris H. StoesselBodega Bay, California

Jan E. SundgrenLinkoping UniversityLinkoping, Sweden



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Preface

This volume covers a wide range of topics relating to the fabrication,characterization, and application of what we know as hard coatings. This bookproject dates back many years to a proposed collaboration with Professor Dr.Christian Weissmantel, who suggested a coedited volume with Professor Bunshah.Unfortunately, Professor Weissmantel passed away and it was many years beforethe project could be started.

The contributors to this volume represent the senior workers in this fieldover the past twenty years, and their names will be well known to those workingin the field. It is a distinctly international list, representing the countries and labsthat have been at the forefront of hard coatings work. It should be noted that many,if not all, of these authors are regular participants in the annual InternationalConference on Metallurgical Coatings and Thin Films (ICMTF), a conferencefounded by Professor Bunshah more than twenty-five years ago, and still vibrantand growing each year.

The volume is roughly organized into three areas: fabrication, characteriza-tion, and applications. The first chapter is a general introduction to the field of hardcoatings and wear-resistant surfaces by Professor Bunshah. In this brief chapter,Bunshah describes some of the earliest work with these materials, and then definessome of the terms used throughout the volume. This chapter is followed by twogeneral chapters on deposition technology. The first is also by Bunshah, and coversthe traditional vacuum-based thin-film techniques such as evaporation, sputterdeposition, and chemical vapor deposition. This chapter is quite useful in givingthe reader a wide overview of these topics along with the references and resourcesfor more detailed explanations. The second deposition chapter (Ch. 3) by ProfessorKnotek describes alternate techniques used for thermal spraying of hard coatings



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at high rates over large areas. These techniques and technologies are veryapplicable to the commercial uses of hard coatings.

The fourth through sixth chapters introduce the science of characterizingand measuring hard coatings or films. The first chapter in this section, byProfessors Hultman (Linkoping, Sweden) and Sundgren (Chalmers, Sweden), isa very detailed and systematic overview of the relationships between the physicalproperties of these films and composites, and the underlying structure of thematerial. These two professors are without peer in the world for their fundamentalcontributions to the science of hard coatings and multilayers, and the chapter is agood introduction to the field. The second characterization chapter, by Bull(Newcastle, UK) and Rickerby (Harwell, UK), explores some of the practicalcharacterization techniques used to evaluate hard materials. These include tech-niques for hardness measurement, adhesion, and stress. The third characterizationchapter, by Bhushan and Gupta (Ohio State University), takes this a step farther,examining the tribological properties of films. This includes hardness and adhe-sion, as well as the measurement of friction and wear. These latter topics are keyto the applications of hard materials, which are generally used to protect underly-ing softer materials.

The seventh and eighth chapters describe applications, and are broken intotwo areas: coatings used for cutting tools, and coatings used for non-cuttingapplications. In each case, the key advantage of hard coatings is that they can beused to increase the quality and lifetime of tools of various types. These chaptersdescribe just some of the many applications. The ninth chapter covers a range ofmaterials somewhat different from the conventional hard coatings, which are oftennitrides or oxides (of metals). This chapter explores cubic boron nitride anddiamond-like films, and covers deposition, characterization, and application in thesingle chapter. This materials set has some very unique properties and the field isstill rapidly evolving.

Finally, Professor Bunshah provides a summary chapter with comments oneach of the areas in the volume. In addition, he makes some suggestions andpredictions for future work and applications. In many ways, this chapter is mostvaluable because it sums up a lifetime of experience and wisdom, and puts someperspective on the field.

As mentioned in the Memoriam, this project is the last volume in the ratherprodigious output of Professor Bunshah. It is fitting, though, that this volume hascome together shortly after his death and it serves as a testament to his contribu-tions over the many years.

Stephen RossnagelYorktown Heights, NYJune, 2000



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Handbook of Hard Coatings, R F Bunshah · HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by...

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