Diamond and Diamond-like Films and Coatings

NATO ASI Series Ad'v~nced Science Institutes Series

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The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division

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Series B: Physics

Diamond and Diamond-like Films and Coatings Edited by

Robert E. Clausing Oak Ridge National Laboratory Oak Ridge, Tennessee

Li nda L. Horton Oak Ridge National Laboratory Oak Ridge, Tennessee

John C. Angus Case Western Reserve University Cleveland, Ohio

and

Peter Koidl Fraunhofer Institut fur Angewandte Festkorperphysik Freiburg, Germany

Plenum Press New York and London Published in cooperation with NATO Scientific Affairs Division

Proceedings of a NATO Advanced Study Institute on Diamond and Diamond-like Films and Coatings, held July 22-August 3, 1990, in Castelvecchio, Pascoli, Italy

Library of Congress Cataloging-in-Publication Data

NATO Advanced Study Institute on Diamond and Diamond-like Films and Coatings (1990 : Castelvecchio Pascali. Italy)

Diamond and diamond-like films and coatings I edited by Robert E. Clausing '" let al.l.

p. cm. -- (NATO ASI series. Series B. Physics; v. 266) "Proceedings of a NATO Advanced Study Institute on Diamond and

Diamond-L1ke Films and Coatings. held July 22-August 3. 1990, in Castelvecchio Pascali. Italy"--T.p. verso.

"Published in cooperation with NATO Scientific Affairs Oivision." Includes bib 1 iographical references and index. lSBN-13: 978-1-4684-5969-2 e-lSBN-13: 978-1-4684-5967-8 DOl: 10.1007/978-1-4684-5967-8 1. Diamonds. Artificial--Congresses. 2. Diamond thin films-

-Congresses. I. ClaUSing. Robert E. II~ North Atlantic Treaty Organizatl0n. Scientific Affairs Division. III. Title. IV. Series. TP873.5.D5N38 1990 666' .88--dc20

ISBN-13: 978-1-4684-5969-2

© 1991 Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1991

A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013

All rights reserved

91-20196 CIP

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

The major support for the Institute was provided by the Scientific Affairs Division of NATO. Significant additional support was provided by:

Metals and Ceramics Division, Oak Ridge National Laboratory, USA Fraunhofer Institut fiir Angewandte Festkorperphysik, FRG National Science Foundation, USA Consorzlo Instituto Nazionale Fisica della Materia, Italy Politecinico di Torino, Italy Office of Naval Research, USA Nano Instruments, Inc., USA European Research Office, United States Army Applied Science and Technology, Inc., USA Genasystems, USA Crystallume, Inc., USA

The home institutions of the directors provided much direct and indirect support for the planning and organization of the Institute. Their assistance, cooperation, and leniency are gratefully acknowledged.

The editors

Dr. R. E. Clausing Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge TN, USA

Prof. J. C. Angus Chemical Engineering Dept., Case Western Reserve University, Cleveland OH, USA

Dr. L. L. Honon Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge TN, USA

Prof. Peter. Koldl Fraunhofer Instltut fur Angewandte Festkorperphyslk Frelburg, FRG

v

PREFACE

Diamond films grown by activated chemical vapor deposition have superlative thermal, mechanical, optical, and electronic properties combined with a very high degree of chemical inertness to most environments. These properties, together with the ability to fabricate films and shapes of considerable size, promise an exciting new material with many applications. Some applications are on the verge of commercialization but many await a few more technological developments. Diamond-like films are already employed in both commercial and military applications. The popular press, as well as the scientific and technological and industrial communities, are increasingly interested in the potential for future development of these materials.

Although there are many technical papers and review articles published, there is no Single comprehensive introduction to these technologies. The Scientific Affairs Division of NATO recognized the need and the future importance of these technologies and authorized an Advanced Study Institute on diamond and diamond-like films. NATO Advanced Study Institutes are high level teaching activities at which a carefully defined subject is presented in a systematic and coherently structured program. The subject is treated in considerable depth by lecturers eminent in their fields and of international standing. The presentations are made to students who are scientists in the field or who possess an advanced general scientific background. The primary objectives of an Advanced Study Institute are to contribute to dissemination of advanced knowledge not yet available in standard university courses and to the formation of contacts among scientists from different countries. Participation in the ASI is the primary instrument, however, publication of the work presented in the basic lectures and status reports also contributes to these objectives.

This book is the record of the proceedings of "The NATO Advanced Study Institute on Diamond and Diamond-like Films and Coatings," held at II Ciocco International Tourist and Conference Center, Castelvecchio, Pascoli, (Tuscany), Italy from July 22 to August 3, 1990. The Institute brought together scientists and engineers from various disciplines to review, discuss, and clarify our current understanding of (1) the growth of diamond and diamond-like films, (2) the characterization of these materials, (3) the optical, physical, and mechanical properties of these films, (4) the relationship of these properties to structure and processing, and (5) the current and potential technological applications of these new diamond and diamond-like materials.

The book has been divided into parts according to the topics discussed. In each part the tutorial lectures are presented first, followed by the contributed papers. The tutorial lectures by world renowned experts review fundamental concepts and the state of the art. At the Institute, they provided the background for

vii

seminar discussions and the presentation and examination of current research findings. Most of the review articles contain extensive bibliographies. Many of the contributed papers present significant new results in this rapidly changing field, others are simply progress reports reflecting the current state of the art in the author's laboratory. It is hoped that this book, with its mixture of papers will serve as an excellent introduction to the field. It combines reviews of the basic science and technology needed to understand the creation and application of diamond and diamond-like materials with the current status of the technology.

We thank all of the chairmen, lecturers, and participants who contributed to the discussions at the meeting and who also provided manuscripts for this book.

Much of the success of this meeting is owed to the experience and organizational expertize of Dr. C. J. McHargue. He first suggested the need for this ASI and helped the directors develop the program and conference format. He also took care of the innumerable details of arrangements and communications with participants and the hotel.

The International Advisory Committee provided guidance and assistance in many ways, including program and financial matters. We thank them for all their help.

The hotel, its facilities and staff contributed much to the success of the Institute in spite of the unusually hot weather. The hotel is a first class resort but is sufficiently isolated to remove outside distractions. It provides excellent facilities for an institute such as ours and easy access to the cultural and historical attractions of Tuscany. The entire staff, especially Mr. Bruno Giannasi, deserves our special thanks.

We also express our thanks to others whose efforts made the Institute work so well: Lee Heatherly who helped with the audio-visual equipment, and Ms. Lou Pyatt who provided expert secretarial help. Ms. Julia Clausing and Ms. Linda Heatherly were always willing, and helped at registration, poster sessions and in other ways e.g., by providing a program of activities for accompanying persons.

R. E. Clausing

viii

Synopsis of the Institute

The Institute was divided into three parts: (I) fundamental concepts, (II) diamond-like films and coatings and (III) CVD diamond films. The first part, on fundamentals, provided a background for understanding of: (1) the structure and basic properties of diamond and diamond-related materials, (2) the basic physics and chemistry of plasmas and the plasma-surface interactions involved in film synthesis, and (3) the characterization methods appropriate for the films and the manufacturing processes. The second part treated the deposition, properties and use of diamond-like films and coatings. The third part included; (1) the practical and theoretical aspects of nucleation and growth of CVD diamond films; (2) specific preparation techniques; (3) characterization, properties and applications of these films; and (4) some of the directions of current research and development including those specifically for electronic devices and high rate deposition processes. Although the theme of institute was the science and technology of diamond materials, there was also discussion of boron nitride, silicon carbide, and other phases in the composition tetrahedron C-8-N-Si.

The technology and applications for diamond and diamond-like materials continue to develop rapidly. Understanding of the synthesis, structure, and properties of these new materials, however, lags behind the technology. There was a strong sense of excitement and anticipation concerning crystalline CVD diamond materials. All of the aspects of growth, characterization and use were eagerly discussed, but the critically important nucleation and growth processes and the roles atomic hydrogen and oxygen in these processes received most attention.

"State of the art," high rate, CVD diamond deposition processes were reviewed and discussed to ascertain the common characteristics which lead to deposition rates of 100 to 1000 microns per hour (compared with the usual one micron per hour deposition rates for films made by the more common low pressure, activated CVD methods.) Film quality and uniformity were also discussed.

A panel discussion at the end of the meeting addressed the needs and opportunities in the synthesis of CVD diamond. The key scientific needs are those related to modeling the nucleation and growth processes, to elucidation of the critical roles of atomic hydrogen, and to the mechanisms of carbon addition to the growing surfaces. The development and more extensive use of in situ diagnostics for both surface and gas phases are important to solving these issues. The more immediate practical questions concern the identification of the growth rate limiting steps, the relation of growth parameters to the resulting film structure, and the dependence of properties on structure.

ix

The meeting was successful from all points of view. The response to the initial meeting announcements was very good; the 105 selected participants formed a well-balanced group from industry, government laboratories, university faculty and graduate students. Seventeen countries were represented. The lecturers, who were chosen from the pioneers and current leading experts in the world, prepared excellent presentations and were very well received. The extended discussion periods were fully utilized with the exchange of information at all levels on an informal basis.

R. E. Clausing

x

CONTENTS

INTRODUCTORY LECTURES

Diamond: Potential and Status M. N. Yoder

Natural Diamond: The Standard J. E. Field

PART I - FUNDAMENTAL CONCEPTS

Electronic Structure of Diamond, Its Defects and Surfaces J. Robertson

Physics of Glow Discharge Plasmas and Plasma/Surface

1

17

37

Interactions During Thin Film Growth . . . . . . . . . . . . . . . . 47 J-E. Sundgren

Reactive Gas Glow Discharges J. W. Coburn

73

Modelling and Simulation of Particle-Surface Interactions . . . . . . 97 R. Smith

Characterization of Diamond and Diamond-like Films P. R. Chalker

Review of Cubic BN and Related Materials R. C. DeVries

PART II - DIAMOND-LIKE FILMS

Classification

Diamond-like Hydrocarbon and Carbon Films . J. C. Angus and Y. Wang

Preparation Techniques for Diamond-like Carbon Y. Catherine

Computer Modeling of C:H Film Growth W. Moller

Amorphous Hydrogenated Carbon Films and Related Materials: Plasma Deposition and Film Properties . .. ..... .

P. Koidl, C. Wild, R. Locher, and R. E. Sah

127

151

173

193

229

243

xi

Mass-Spectroscopy of Sputtered Neutral Particles During the Growth of a-C:H Films .............. .

V. von Bonin and K. G. Tschersich

Preparation and Characterization of Doped a-C:H Films K. Rohwer, P. Hammer, A. Helmbold, D. Bahnemann, D. Meissner, W. Hedderich, R. Hartmann, and W. Ronge

In Situ Plasma and Surface Diagnostics of C:H

267

275

Deposition from ECR Plasmas . . . . . . . . . . . . . . . . . 281 A. Koch, M Engelhard, W. Jacob, W. Moller, and R. Wilhelm

Production of Carbon Cluster Beams and Their Characterisation by Time-of-F1ight Mass Spectroscopy . . . . . . 289

H.-G. Busmann, H. Gaber, T. Muller, and I. V. Hertel

Characterization of Diamond-like Films Prepared by Laser Ablation of Graphite . . . . . . .. ........ 297

E.B.D. Bourdon, W. W. Duley, A. P. Jones, and R. H. Prince

RF Plasma Deposition of a-C:H Films: Diagnostics and Modeling 307 V. Barbarossa, O. Martini, S. Mercuri, R. Tomacie110, and F. Galluzzi

From Amorphous Carbon to Amorphous Diamond-like Carbon B. Andre, J-Ph. Nabot, L. Lombard, and P. Martin

313

The Structure of a-C:H Thin Films . . . . . . . .. 321 P.J.R. Honeybone, R. J. Newport, W. S. Howells, and J. Franks

Properties

Structure and Electronic Properties of Diamond-like Carbon J. Robertson

Conductivity in Amorphous Carbon and Amorphous Hydrogenated Carbon Films . . . . . . . . . . .

D. Das Gupta, F. Demiche1is, and A. Tag1iaferro

Indentation Testing of Thin Films and Hard Materials C. J. McHargue

Electron Spectroscopy on Carbon Based Films: Bulk and Interface Properties . . . . . . . . . . . . . . . .

P. Oe1hafen, D. Ugolini, S. Sche1z, and J.Eitle

The Effect of Deposition Conditions on the Optical and

331

357

363

377

Tribo10gica1 Properties of Annealed Diamo.nd-like Carbon Films . .. 417 A. Grill, V. Patel, and B. S. Meyerson

Band Edges and GAP States by Optical Absorption and Electron Spin Resonance in Amorphous Carbon (a-C) and Hydrogenated Amorphous Carbon (a-C:H) .................. 427

D. Das Gupta, F. Demiche1is, C. F. Pirri, R. Spagnolo, and A. Tag1iaferro

xii

Characterization of the Composition, Electronic Structure and Hardness of Carbon Films Obtained by Ion Implantation, Laser Ablation, and Dual Ion Beam Sputtering . . . . . . .

M. A110uard and J. C. Pivin 434

Post Deposition Treatments and Stability of Diamond-like Films 447 R. Kalish

Aging Processes in Diamond-like Carbon and Carbon/Metal Films . .. 467 L. Martinu

Applications

Applications of Diamond-like (Hard Carbon) Films A. H. Lettington

PART III - DIAMOND FILMS

Nucleation and Growth Mechanisms

Theory and Models for Nucleation and Growth of Diamond Films M. Frenk1ach

A Step Back: Hydrogen Abstraction from Methane Using a Semiempirica1 Molecular Orbital Method . . . . . . . .

S. M. Valone

Investigations of Growth Mechanisms of Diamond Thin Films by Hot Filament Assisted CVD . . . . .. ..... .

J. Mercier, A. M. Bonnot, E. Caigno1, and E. Gheeraert

Carbon Bonding Environments in CVD Diamond Films Investigated Via Solid-State NMR . . . . . .

K. M. McNamara and K. G. Gleason

Deposition Experiments with Separated Atomic Hydrogen and CH4 Sources . . . . . . . . . . . . . . . . . . .

P. Joeris and C. Benndorf

Nucleation and Growth Technology

Methods of Diamond Making T. R. Anthony

481

499

525

533

541

549

555

Nucleation and Growth of Low Pressure Diamond . . . . . . . . . .. 579 B. Lux and R. Haubner

Control of Texture and Defect Structure for Hot-Fi1ament-Assisted CVD Diamond Films

R. E. Clausing, L. Heatherly, and E. D. Specht

Physio-Chemica1 Aspects of Surface Treatments for Diamond Nucleation . . . . . . . . . . . . .

J. J. Dubray, W. A. Yarbrough, and C. G. Pantano

611

619

xiii

Local Heteroepitaxial Diamond Growth on (100) Silicon . D.G.K. Jeng, H. S. Tuan, J. E. Butler, R. F. Salat, and G. J. Fricano

Studies on the Formation of Diamond Nucleation Sites on <100> Silicon Substrates . . . . . . . . . .

J. A. Baglio, B. C. Farnsworth, S. Hankin, C. Sung, J. Hefter, and M. Tabasky

Diagnostics

Hydrogen Dissociation at Hot Filaments: Determination of Absolute Atomic Hydrogen Concentrations . . . . . . .

L. Schafer, U. Bringmann, C.-P. Klages, U. Meier, and K. Kohse-Hoinghaus

Emission Spectroscopy of the Microwave Plasma Used for Diamond Deposition: Importance of the C3 Radical

A. Campargue, M. Chenevier, F. Stoeckel, B. Marcus, M. Mermoux, F. Vinet, and S. Ljungstrom

Ion Energy Distribution at the Substrate in an ECR-Reactor P. Reinke, W. Jacob, and W. Moller

A New Probe for In-Situ Characterization of Diamond Surfaces During Low Pressure Chemical Vapor Deposition

H. K. Schmidt, J. A. Schultz, and Z. Zheng

Characterization

Characerization and Properties of Artificially Grown Diamond P. K. Bachmann and D. U. Wiechert

Mechanical Properties Testing of Diamond and Diamond-like Films by Ultra-Low Load Indentation . . . . . . . . . . .

M. E. O'Hern and C. J. McHargue

Thermal Wave and Raman Measurement of Polycrystalline Diamond Film Quality . . .. ....... .

R. W. Pryor, L. Wei, P. K. Kuo, and R. L. Thomas

Diamond Crystal Growth by Hot Filament CVD and Its Characterization . . . . . . . . . . . . .

P. Ascarelli, S. Fontana, E. Molinari, R. Polini, V. Sessa, M. L. Terranova, and E. Cappelli

In-Vacuo Surface Analysis of Diamond Nucleation and

627

635

643

653

661

669

677

715

723

729

Growth on Si(lll) and Polycrystalline Tantalum . . . . . 737 B. E. Williams, B. R. Stoner D. A. Asbury, and J. T. Glass

TEM and SEM Investigation of the Growth and Texture of Diamond Particles/Films Synthesized by a Flame CVD Process

P. S. Nielsen, K. Madsen, P. Balslev, and P. L. Hansen

xiv

745

Applications

Applications of Diamond Films (Abstract Only) J. M. Pinneo

Turning of Aluminum Alloy Using an Insert with a Brazed Diamond Film . . . . . . . . . . . . . . .

M. Murakawa and S. Takeuchi

Electronic Devices and Applicaitons

Device Application for Diamonds (Abstract Only) . . . . M. W. Geis

Semiconductor Device Development with Homoepitaxial Diamond Films .................. .

S. A. Grot, G. Sh. Gildenblat, C. W. Hatfield, A. R. Badzian, and T. Badzian

Aluminum Metal Point Contact to B-Doped Diamond Films K. Miyata, Y. Matsui, K. Kumagai, S. Miyauchi, K. Kobashi, and A. Nakaue

Tantalum Ohmic Contacts to Diamond by a Solid State

755

757

765

767

773

Reaction Process . . . . .. ....... ..... 781 K. L. Moazed, J. R. Zeidler, M. J. Taylor, and C. A. Hewett

Some Properties of CVD-Diamond Semiconducting Structures 789 A. E. Alexenko and B. V. Spitsyn

Static and Dynamic Electrical Conductivity of Polycrystalline Diamond Films . . . . . . . . . . . . .

G. A. Sokolina, A. A. Botev, L. L. Bouilov, S. V. Bantsekov, O. I. Lazareva, and A. F. Belyanin

Electrical and Optical Properties of Diamond Films Deposited from an Oxy-Acetylene Flame . . . . . . .

Y. Tzeng, C. K. Teh, R. Phillips, A. Joseph, T. Srivinyunon, C. Cutshaw, C. C. Tin, R. Miller, T. H. Hartnett, C. Willingham, A. Ibrahim, and B. H. Loo

Boronated Diamond Films Deposited by Radio Frequency Plasmas T. B. Kustka, R. O. Dillon, and T. Furtak

Radiation Response of Diamond Films . . . . . . . . . N. K. Annamalai, R. F. Blanchard, and J. Chapski

Special Topics

High Rate Versus Low Rate Diamond CVD Methods P. K. Bachmann and H. Lydtin

Origin and Evolution of the Science and Technology of Diamond Synthesis in the USSR ....... .

B. V. Spitsyn

Critical Assessment of State-of-the-Art of Growing Diamond N. Setaka

797

805

813

821

829

855

875

xv

Summary of the Panel Discussions on Needs and Opportunities . . . . R. E. Clausing

Participants

Author Index.

Subject Index

xvi

889

893

903

907