Table Of ContentSensors
Volume 2
Chemical and Biochemical Sensors
9
VCH
Sensors
A Comprehensive Survey
Edited by
W. Gopel (Universitat Tubingen, FRG)
J. Hesse (Zeiss, Oberkochen, FRG)
J. N. Zemel (University of Pennsylvania ,
Philadelphia, PA, USA)
Published
Vol. 1 Fundamentals and General Aspects
(Volume Editors: T. Grandke, W. H. KO)
Vol. 2 Chemical and Biochemical Sensors, Part I
(Volume Editors: W. Gopel, T. A. Jones t, M. Kleitz,
J. Lundstrom, T. Seiyama)
Vol. 4 Thermal Sensors
(Volume Editors: T. Ricolfi, J. Scholz)
Vol. 5 Magnetic Sensors
(Volume Editors: R. Boll, K. J. Overshott)
Remaining volumes of this closed-end series:
Vol. 3 Chemical and Biochemical Sensors, Part I1 (scheduled for 1991)
Vol. 6 Optical Sensors (scheduled for 1991)
Vol. 7 Mechanical Sensors (scheduled for 1992)
Vol. 8 Cumulative Index and Selective Topics (scheduled for 1993)
OVCH Verlagsgesellschaft mbH, D-6940 Weinheim (Federal Republic of Germany), 1991
Distribution
VCH, 0.B ox 101161, D-6940 Weinheim (Federal Republic of Germany)
P.
Switzerland: VCH, P. 0.B ox, CH-4020 Base1 (Switzerland)
United Kingdom and Ireland: VCH (UK) Ltd., 8 Wellington Court, Wellington Street,
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USA and Canada: VCH, Suite 909,220 East 23rd Street, New York, NY 10010-4606 (USA)
ISBN 3-527-26768-9 (VCH, Weinheim) ISBN 0-89573-674-8 (VCH, New York)
Sensors
A Comprehensive Survey
Edited bv
W Gopd, J. Hesse, J. N. Zemel
Volume 2
Chemical and Biochemical Sensors
Part I
Edited by
t,
W. Gopel, T. A. Jones M. Kleitz,
J. Lundstrom, and T. Seiyama
- - -
Weinheim New York Base1 Cambridge
Series Editors:
Prof. Dr. W. Gopel Prof. Dr. J. Hesse Prof. Dr. J. N. Zemel
Institut fur Physikalische und Carl Zeiss, Center for Sensor Technology
Theoretische Chemie der Universitat ZB ,,Entwicklung" University of Pennsylvania
Auf der Morgenstelle 8 Postfach 1380 Philadelphia, PA 19104-6390, USA
D-7400 Tubingen, FRG D-7082 Oberkochen, FRG
Volume Editors:
Prof. Dr. W. Gopel Dr. M. Kleitz Prof. J. Lundstrom Prof. T. Seiyama
see above L.I.E.S./ E.N.S.E. E.G Linkoping Institute of Tokuyama Soda Co., Ltd.
Dr. T. A. Jones t Domaine Universitaire, Technology Tenjin 1-10-24
Health and Safety B.P. 75 Dept. of Physics and Chuo-ku, Fukuoka-shi,
Executive F-38402 Saint-Martin Measurement Technology Japan 810
Sheffield, UK d'H&res,F rance S-58183 Linkoping, Sweden
This book was carefully produced. Nevertheless, authors, editors and publisher do not warrant the
information contained therein to be free of errors. Readers are advised to keep in mind that statements,
data, illustrations, procedural details or other items may inadvertently be inaccurate.
Published jointly by
VCH Verlagsgesellschaft mbH, Weinheim (Federal Republic of Germany)
VCH Publishers Inc., New York, NY (USA)
Editorial Directors: Dip1.-Phys. W. Greulich, Dip1.-Chem. Dr. M. Weller, N. Banerjea-Schultz
Production Manager: Dipl.-Wit.-Ing. (FH) H.-J. Schmitt
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data:
Sensors: a comprehensive survey: Vol2. Chemical
and biochemical sensors, Part I. - (Sensors)
I. Goepel, W. 11. Jones, T. A. 111. Kleitz, M.
502.8
ISBN 3-527-26768-9
Deutsche Bibliothek Cataloguing-in-Publication Data:
Sensors : a comprehensive survey / ed. by W. Gouel .. . -
Weinheim ; Basel (Switzerland) Cambhdge ; New York, NY :
VCH.
NE: Gopel, Wolfgang [Hrsg.]
Vol. 2. Chemical and biochemical sensors. -Part 1. Ed. by W.
Gopel . .. - 1991
ISBN 3-527-26768-9 (Weinheim .. .)
ISBN 0-89573-674-8 (New York)
OVCH Verlagsgesellschaft mbH, D-6940 Weinheim (Federal Republic of Germany), 1991
Printed on acid-free paper
All rights reserved (including those of translation into other languages). No part of this book may be reproduced
in any form - by photoprinting, microfilm, or any other means -nor transmitted or translated into a machine
language without written permission from the publishers. Registered names, trademarks, etc. used in this book,
even when not specifically marked as such are not to be considered unprotected by law.
Composition: Filmsatz Unger + Sommer GmbH, D-6940 Weinheim.
Printing: DiesbachMedien, D-6940 Weinheim.
Bookbinding: GroDbuchbinderei J. Schaffer, D-6718 Grunstadt.
Printed in the Federal Republic of Germany
Preface to the Series
The economic realities of productivity, quality, and reliability for the industrial societies of
the 21st century are placing major demands on existing manufacturing technologies. To meet
both present and anticipated requirements, new and improved methods are needed. It is now
recognized that these methods must be based on the powerful techniques employing com-
puter-assisted information systems and production methods. To be effective, the measure-
ment, electronics and control components, and sub-systems, in particular sensors and sensor
systems, have to be developed in parallel as part of computer-controlled manufacturing
systems. Full computer compatibility of all components and systems must be aimed for. This
strategy will, however, not be easy to implement, as seen from previous experience. One major
aspect of meeting future requirements will be to systematize sensor research and development.
Intensive efforts to develop sensors with computer-compatible output signals began in the
mid 1970’s ; relatively late compared to computer and electronic measurement peripherals.
The rapidity of the development in recent years has been quite remarkable but its dynamism
is affected by the many positive and negative aspects of any rapidly emerging technology. The
positive aspect is that the field is advancing as a result of the infusion of inventive and finan-
cial capital. The downside is that these investments are distributed over the broad field of
measurement technology consisting of many individual topics, a wide range of devices, and
a short period of development. As a consequence, it is not surprising that sensor science and
technology still lacks systematics. For these reasons, it is not only the user who has difficulties
in classifying the flood of emerging technological developments and solutions, but also the
research and development scientists and engineers.
The aim of “Sensors” is to give a survey of the latest state of technology and to prepare
the ground for a future systematics of sensor research and technology. For these reasons the
publishers and the editors have decided that the division of the handbook into several volumes
should be based on physical and technical principles.
Volume 1 (editors: T. GrandkeBiemens (FRG) and W. H. Ko/Case Western Reserve Univer-
sity (USA)) deals with general aspects and fundamentals : physical principles, basic technolo-
gies, and general applications.
Volume 2 and 3 (editors: W. GOpel/Tubingen University (FRG), T. A. Jones ?/Health and
Safety Executive (UK), M. Kleitz/LIE-NSEEG (France), L. LundstrOm/LinkOping University
(Sweden) and T. Seiyama/Tokuyama Soda Co. (Japan)) concentrate on chemical and
biochemical sensors.
Volume 4 (editors : J. Scholz/Sensycon (FRG) and T. Ricolfi/Consiglio Nazionale Delle
Ricerche (Italy)) refers to thermal sensors.
Volume 5 (editors: R. Boll/Vacuumschmelze (FRG) and K. J. Overshott/Gwent College
(UK)) deals with magnetic sensors.
Volume 6 (editors : E. Wagner and K. (FRG) and
Spenner/Fraunhofer-Gesellschaft
R. Dandliker/Neuchbtel University (Switzerland)) treats optical sensors.
Volume 7 (editors : N. F. de Rooij/Neuchbtel University (Switzerland), B. Kloeck/Hitachi
(Japan) and H. H. Bau/University of Pennsylvania (USA)) presents mechanical sensors.
Each volume is, in general, divided into the following three parts: specific physical and
technological fundamentals and relevant measuring parameters ; types of sensors and their
technologies ; most important applications and discussion of emerging trends.
VI Preface to the Series
It is planned to close the series with a volume containing a cumulated index.
The series editors wish to thank their colleagues who have contributed to this important
enterprise whether in editing or writing articles. Thank is also due to Dip1.-Phys. W. Greulich,
Dr. M. Weller, and Mrs. N. Banerjea-Schultz of VCH for their support in bringing this series
into existence.
W. GBpel, Tiibingen J. Hesse, Oberkochen J. N. Zemel, Philadelphia, PA
August 1991
Planning “Sensors”, it soon became clear that chemical and biochemical sensors would
have to be treated in two volumes to appropriately present the wealth of material.
Thus, these volumes present for the first time a comprehensive description of chemical and
biochemical sensors with emphasis placed upon both, technical and scientific fundamentals
and applications. The aim is to offer well-funded knowledge to scientists and technicians and
to show todays technical capabilities in this sensor field. Furthermore, both volumes together
are intended to foster the future developments and applications of sensors and at the same
time serve as a useful reference work.
The arrangement of the material presented here deviates in some way from that of the other
volumes in the series “Sensors”, which are devoted to physical sensors (mechanical, thermal,
magnetic, optical sensors). With those sensors the internal structure of each single volume
follows a classification by the input signal of the first transduction principle, which in most
cases is identical with a classification according to the measurand. (For a complete discussion
of sensor definitions and classifications see Volume 1, Chapter 1.). The number of meas-
urands in chemical and biochemical systems, however, is many orders of magnitude larger
than in physical systems because of the huge number of different compounds which can occur
in gaseous, liquid, and solid media. Therefore another structuring criterion had to be used.
As described in detail in Chapter 1 of the present volumes, different types of (bio-)chemical
sensors may be classified according to the different sensor properties used for the detection
of chemical state, ie, of concentrations, partial pressures, or activities of particles. We adopted
this classification to organize the “core” of the present volumes which consists of a descrip-
tion of “basic sensors” (like liquid and solid electrolyte sensors, etc.). For the sake of com-
pleteness, the core should be surrounded by a “shell” of articles devoted to other important
aspects of the field:
- physical and chemical parameters and measurands;
- the theoretical physical or physico-chemical background underlying the sensing mecha-
nisms (selected textbook knowledge on mechanics, optics, thermodynamics, kinetics,
statistics, etc.);
- the technology to produce sensor elements or components (thin-film, thick-film, ceramics
technologies, etc.) ;
- applications (car engine regulation, environmental control, etc.).
We tried to cover all these aspects by organizing the books in the following way:
First volume :
- Definitions, typical examples for chemical and biochemical sensors, and some historical
remarks are given in Chapters 1 and 2.
- Chemical sensor technologies and interdisciplinary tasks to design chemical sensors are
described in Chapter 3.
VIII Preface to the Volumes “Chemical and Biochemical Sensors”
- Physical and physical chemistry basics of different detection principles and also pattern
recognition approaches for multicomponent analysis with sensor arrays are described in
Chapters 4-6.
- The major part of the volumes consists of a careful description of basic sensors in
Chapters 7- 13. They include liquid electrolyte sensors, solid electrolyte sensors, electronic
conductivity and capacitance sensors, field effect sensors, calorimetric sensors, op-
tochemical sensors, and mass sensitive sensors.
Second volume :
- Biosensors often make use of transducer properties of the basic sensors mentioned above
and usually have additional biological components. They are therefore described in a
separate Chapter 14.
- Application aspects are dealt with in Chapters 15-25. Here, the possibilities and limita-
tions of sensors if compared with the conventional instrumentation in analytical chemistry
and calibration aspects are described first. Specific facettes of certain fields of applications
are then presented by specialists from different fields including environmental, biotechno-
logical, medical, or chemical process control.
A major input to the present books originally came from Dr. T. A. Jones from the National
Health and Safety Executive in Sheffield, U. K. He was a distinguished scientist in chemical
sensor basic research and an expert in the particular field of combustable gas sensors. In 1989
he passed away. We could like to take the opportunity here to thank him for his input and
enthusiastic support in the planning phase of the volumes on chemical and biochemical sen-
sors.
After all this effort, the editors would now like to thank all participating authors for their
contributions and their help in structuring the book by coordinating their individual chapters
to the overall guidelines. The editors would also like to thank Dr. Klaus Schierbaum and the
staff of VCH, particularly the editorial staff Mrs. N. Banerjea-Schultz and Dip1.-Phys.
W. Greulich for their professional input and patience.
Wolfgang Gtipel, Michel Kleitz, Ingemar Lundstrtim, Tetsuro Seiyama
Tubingen, Grenoble, Linktiping, Fukuoka
August 1991
Contents
Volume 2 : Chemical and Biochemical Sensors, Part I
List of Contributors . . . . . . . . . . . . . . . . . . . . . . XI1
1 Definitions and Typical Examples . . . . . . . . . . . . . . . . 1
u! Gopel, K.-D. Schierbaum
2 Historical Remarks . . . . . . . . . . . . . . . . . . . . . . . 29
u! Gopel, T. A. Jones, T. Seiyama, J. N. Zemel
3 Chemical Sensor Technologies : Empirical Art and Systematic Research 61
u! Gopel
4 Specific Molecular Interactions and Detection Principles . . . . . . 119
u! Gopel, K.-D. Schierbaum
5 Specific Features of Electrochemical Sensors . . . . . . . . . . . . 159
H.-D. Wiemhofer, K. Cammann
6 Multicomponent Analysis in Chemical Sensing . . . . . . . . . . . 191
S. Vaihinger, u! Gopel
7 Liquid Electrolyte Sensors : Potentiometry, Amperometry, and Conduc-
tometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
E Oehme
8 Solid State Electrochemical Sensors . . . . . . . . . . . . . . . . 341
M. Kleitz, E. Siebert, I? Fabrx J. Fouletier
9 Electronic Conductance and Capacitance-Sensors . . . . . . . . . . 429
u! Gopel, K.-D. Schierbaum
10 Field Effect Chemical Sensors . . . . . . . . . . . . . . . . . . 467
Device Principles
I. Lundstrom
Ion-Sensitive FETs
A. van den Berg, B. H. van der Schoot, H. H. van den Vlekkert
Field Effect Gas Sensors
M. Armgarth, C. J. Nylander
11 Calorimetric Chemical Sensors . . . . . . . . . . . . . . . . . . 529
T A. Jones, I? Walsh
12 Optochemical Sensors . . . . . . . . . . . . . . . . . . . . . . 573
0. Wolfbeis, G. E. Boisde, G. Gauglitz
X Contents
13 Mass-Sensitive Devices . . . . . . . . . . . . . . . . . . . . . 647
M. S. Nieuwenhuizen, A. Venema
Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
List of Symbols and Abbreviations . . . . . . . . . . . . . . . . 703
Volume 3 : Chemical and Biochemical Sensors, Part I1
(Contents given as an overview)
List of Contributors
14 Specific Features of Biosensors
H.-L. Schmidt, K Schuhmann, E K Scheller, t;: Schubert
15 Chemical Sensors and Instrumentation in Analytical Chemistry
K Gopel, M. Oehme
16 Calibration of Gas Sensors
K. Kaltenmaier
17 Applications of Optochemical Sensors for Measuring Chemical Quanti-
ties
0. Wolfbeis, G. E. Boisde
18 Applications of Optochemical Sensors for Measuring Environmental and
Biochemical Quantities
0. Wolfbeis
19 Sensors and Instrumentation in Environmental Control
K. Colbow, K. Colbow
20 Humidity Control
H. Arai, T Seiyama
21 Biosensors for Monitoring Pesticides in Water
I? Krdmer, R. D. Schmid
22 Sensors in Biotechnology
T Scheper, K. E Reardon
23 Clinical and Respiration Gas Analysis
H. Albrecht
