Table Of ContentThe Physics and
Chemistry of Si0
2
and the Si-Si0
2
Interface
The Physics and
Chemistry of Si0
2
and the Si-Si0
2
Interface
Edited by
C. Robert Helms
Stanford University
Stanford, California
and
Bruce E. Deal
Fairchild Research Center
National Semiconductor
Santa Clara, California
Springer Science+Business Media, LLC
Library of Congress Cataloging in Publication Data
Symposium on the Physics and Chemistry of SiO, and the Si-SiO, Interface (1988:
Atlanta, Ga.)
The physics and chemistry of SiO, and the Si-SiO, interface I edited by C. Robert
Helms and Bruce E. Deal.
p. em.
"Proceedings of the Symposium on the Physics and Chemistry of SiO, and the Si
SiO, Interface, held May 15-20, 1988, at the 173rd Meeting of The Electrochemical
Society, in Atlanta, Georgia"-T.p. verso.
Includes bibliographies and index.
ISBN 978-1-4899-0776-9 ISBN 978-1-4899-0774-5 (eBook)
DOI 10.1007/978-1-4899-0774-5
1. Silica-Congresses. 2. Surfaces (Physics)-Congresses. 3. Surface chemistry
Congresses. I. Helms, C. Robert. II. Deal, Bruce E. III. The Electrochemical Society,
Meeting (173: 1988: Atlanta, Ga.) IV. Title.
QC585.75.S55S94 1988 88-28168
546'.6832-dcl9 CIP
This limited facsimile edition has been issued
for the purpose of keeping this title available
to the scientific community.
1098 765 43
Proceedings of the symposium on The Physics and Chemistry of SiO,
and the Si-SiO, Interface, held May ·15-20, 1988, at the
173rd meeting of The Electrochemical Society, in Atlanta, Georgia
© 1988 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1988
All rights reserved
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
Proceedings of tbe Symposium beld at tbe
173rd Meeting of Tbe Electrocbemical
Society in Atlanta, Georgia on May 15-20, 1988
CONFERENCE CHAIRMAN
C. Robert Helms
Stanford University
CONFERENCE CO-CHAIRMEN
Bruce E. Deal Edward H. Poindexter Eugene A. Irene
National Semiconductor U.S. Army ET & DL University of North Carolina
CONFERENCE ORGANIZING COMMITTEE
K. L. Brower, Sandia N. M. Johnson, Xerox
R. A. Devine, CNET R. DeKeersmaecker, IMEC
D. J. DiMaria, IBM J. Maseljian, JPL
R. H. Doremus, RPI E. H. Nicollian, Univ. of N. C.
P. V. Dressendorfer, Sandia Y. Nishi, HP
A. H. Edwards, Army.ET & DL S. I. Raider, IBM, ECS
F. J. Feigl, Lehigh S. Rigo, Univ. of Paris
L. C. Feldman, AT & T Bell Labs J. Ruzyllo, Pennsylvania State
D. L. Griscom, NRL M Schulz, Univ. ofErlangen
F. J. Grunthaner, JPL M Stroscio, ARO
P. 0. Hahn, Wacker T. Sugani, Univ. of Tokyo
F. D'Heurle, IBM J. B. Wagner, Arizona State, ECS
G. Hollinger, Univ. of Lyon G. Wright, ONR
W. Holton, SRC D. R. Young, Lehigh
y
PREFACE
The properties of Si02 and the Si-Si02 interface provide the key foundation onto
which the majority of semiconductor device technology has been built Their study has
consumed countless hours of many hundreds of investigators over the years, not only in
the field of semiconductor devices but also in ceramics, materials science, metallurgy,
geology, and mineralogy, to name a few. These groups seldom have contact with each
other even though they often investigate quite similar aspects of the Si02 system. Desiring
to facilitate an interaction between these groups we set out to organize a symposium on the
Physics and Chemistry of Si()z and the Si-Si()z Interface under the auspices of The
Electrochemical Society, which represents a number of the appropriate groups. This
symposium was held at the 173rd Meeting of The Electrochemical Society in Atlanta,
Georgia, May 15-20, 1988.
These dates nearly coincided with the ten year anniversary of the "International
Topical Conference on the Physics of Si02 and its Interfaces" held at mM in 1978. We
have modeled the present symposium after the 1978 conference as well as its follow on at
North Carolina State in 1980. Of course, much progress has been made in that ten years
and the symposium has given us the opportunity to take a multidisciplinary look at that
progress. One of the major accomplishments of the IBM conference was the preparation of
a conference proceedings which still serves as an exceedingly valuable reference, even after
ten years. It is our hope and expectation that the present volume will be just as useful for
the coming ten years.
In addition to ourselves, Ed Poindexter and Gene Irene served as symposia
co-chairmen. With help from the organizing committee listed on a previous page, we set
out to construct a program for the symposium leading to papers for this book that bridged
the appropriate disciplines, provided sufficient review and tutorial material and at the same
time presented the latest advancements in our understanding of the Si-Si02 system Of the
sixty articles published here, twenty seven were in vi ted papers providing both for review
and discussion of new hot topics.
The symposium was divided into seven sessions leading to six chapters in this
book. Preceding the papers themselves each chapter is introduced and summarized by a
member of the organizing committee who we felt would provide a critical assessment of the
body of work. The first chapter deals with the processes used to grow Si()z on silicon and
mechanisms responsible for those growth processes. This chapter, introduced and
summarized by J. Blanc, contains what to some might seem a smprising cross-section of
divergent views of the topic of Si oxidation.
In the second chapter, introduced by Dave Griscom, we discuss the general topic of
the thermal and structural properties of Si02 with particular emphasis on the role of
hydrogen and the effect of processing on oxide chemistry and bonding.
As important as the chemistry and bonding of Si02 are to silicon device structures,
a key factor that makes the Si-Si(h system so well behaved is the unique properties of the
interface itself. In the third chapter, progress in our understanding of the structure,
chemistry, bonding and morphology of the Si-Si(h interface is reviewed. Key findings
vii
are presented relating to the role of SiOx bondin~ configurations and the importance of
crystalline SiO:z near the interlace. In addition, ~nt theoretical progress in our
understanding of the electronic structure and bonding of the Si-SiO:z interface is presented.
Although the level of chemical :Perfection of the Si-SiO:z interface that can be
achieved is hard to comprehend, it still contains defects which can control defect properties.
The nature of these defects is the subject of the fourth chapter introduced by Ed Poindexter
and Max Schulz. Recent breakthroughs in our understanding of the relationship between
Si(h defects and those which control MOS device properties are discussed along with
recent reports of measurements of the trapping and detrapping of single e-defects.
A major new focus in the last few years has been the effect of the silicon surface
condition prior to oxidation as well as the effect of the oxidation process itself on other
important phenomena especially relating to defects. These topics are discussed in Chapter
5, introduced by Gene Irene. Finally in Chapter 6, introduced by Paul Dresssendorfer, we
discuss the current state of the art in understanding canier transport and tunneling in Si(h.
The success of the symposium and the excellent quality of the papers in this book
was due to the efforts of our c<rehairman, the organizing committee, and of course all the
authors, who we would like to take this opportunity to thank. In addition we would also
like to acknowledge The Electrochemical Society for providing us with an administrative
framework and the financial support which made our job so much easier.
C. Robert Helms
Bruce E. Deal
Palo Alto, California
June, 1988
viii
CONTENTS
I. GROWTH MECHANISMS OF SI02 FILMS
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
J. Blanc
Historical Perspectives of Silicon Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Bruce E. Deal
Oxidation of Silicon: Tests of Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Robert H. Doremus
Silicon Oxidation Models Based on Parallel Mechanisms . . . . . . . . . . . . . . . . . 25
C. R. Helms and J. de Larios
The Role of SiO in Si Oxidation at a Si-Si{h Interface . . . . . . . . . . . . . . . . . . . 35
S. I. Raider
Uncertainty Analysis of Analytic Oxidation Models..................... 43
Zhi-Min Ling, Luc H. Dupas, and Kristin M. De Meyer
Modeling of the Oxide Growth in a Chlorine Ambient . . . . . . . . . . . . . . . . . . . 53
Zhi-Min Ling, Luc H. Dupas, and Kristin M. De Meyer
Silicon Oxidation Studies: A Review of Recent Studies
on Thin Film Silicon Dioxide Formation . . . . . . . . . . . . . . . . . . . . . . . 61
Eugene A. Irene
Si Oxidation Mechanisms as Studied by Oxygen Tracer Methods............ 75
S.Rigo
The Oxidation of Silicides on Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
F. M. d'Heurle
Oxidation Kinetics of Si in Dry COz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Tadashi Sakon and J. B. Wagner, Jr.
A Novel Silicon Oxidation Method---JfF Enhanced Oxidation.. . . . . . . . . . . . . 103
Long Wei, Xu Yuan-sen, and Zheng Yang-shu
Thermal Oxidation of Silicon in an Afterglow Gas . . . . . . . . . . . . . . . . . . . . . . Ill
Andrew M. Hoff and Jerzy Ruzyllo
ix
Deposition of Si(h Thin Films by Remote Plasma Enhanced
Chemical Vapor Deposition (Remote PECVD).................... 119
D. V. Tsu, S. S. Kim, and G. Lucovsky
Anodic Si(h for Low Temperature Gate Dielectrics . . . . . . . . . . . . . . . . . . . . . . 129
Keyvan Sayyah
ll. THERMAL AND STRUCTURAL PROPERTIES OF Si02
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
D. L. Griscom
Local Atomic Structure of Thermally Grown Si(h Films . . . . . . . . . . . . . . . . . . 139
G. Lucovsky, J. T. Fitch, E. Kobeda, and E. A. Irene
Structural Relaxation and Growth of Si(h Films on Si.................... 149
R. W. Rendell and K. L. Ngai
Structural Relaxation Effects in Dry Thermal Silicon
Dioxide Films on Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
L. M. Landsberger and W. A. Tiller
Molecular Diffusion in a-Si(h: Its role in Annealing
Radiation-Induced Defect Centers..... . . . . . . . . . . . . . . . . . . . . . . . . 169
Robert L. Pfeffer
Current-Induced Charges and Hydrogen Species
Distributions in MOS Silicon Dioxide Films . . . . . . . . . . . . . . . . . . . . . . 177
R. Gale, H. Chew, F. J. Feigl, and C. W. Magee
lli. THE ATOMIC AND ELECTRONIC STRUCTURE
OF THE Si-Si02 INTERFACE
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
C. R. Helms
The Structure of the Si/Si<h Interface: A Review . . . . . . . . . . . . . . . . . . . . . . . . 189
A. Ourmazd and J. Bevk
The Stoichiometry and Structure of the Si/Si<h Interface:
Ion Scattering Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
L. C. Feldman
Scanning-Tunneling Microscopy and Spectroscopy of
Silicon Dangling Bond Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
R. J. Hamers and R. H. Koch
The Microstructure of Si(h-Si(100) Interfaces Investigated
by XPS and HRTEM..................................... 211
G. Hollinger, R. Saoudi, P. Ferret, and M. Pitaval
Microscopic Structure of the Si<h-Si Interface.......................... 219
F. J. Himpsel, F. R. McFeely, A. Taleb-Ibrahimi,
J. A. Yarmoff, and G. Hollinger
ARXPS Analysis of Si-Si02 Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
J. Halbritter
X
Dependence of Si()z-Si Interface Sttuctures
on Oxidation Process . . • . . . . . • . • . . . . . . . • . . . . . . . . . . . . . . . . . . . 235
Takeo Hattori, Hiroaki Yamagishi, Noboru Koike,
Keitaro Imai, and Kikuo Ya mabe
The Effect of Electrostatic Screening on Energy Positions of
Spectra Near Si(h-Si Interfaces . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
R. Browning, M. A. Sobolewski, and C. R. Helms
A Physical Model for the Observed Dependence of the
Metal-Semiconductor Work Function Difference
on Substrate Orientation . . • . . . . . . . . . • . . . . . . • . . . . . . . . . . . • . . . . 251
Hisham Z. Massoud and James D. Plummer
Theoretical Calculations of the Electronic Sttucture in
the Si-Si02 Systems • . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Michel Lannoo
Theory of Defects in the MOS System . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . 271
Arthur H. Edwards
IV. DEFECTS, IMPURITIES, AND DAMAGE
MECHANISMS IN Si-Si02 SYSTEMS
Introduction . . . . . • • . . . . . . • . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
E. H. Poindexter and M Schulz
Nature of Radiation-Induced Point Defects in Amorphous
Si02 and their Role in Si(h-on-Si Sttuctures . . • . . . . . . . . • . . . . . . . . . . 287
D. L. Griscom, D. B. Brown, and N. S. Sales
Chemical and Sttuctural Features of Inherent and
Process-Induced Defects in Oxidized Silicon . . • • . . • . • . . . . . . . . . . . . . 299
Edward H. Poindexter, Philip J. Caplan and Gary J. Geraidi
Chemical Kinetics of Hydrogen and P., Centers . . . • . • . . . . . . . . . . . . . . . . . . . 309
K. L. Brower
Electronic and Optical Properties of Silicon Dangling-Bond
Defects at the Si-Si<>l Interface . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . 319
N. M. Johnson
Transient Spectroscopy on Individual Interface Traps in MOSFETS . . . . . . . . . . . . 327
A. Karwath and M Schulz
Observation of "1/f-Noise States" in Conductance
Measurements on MOS Sttuctures • . • . . . . . . • . • . • . . . . . . . . . . . . . . . 335
M. I. Uren, M I. Kirton, and S. Collins
The Gate-Voltage Dependence of Trapping into
Individual Si:Si(h Interface States . • . . • . . • . . . • . . • . . . . . . . . . . . . . . 341
M.J. Kirton, M.J. Uren, and S. Collins
Step Heights of Switching Effects of Single
Interface Traps in MOSFETS . . . . . . . . . . . . • . . • . . . . . . . . . . . • . . . . . 349
o. Jantsch and R. Kircher
xi
