Surface Infrared and Raman Spectroscopy: Methods and Applications

278 Pages·1995·17.188 MB·English

by  W. Suëtaka (auth.)

Surface Infrared and
Raman Spectroscopy
Methods and Applications
METHODS OF SURFACE CHARACTERIZATION
Series Editors:
Cedric J. Powell, National Institute a/Standards and Technology. Gaithersburg. Maryland
Alvin W. Czandema, Solar Energy Research Institute. Golden. Colorado
David M. Hercules, University 0/ Pittsburgh. Pittsburgh. Pennsylvania
Theodore E. Madey, Rutgers. The State University o/New Jersey.
New Brunswick. New Jersey
John T. Yates, Jr., University a/Pittsburgh. Pittsburgh. Pennsylvania
Volume 1 VIBRA TIONAL SPECTROSCOPIES
OF MOLECULES ON SURFACES
Edited by John T. Yates, Jr., and Theodore E. Madey
Volume 2 ION SPECTROSCOPIES FOR SURFACE ANALYSIS
Edited by A. W. Czandema and David M. Hercules
Volume 3 SURF ACE INFRARED AND RAMAN SPECTROSCOPY
Methods and Applications
W. Suet aka with the assistance of John T. Yates, Jr.
A Continuation Order Plan is available for this series. A continuation order will bring delivery of
each new volume immediately upon pUblication. Volumes are billed only upon actual shipment.
For funher information please contact the publisher.
Surface Infrared and
Raman Spectroscopy
Methods and Applications
w.
Suetaka
Professor Emeritus
Tohoku University
Tsuchiura.Japan
With the assistance of
John T. Yates, Jr.
University ofP ittsburgh
Surface Science Center
Pittsburgh. Pennsylvania
Springer Science+Business Media, LLC
Library of Congress Cataloging-in-Publication Data
On file
ISBN 978-1-4899-0944-2 ISBN 978-1-4899-0942-8 (eBook)
DOI 10.1007/978-1-4899-0942-8
© Springer Science+Business Media New York 1995
Originally published by Plenum Press, New York in 1995
Softcover reprint of the hardcover 1st edition 1995
1098765432 1
AH 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
About the Series
A large variety of techniques are now being used to characterize many different
surface properties. While many of these techniques are relatively simple in con
cept, their successful utilization involves employing rather complex instrumen
tation, avoiding many problems, discerning artifacts, and carefully analyzing
the data. Different methods are required for handling, preparing, and processing
different types of specimen materials. Many scientists develop surface charac
terization methods, and there are extensive developments in techniques reported
each year.
We have designed this series to assist newcomers to the field of surface
characterization, although we hope that the series will also be of value to more
experienced workers. The approach is pedagogical or tutorial. Our main ob
jective is to describe the principles. techniques. and methods that are considered
important for surface characterization, with emphasis on how important surface
characterization measurements are made and how to ensure that measurements
and interpretations are satisfactory, to the greatest extent possible. At this time,
we have planned four volumes, but others may follow.
The first volume brought together a description of methods for vibrational
spectroscopy of molecules on surfaces. Most of these techniques are still under
active development; commercial instrumentation is not yet available for some
techniques, but this situation could change in the next few years. The current
state of the art of each technique was described as were their relative capabil
ities. An important component of the first volume was the summary of the rele
vant theory.
This book is the first of two volumes that contain descriptions of the tech
niques and methods of electron and ion spectroscopies which are in widespread
use for surface analysis. These two volumes are and will be largely concerned
with techniques for which commercial instrumentation is available. The books
vi Preface
are intended to fill the gap between a manufacturer's handbook, and review
articles that highlight the latest scientific developments.
A fourth volume will deal with techniques for specimen handling, beam
artifacts, and depth profiling. It will provide a compilation of methods that have
proven useful for specimen handling and treatment, and it will also address the
common artifacts and problems associated with the bombardment of solid sur
faces by photons, electrons, and ions. A description will be given of methods for
depth profiling.
Surface characterization measurements are being used increasingly in di
verse areas of science and technology. We hope that this series will be useful in
ensuring that these measurements can be made as efficiently and reliably as
possible. Comments on the series are welcomed, as are suggestions for volumes
on additional topics.
C. J. Powell
Gaithersburg, Maryland
A. W. Czandema
Golden, Colorado
D. M. Hercules
Pittsburgh, Pennsylvania
T. E. Madey
New Brunswick, New Jersey
J. T. Yates, Jr.
Pittsburgh, Pennsylvania
Preface
Infrared (IR) and Raman spectroscopy may seem to be old-fashioned ap
proaches to surface characterization because of the emergence of many modem
techniques to study surfaces. However, these techniques provide detailed mo
lecular-level information about the surface species present in ultrahigh vacuum
environments as well as in various absorbing media. Furthermore, many varia
tions have been developed in recent years and are still emerging. As a result,
IR and Raman spectroscopy have been greatly improved in sensitivity and
today are easily applied to the in situ and real-time observation of solid surfaces
in liquid and gaseous media as well as of solid/solid interfaces. For this reason,
these techniques are widely employed in the investigation of heterogeneous
catalysis, electrode processes, growth of thin films, corrosion and its inhibition,
lubrication, adhesion, and surface treatment of engineering materials.
There are many excellent books that treat surface IR or Raman spectro
scopy from the viewpoint of pure science. However, there exist only a few
books that treat both IR and Raman spectroscopies for engineers and re
searchers in applied science using the best knowledge of the author. This book
is written, therefore, for those who are not spectroscopists but who are working
or beginning to work with IR and Raman spectroscopy in the investigation of
surfaces of practical materials. Consequently, this book does not contain de
tailed theoretical treatments, and only basic knowledge of vibrational spectro
scopy is required for understanding the discussions in this book. Applications
of IR and Raman spectroscopy to the investigation of a variety of real surfaces
are illustrated. Typical results obtained for species on clean and well-defined
surfaces in ultrahigh vacuum environments are also included in this book for
better understanding of the basic principles governing various surface phe
nomena.
I should like to express my most heartfelt thanks to Professor N. Sheppard
viii Preface
for encouraging me to write this book and for kind arrangements for publica
tion. I am particularly indebted to Professor J. T. Yates, Jr., who read the entire
manuscript and pointed out a number of mistakes. His detailed and perspica
cious comments and suggestions have substantially improved the manuscript.
The editorial staff of Plenum Publishing Corporation provided valuable advice
all along the route from manuscript to printed volume.
I am also most grateful to the following scientists for supplying the
reprints and preprints: Professor A. M. Bradshaw (Berlin), A Campion (Aus
tin), Dr. Y. J. Chabal (Murray Hill), Professor J.-N. Chazalviel (Palaiseau), Dr.
M. K. Debe (St. Paul), Dr. J. G. Gordon II (San Jose), Professor R. G. Greenler
(Milwaukee), Professor A Hatta (Sendai), Dr. F. M. Hoffman (Annandale),
Professor H. Ishida (Cleveland), Professor C. Lamy (Poitiers), Dr. C. A Mel
endres (Argonne), Professor H. Metiu (Santa Barbara), Professor M. Osawa
(Sendai), Professor A Otto (Dfisseldort), Professor N. Sheppard (Norwich), Dr.
J. D. Swalen (San Jose), Professor R. G. Tobin (East Lansing), Professor
Vo-Van Truong (Moncton) and Professor J. T. Yates, Jr. (Pittsburgh). Thanks
are also due to the following publishers for permission to reproduce figures and
tables appearing in this book: Academic Press Inc., American Chemical So
ciety, American Institute of Physics, Chemical Society of Japan, Editions
Gauthier-Villars, Elsevier Sequois S. A, Elsevier Science Publishers B.V.,
Industrial Publishing & Consulting, Inc., Japanese Society of Tribologists,
Japan Institute of Metals, Japan Society of Analytical Chemistry, Pergamon
Press Ltd., Plenum Publishing Corporation, Publication Office of Japanese
Journal of Applied Physics, The Royal Society, Society for Applied Spectro
scopy and Spectroscopical Society of Japan.
w.
Suetaka
Tsuchiura, Japan
Prerace Ix
Prefatory Note
The surface vibrational spectroscopies provide incisive information about the
chemical species present on surfaces through the use of group frequency
assignment methods. This book deals with many of the optical vibrational
spectroscopy methods which are employed by research workers and tech
nicians in the field. This book is a fitting sequel to Vibrational Spectroscopy
of Molecules on Surfaces in this series, Methods of Surface Characterization,
Volume 1, Plenum Press, New York (1987), edited by J. T. Yates, Jr. and T.
E. Madey. The reader will find excellent descriptions of the physical basis for
the various optical methods as well a many examples of the use of these
methods to solve problems of importance in a variety of technologies.
John T. Yates, Jr.
Pittsburgh, Pennsylvania