Semiconductor Sensors in Physico-Chemical Studies HANDBOOK OF SENSORS AND ACTUATORS i , i , Series Editor: S. Middelhoek, Delft University of Technology, The Netherlands .... ---... ...," .. ... ,.... ...:;.;-~..~ ..,. / ....... .,....;,</-\-,.,..-..,, /",< C:X'-o< :.< ':~W" .... ", !~," .,~; ',X ~" ,',. ".,..,"~;.'~ x/"%..." "v" \\\..// Volume 1 Thick Film Sensors (edited by M. Prudenziati) Volume 2 Solid State Magnetic Sensors (by C.S. Roumenin) Volume 3 Intelligent Sensors (edited by H. Yamasaki) Volume 4 Semiconductor Sensors in Physico-Chemical Studies (edited by L. Yu. Kupriyanov) Volume 5 Mercury Cadmium Telluride Imagers (by A. Onshage) Volume 6 Micro Mechanical Systems (edited by T. Fukuda and W. Menz) Volume 7 Measuring Current, Voltage and Power (by K. Iwansson, G. Sinapius and W. Hoomaert) Volume 8 Micro Mechanical Transducers Pressure Sencors, Accelerometers and Gyroscopes (by M.-H. Bao) HANDBOOK OF SENSORS AND ACTUATORS 4 , , , , ,, ,, ,, , Semiconductor Sensors in Physico- Chemical Studies Edited by L. Yu. Kupriyanov Department of Chemical Sensors Karpov Institute of Physical Chemistry Moscow, Russia Translated from Russian by V. Yu. Vetrov ELSEVIER Amsterdam - Boston - London - New York- Oxford - Paris San Diego - San Francisco - Singapore - Sydney- Tokyo ELSEVIER SCIENCE B.V Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands (cid:14)9 1996 Elsevier Science B.V All rights reserved. This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. 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Notice No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made. pp. 219-279: Copyright not transferred. First edition 1996 Second impression 2002 Library of Congress Cataloging in Publication Data Poluprovodnlkovye sensory v ftzlko-khtalchesklkh lssledovanl~kh. English Semiconductor sensors in physlco-chemlcal studies / edited by L.Yu. Kuprtyanov. p. cm. -- (Handbook oF sensors and actuators . v. 4) Includes bibliographical references. ZSBN 0-444-82261-5 (acid-Free paper) 1. Chemical detectors. 2. Semiconductors. I. Kupr]yanov, L. Yu. II. Series. TP159.C46P6513 1996 543',0871--dc20 96-5829 CIP ISBN: 0-444-82261-5 The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper). Printed in The Netherlands. Introduction to the Series The arrival of integrated circuits with very good performance/price ratios and relatively low- cost microprocessors and memories has had a profound influence on many areas of technical endeavour. Also in the measurement and control field, modern electronic circuits were introduced on a large scale leading to very sophisticated systems and novel solutions. However, in these measurement and control systems, quite often sensors and actuators were applied that were conceived many decades ago. Consequently, it became necessary to improve these devices in such a way that their performance/price ratios would approach that of modern electronic circuits. This demand for new devices initiated worldwide research and development programs in the field of "sensors and actuators n. Many genetic sensor technologies were examined, from which the thin- and thick-film, glass fiber, metal oxides, polymers, quartz and silicon technologies are the most prominent. A growing number of publications on this topic started to appear in a wide variety of scientific journals until, in 1981, the scientific journal Sensors and Actuators was initiated. Since then, it has become the main journal in this field. When the development of a scientific field expands, the need for handbooks arises, wherein the information that appeared earlier in journals and conference proceedings is systematically and selectively presented. The sensor and actuator field is now in this position. For this reason, Elsevier Science took the initiative to develop a seres of handbooks with the name "Handbook of Sensors and Actuators" which will contain the most meaningful background material that is important for the sensor and actuator field. Titles like Fundamentals of Transducers, Thick Film Sensors, Magnetic Sensors, Micromachining, Piezoelectric Crystal Sensors, Robot Sensors and Intelligent Sensors will be part of this seres. The series will contain handbooks compiled by only one author, and handbooks written by many authors, where one or more editors bear the responsibility for bringing together topics and authors. Great care was given to the selection of these authors and editors. They are all well known scientists in the field of sensors and actuators and all have impressive international reputations. Elsevier Science and I, as Editor of the series, hope that these handbooks will receive a positive response from the sensor and actuator community and we expect that the series will be of great use to the many scientists and engineers working in this exciting field. Simon Middelhoek vi PUBLISHER'S NOTE We are pleased to present to you this book on Semiconductor Sensors in Physico-Chemical Studies, edited by Dr. Leonid Kupriyanov of the Karpov Institute of Physical Chemistry in Moscow. Translated from Russian by a professional translator, the prose still retains some of its local flavour although, we trust, it is clearly understandable throughout. Had we further polished the language we would not only have lost at least another six months in bringing the book to you but we would also have incurred costs which would have been reflected in a higher price. We trust you will not find the readability of the text detracts unduly from your appreciation of this work, which we feel makes a most worthwhile contribution to the available literature in this field. Mark Eligh Publishing Editor VIeQI ABSTRACT The monograph is devoted to scientific basis of semiconductor chemical sensors technique. Its attention is focused at the usage of semi- conductor sensors in the precision physico-chemical studies. The mono- graph expounds physical and chemical basis underlying the semiconduc- tor sensor method, discusses the mechanism of processes occurring under interaction of gas with semiconductor adsorbent surface, leading to changed electrophysical parameters of the latter. The monograph is intended for the scientists and engineers special- ized in physical-chemistry of heterogeneous and heterogeneous- homogeneous processes and designing of semiconductor chemical sensors. viii List of Contributors: Prof. L A.Myamikov ( Chapters 3,4 ) Chiefo f Department of Chemical Sensors, Karpov Institute ofP hysieal Chemistry, Moscow, Ru~a. Dr. V.YL S ~ ( Chaptm 1,2 ) Sentor Researeher, D~artment of Clu~cal Smsors, Karpov Institute ofP hysical Chemts~, Moscov, aussid . Dr. L Yu. Kupriyanov ( Chapter 5 ) Senior Researcl~r, Department of Chontcal Sensors, Karpov Institute ofP hysical Chemistry,M oscov, Russia. Dr. S.~_ 7_z~z~ov ( Ch,p~r 6 ) Senior Researcher, Department o/Chemical Sensors, Karpov Institute o/Physical ChemEmy, Moscov, Rusaa. Present addv~: LSI Logic Corporation, 3115 Alfred St~ee~ MS J-201, Ssnta Clam, CA 95054, USA. ix CONTENTS Introduction ........................................................................ Chapter 1 Physical and chemical basics of the method of semi- conductor sensors ................................................. 1.1. What are the semiconductor chemical sensors9 1.2. The role of electronic theory of chemisorption in developing ideas on effects of adsorption on electrical and physical properties of semiconduc- tor adsorbents ............................................. 10 1.3. Various forms of adsorption .......................... 13 1.4. Adsorption isotherms ................................... 17 1.5. Kinetics of adsorption .................................. 20 1.6. Characteristic temperature intervals of gas- solid body interaction .................................. 23 1.7. Effect of adsorption on electrophysical proper- ties of semiconductors .................................. 25 1.7.1. Chemisorption induced band bending in semiconductor ............................................. 26 1.7.2. The effect of adsorption charging of the surface on the value of conductivity of surface- adjacent layers and semiconductor adsorbent work function ............................................. 35 1.8. Role of recharging of biographic surface states during chemisorption charging of a semiconduc- tor surface .................................................. 41 t.9. The kinetic of adsorption charging of the surface of semiconductor under relaxation of biographic surfacing charge .......................................... 45 1.10. The effect of adsorption surface charging on electrophysical characteristics of polycrystalline semiconductor adsorbents .............................. 51 1.10.1. Adsorption of acceptor particles ......... 55 t. 10.2. Adsorption of donor particles ............. 67 1.t0.3. Adsorption response of electrophysical characteristics of semiconductor sensors made of barrier-disordered polycrystalline oxides ......... 72 1.11. The effect of adsorption on concentration of the surface and volume interstitial defects in semi- conductor adsorbent and resultant change in electric conductivity .................................... 81