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Thin Films and Nanostructures Advances in Plasma-Grown Hydrogenated Films Volume 30 Serial Editors VLADIMIR AGRANOVICH DEB()RAH TAYLOR Institute of Spectroscopy Motorola Russian Academy of Sciences Austin, Texas Moscow, Russia Honorary Editors MAURICE H. FRANCOMBE STEPHEN M. ROSSNAGEL ABRAHAM ULMAN Department of Physics IBM Corporation. Alstadt-Lord-Mark Professor and Astronomy T. J. Watson Research Center Department of Chemistry Georgia State University Yorktown Heights, New York Polymer Research blstitute Atlanta, Georgia Polytechnic University Brooklyn, New York Editorial Board DAVID L. ALLARA JEROME B. LANDO Pennsylvania State University Case Western Reserve University ALLEN J. BARD University of Texas, Austin HELMUT M()HWALD University of Mainz MASAMICHI FUJIHIRA Tokyo Institute of NICOLAI PLATE Technology Russian Academy of Sciences GEORGE GAINS HELMUT RINGSDORF Rensselaer Polytechnic University of Mainz Institute GIACINTO SCOLES PHILLIP HODGE Princeton University University of Manchester JEROME D. SWALEN JACOB N. ISRAELACHIVILI International Business University of California Machines Corporation Santa Barbara MATTHEW V. TIRRELL MICHAEL L. KLEIN University of Minnesota, University of Pennsylvania Minneapolis HANS KUHN GEORGE M. WHITESIDES MPI Gottingen Harvard University Recent volumes in this serial appear at the end of this volunle Thin Films and Nanostructures Advances in Plasma-Grown Hydrogenated Films Edited by Maurice H. Francombe Department of Physics and Astronomy Georgia State UniversiO' Atlanta, Georgia VOLUME 30 ACADEMIC PRESS An Elsevier Science Imprint San Diego San Francisco New York Boston London Sydney Tokyo This book is printed on acid-free paper. @ Compilation copyright (cid:14)9 2002 by ACADEMIC PRESS All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopy, recording, or any information storage and retrieval system, without permission in writing from the publisher. The appearance of the code at the bottom of the first page of a chapter in this book indicates the Publisher's consent that copies of the chapter may be made for personal or internal use of specific clients. This consent is given on the condition, however, that the copier pay the stated per copy fee through the Copyright Clearance Center, Inc. (222 Rosewood Drive, Danvers, Massachusetts 01923), for copying beyond that per- mitted by Sections 107 or 108 of the U.S. Copyright Law. This consent does not extend to other kinds of copying, such as copying for general distribution, for advertising or promotional purposes, for creating new collective works, or for resale. Copy fees for pre-2002 chapters are as shown on the title pages. If no fee code appears on the title page, the copy fee is the same as for current chapters. 1079-4050/2002 $35.00. Explicit permission from Academic Press is not required to reproduce a maximum of two figures or tables from an Academic Press chapter in another scientific or research publication provided that the material has not been credited to another source and that full credit to the Academic Press chapter is given. The articles in this book are selected from the Academic Press multi-volume work titled Handbook of Thin Film Materials, edited by Hari S. Nalwa, and are uniquely arranged to focus on current advances in surface science. Academic Press An Imprint of Elsevier Science 525 B Street, Suite 1900, San Diego, California 92101-4495, USA http ://www. ac ademicpre s s. corn Academic Press Harcourt Place, 32 Jamestown Road, London NW1 7BY, UK http://www.academicpress.com International Standard Book Number: 0-12-533030-8 International Standard Serial Number: 1079-4050 PRINTED IN THE UNITED STATES OF AMERICA 01 02 03 04 05 CO 9 8 7 6 5 4 3 2 1 Contents Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix Methods of Deposition of Hydrogenated Amorphous Silicon for Device Applications Wilfried G. J . H . M . van Sark 1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2. Research and Industrial Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 1.3. Physics and Chemistry of PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 1.4. Plasma Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 1.5. Plasma Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 I .6 . Relation between Plasma Parameters and Material Properties . . . . . . . . . . . . . . . 108 1.7. Deposition Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 I .8 . Modifications of PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 1.9. Hot Wire Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 1.10. Expanding Thermal Plasma Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . 163 1.1 1 . Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169 1.12. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191 Growth. Structure. and Properties of Plasma-Deposited Amorphous Hydrogenated Carbon-Nitrogen Films D . I;: Franceschirii 2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 2.2. Amorphous Hydrogenated Carbon Films . . . . . . . . . . . . . . . . . . . . . . . . . . 219 2.3. Nitrogen Incorporation Into a-C:H Films . . . . . . . . . . . . . . . . . . . . . . . . . . 227 2.4. Characterization of a-C(N):H Film Structure . . . . . . . . . . . . . . . . . . . . . . . . 246 2.5. Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 2.6. Optical and Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277 V This Page Intentionally Left Blank Contributors Methods of Deposition of Hydrogenated Amorphous Silicon for Device Appli- cations: Wilfried G. J. H. M. van Sark, Debye Institute, Utrecht University, NL-3508 TA Utrecht, The Netherlands Growth, Structure, and Properties of Plasma-Deposited Amorphous Hydro- genated Carbon-Nitrogen Films: D. E Franceschini, Instituto de Ffsica, Uni- versidade Federal Fluminense, Avenida Litor~nea s/n, Niter6i, RJ, 24210-340, Brazil vii This Page Intentionally Left Blank Preface Starting with Volume 30, the title of the series, Thin Films, is being changed to Thin Films and Nanostructures. We feel that this new title reflects more accurately the rapidly growing inclusion of research and development efforts on nanostructures, especially in relation to novel solid-state device formats. The material presented in Volume 30 of this series complements and extends the subject matter published in Volume 29, which reviewed Non-Crystalline Films for Device Structures and dealt primarily with gate-dielectric and passivating layers. Volume 30, titled Advances in Plasma-Grown Hydrogenated Films, contains two chapters covering in detail the plasma preparation and properties of hydrogenated amorphous semiconductor layers and their emerging applications in opto- electronic devices and arrays. As was the case with Volume 29, the review articles included in this volume were selected from the new multi-volume work, Hand- book of Thin Film Materials, edited by Dr. Hari Singh Nalwa for publication by Academic Press. Investigation of amorphous semiconductor films for use in a wide variety of applications has received considerable attention for approximately the past four decades. Since the mid-1960s interest has focused on hydrogenated amorphous silicon, initially for potential use in low-cost large-area solar-cell instal- lations. Chapter 1 offers a complete and well-documented survey, authored by W. G. J. H. M. van Sark, discussing the deposition of these films for a number of important device applications. The main deposition approach considered involves several versions of plasma enhances chemical vapor deposition (PECVD), us- ing multi-chambered, load-locked vacuum systems, affording the ability to grow multi-layered (junction) structures under UHV background conditions. Material aspects are treated, including the role of hydrogen in the plasma for passivation and reduction of defects in the a-Si:H layers. Further sections include detailed descriptions of equipment and techniques, the physics and chemistry of PECVD, plasma modeling and analysis, modifications of PECVD, and discussions of applications in active matrix displays, light and chemical sensors, loudspeakers, etc. The critical need to improve material properties and intrinsic stability of a-Si:H, e.g., by working with discharge conditions that are "at the edge of crystallinity," is stressed. Chapter 2, authored by D. F. Franceschini, addresses the growth, structure, and properties of plasma-deposited amorphous hydrogenated carbon-nitrogen films. The approach seeks to exploit the diamond-like properties of the hypothetical compound fl-C3N4 (with the fl-Si3N4 structure) by incorporating nitrogen in plasma-deposited hard amorphous hydrogenated carbon (a-C:H) films. Films in ix