Chemical Sensors: Comprehensive Sensor Technologies, Vol. 4: Solid State Sensors

CHEMICAL SENSORS
COMPREHENSIVE SENSORS TECHNOLOGIES

VOLUME 4: SOLID-STATE DEVICES
CHEMICAL SENSORS
COMPREHENSIVE SENSORS TECHNOLOGIES
VOLUME 4: SOLID-STATE DEVICES
EDITED BY
GHENADII KOROTCENKOV
GWANGJU INSTITUTE OF SCIENCE AND TECHNOLOGY GWANGJU, REPUBLIC OF KOREA
MOMENTUM PRESS, LLC, NEW YORK
Chemical Sensors: Comprehensive Sensors Technologies. Volume 4: Solid-State Devices Copyright Momentum Press, LLC, 2011 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any meanselectronic, mechanical, photocopy, recording or any other except for brief quotations, not to exceed 400 words, without the prior permission of the publisher. First published in 2011 by Momentum Press, LLC 222 East 46th Street, New York, NY 10017 www.momentumpress.net ISBN-13: 978-1-60650-233-4 (hard back, case bound) ISBN-10: 1-60650-233-6 (hard back, case bound) ISBN-13: 978-1-60650-235-8 (e-book) ISBN-10: 1-60650-235-2 (e-book) DOI forthcoming Cover design by Jonathan Pennell Interior design by Derryfield Publishing, LLC First Edition: March 2011 10 9 8 7 6 5 4 3 2 1 Printed in the United States of America
CONTENTS
PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES PREFACE TO VOLUME 4: SOLID-STATE DEVICES ABOUT THE EDITOR CONTRIBUTORS 1 INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES G. Korotcenkov B. K. Cho 1 Definitions and Classifications 2 A Brief History of Chemical Sensors 3 Motivations for Design of Chemical Sensors 4 What Determines Success in Chemical Sensor Design? 5 Materials for Chemical Sensors 5.1 Metal Oxides 5.2 Polymers 5.3 New Trends in Sensing Materials 6 Some Useful Definitions 7 Acknowledgments References 2 SENSING AND SAMPLING STRATEGIES M. Z. Atashbar S. Krishnamurthy 1 Introduction 2 Sensing Parameters 2.1 Sensitivity xv xix xxi xxiii 1
1 7 9 15 17 17 19 21 29 34 34 39
39 39 40
vi CONTENTS
2.2 2.3 2.4 2.5 2.6
Selectivity Response and Recovery Rates Saturation Resolution Noise
40 41 42 42 42 43 43 44 44 45 48 49 51
3 Sensor Fundamentals 4 Sensor Test Methods 5 Sensor Calibration 6 Repeatability and Stability of Sensors 7 Signal Sampling and Data Processing 8 Signal Processing for Single Sensors 9 Signal Processing in a Multisensor Environment References 3 CONDUCTOMETRIC METAL OXIDE GAS SENSORS: PRINCIPLES OF OPERATION APPROACHES TO FABRICATION G. Korotcenkov V. Sysoev
AND
53
1 Introduction 2 Fundamentals of Gas Sensing Effects in Metal OxideBased Sensors: Main Principles of Metal Oxide Gas Sensor Operation 2.1 Bulk-Conduction Model: Solid ElectrolyteBased Conductometric Gas Sensors (High-Temperature Operation) 2.2 Ionsorption Model (Chemiresistors, Low-Temperature Operation) 2.3 Requirements for Metal Oxides to be Used at Low and High Temperatures 2.4 Advantages and Disadvantages of Low- and High-Temperature Operation of Gas Sensors 3 Metal Oxides Employed in Conductometric Gas Sensors 3.1 High-Temperature Sensors (Solid ElectrolyteBased Sensors) 3.2 Low-Temperature Sensors (Chemiresistors) 4 Approaches to Gas Sensor Fabrication 4.1 Ceramic Sensors 4.2 Planar Sensors 4.3 Features of Thick-Film Technology 4.4 Thin-Film Technology 4.5 Kinetics of Metal Oxide Gas Sensor Response: Processes Controlling the Rate of Sensor Response
53 54 54 55 65 66 67 67 70 77 78 81 86 90 93
CONTENTS vii
4.6 The Role of Thermal Treatments in Gas Sensor Fabrication 4.7 Material Requirements for Packaging of Gas Sensors 5 Other Approaches to the Design of Conductometric Gas Sensors 5.1 Conductometric Sensors Based on 1-D Nanostructures 5.2 One-Electrode Gas Sensors 6 Miniaturization and Microfabrication 6.1 Microfabrication 6.2 Integrated Conductometric Gas Sensors 6.3 Advantages and Disadvantages of Microfabrication 7 Approaches to Optimization (Improvement) of Conductometric Gas Sensor Parameters 7.1 Structure Control 7.2 Bulk Doping and Surface Modification 7.3 Engineering Approaches to Improving Sensitivity 7.4 Approaches for Improving Gas Sensor Selectivity 7.5 Approaches to Optimizing the Rate of Sensor Response 7.6 Stability 8 Sensor Manufacturers 9 Outlook for the Future References 4 WORK FUNCTIONBASED GAS SENSORS: SCHOTTKY- AND FET-BASED DEVICES C. Senft P. Iskra I. Eisele W. Hansch 1 Introduction 2 Theoretical Background: Gas Adsorption and Work Function Change 2.1 Gas Adsorption on Solid Surfaces 2.2 The Work Function 3 Transducers 3.1 Basic Principles of Gas-Sensing Devices 3.2 Transducers for Interfacial Work Function Changes 3.3 Transducers for Surface Work Function Changes 3.4 Transducers for High-Temperature Operation 4 Application Example: The Temperature-Controlled Phase-Transition FET (TPT-FET) 4.1 Introduction 4.2 The Sensing Effect
96 98 99 99 105 118 118 126 128 129 129 139 144 147 153 154 160 161 161 187
187 189 189 191 192 192 193 197 203 211 211 213
viii CONTENTS
4.3 4.4 4.5 4.6 4.7 4.8
Fabrication of the Sensor Work Function Change at Constant Temperature Temperature Dependence of the Work Function Change Operation of Temperature-Controlled Sensors Response Time The TPT-FET: A Benchmark
214 214 218 219 221 222 223 223 229
5 Summary References 5 CAPACITANCE-TYPE CHEMICAL SENSORS S. Chatzandroulis V. Tsouti I. Raptis D. Goustouridis 1 Introduction 2 Permittivity Sensors 2.1 Parallel-Plate Sensors 2.2 Interdigitated Electrode Sensors 2.3 Capacitance-Type Chemical Sensors on Flexible Substrates 2.4 Materials Used in Capacitance-Type Chemical Sensors 3 Bimorph Capacitance-Type Chemical Sensors 3.1 Parameters for Effective Chemical Sensing 3.2 Cantilever Bimorph Sensors 3.3 Membrane Bimorph Sensors 4 Outlook for Capacitance-Type Chemical Sensors References 6 GAS SENSORS USING PYROELECTRIC AND THERMOELECTRIC EFFECTS W. Shin M. Nishibori I. Matsubara 1 Fundamentals of Sensor Operation 1.1 Pyroelectricity 1.2 Thermoelectricity 2 Materials of Thermal Energy Conversion 2.1 Pyroelectric Materials 2.2 Thermoelectric Materials
229 230 231 232 237 238 244 245 247 249 252 255 261
261 261 262 262 263 264
CONTENTS ix
3 Fabrication and Packaging 3.1 Transducer Films 3.2 Catalyst Deposition 3.3 Membrane Structure by Bulk Wet Etching 4 Parameters 4.1 Transducer Performance 4.2 Detectivity of Pyroelectric Devices 4.3 Seebeck Coefficients of Thermoelectric Devices 4.4 Catalyst Performance 4.5 Catalyst Parameters 5 Approaches to Optimization of Sensor Parameters 5.1 5.2 5.3 5.4 5.5 Pyroelectric Sensors AC Pyroelectric Sensors Thermoelectric Sensors Long-Term Stability of the Ceramic Catalyst Gas Selectivity
266 266 267 268 269 269 270 270 271 272 272 272 273 274 277 279 280 283 283 287 287 288 292 292 299 301 303 305 309 309 312 313 315 315
6 Fields of Application and Market for Sensors 7 Summary References 7 CALORIMETRIC SENSORS R. E. Cavicchi 1 Introduction 2 Fundamentals of Calorimetric Sensor Operation 3 Catalytic Bead Devices 4 Thin-Film and MEMS Devices 5 Materials 6 Poisoning 7 Signal Analysis and Operating Modes 8 Packaging 9 Applications 9.1 Gas Detection 9.2 Biological Applications 9.3 Safety 10 Conclusions References
x CONTENTS
MICROCANTILEVER-BASED CHEMICAL SENSORS S. K. Vashist G. Korotcenkov 1 Introduction 2 Microcantilevers and Their Modes of Operation 2.1 Operating Modes for Cantilever Mass Sensors 3 Microcantilever Deflection Detection Methods 3.1 Optical Method 3.2 Piezoresistive Method 3.3 Capacitive Method 3.4 Piezoelectric Method 3.5 Interferometry Method 3.6 Optical Diffraction Grating Method 3.7 Charge-Coupled Device Detection Method 4 Resonant Operating Mode 4.1 Mechanical Properties of Microcantilevers 4.2 Mass Resolution Limitations 4.3 Influence of Surrounding Conditions 5 Bending Behavior of Microcantilevers 6 Excitation Techniques 7 Fabrication of Microcantilevers 7.1 Silicon-Based Microcantilevers 7.2 Polymer-Based Microcantilevers 8 Surface Functionalization 8.1 General Strategy 8.2 Sorption-Induced Effects and Their Influence on Cantilever Operation 8.3 Functionalization Methods 8.4 Immobilization of Bioreceptors 9 Microcantilever-Based Sensors 10 Applications of Cantilever-Based Chemical Sensors 10.1 Gas Sensing 10.2 Detection of Herbicides 10.3 Detection of Metal Ions 10.4 Humidity Sensing 10.5 Detection of Volatile Organic Compounds 10.6 Detection of Tributyrin 10.7 Monitoring of Missile Storage and Maintenance Needs 10.8 pH Sensing
321
321 322 323 324 325 326 327 328 328 328 328 329 329 330 331 332 334 335 337 340 342 342 343 345 348 349 351 351 355 355 356 356 359 359 359
CONTENTS xi
11 Biosensing Applications 11.1 Detection of DNA 11.2 Detection of Prostate-Specific Antigen 11.3 Detection of Hydrogen Peroxide 11.4 Detection of Myoglobin 11.5 Detection of Lipoproteins 11.6 Detection of Glucose 12 Ultrasensitive Nanocantilevers 13 An Electronic Nose Based on a Micromechanical Cantilever Array 14 Commercial Status 15 Outlook and Future Trends References 9 THE QUARTZ CRYSTAL MICROBALANCE M. Voinova M. Jonson 1 Introduction 1.1 Short History of the QCM Approach 1.2 Principle of Biosensoring 2 Piezoelectric Materials 2.1 Piezoelectric Materials Other Than Quartz 2.2 Quartz as a Piezoelectric Material 3 Basics of QCM Operation 3.1 Principles of the QCM 3.2 Construction and Stability of the QCM 3.3 Configuration of QCM Electrodes 3.4 Miniaturization and Integration in Arrays; the MQCM 3.5 QCM-D Technique 3.6 Some Disadvantages of the QCM 4 Theoretical Analysis of the QCM Response 4.1 Physical Analysis of the Propagation of Transverse Shear Waves in a Loaded Quartz Resonator 4.2 Equivalent Circuit Models 4.3 Simultaneous Viscoelastic and Liquid Loading of the Quartz Resonator: Three Models 4.4 Newtonian LiquidLoaded Quartz Resonator 4.5 Thin Viscoelastic Layer Loading 4.6 Mass Loading of the Quartz Resonator: A Short Summary
360 360 361 361 362 362 362 363 364 367 367 368 377
377 378 380 381 381 384 386 386 387 391 394 395 397 397 397 403 406 407 409 410
xii CONTENTS
5 Applications of QCM-Based Sensors 5.1 Gas Sensors 5.2 QCM Coatings: Basic Requirements for Sensing Layer 5.3 Liquid-Phase Measurements; Electrochemical QCM 5.4 Nanotribology Challenges 5.5 QCM Biosensors: Selected Examples 6 Outlook 7 Quartz Crystal and Quartz Crystal Microbalance Companies 8 Nomenclature 9 Acknowledgments 10 Recommendations for Further Reading References 10 SURFACE ACOUSTIC WAVE SENSORS FOR CHEMICAL APPLICATIONS Adeel Afzal Franz L. Dickert 1 Introduction 2 State-of-the-Art SAW Sensors 2.1 PrincipleThe Piezoelectric Effect 2.2 Piezoelectric Materials 2.3 DesignInterdigital Transducers 2.4 FabricationPhotolithography 2.5 Sensor EffectThe Sauerbrey Equation 2.6 SAW Sensors in Liquids 2.7 SAW Sensor Characteristics 3 Coating Materials 3.1 Nonselective Polymers 3.2 Conductive Polymers 3.3 HostGuest Chemistry 3.4 Imprinting 3.5 Self-Assembled Monolayers 3.6 Other Coating Materials 4 Applications 4.1 Gases 4.2 Organic Vapors 4.3 Liquids 5 Comparing Surface and Bulk Acoustic Wave Devices
410 410 414 415 416 421 428 429 429 431 431 431 447
447 448 448 448 449 450 451 455 456 457 457 458 459 460 462 463 464 464 466 471 471
CONTENTS xiii
6 The Market for SAW Sensors 7 Abilities and Limitations of SAW Sensors 8 Outlook References 11 INTEGRATED CHEMICAL SENSORS M. E. Zaghloul I. Voiculescu 1 Introduction 2 CMOS Technology 2.1 Overview of CMOS Technology 2.2 Micromachining CMOS 2.3 Gas Sensor Fabricated Using Industrial CMOS Technology Developed at Eth Zrich 2.4 Electrochemical Sensors Fabricated Using Standard CMOS Technology 3 NIST CMOS MEMS Technology 3.1 Pecularities of NIST CMOS MEMS Technology 3.2 Conductometric Chemical Gas Sensor Using NIST CMOS MEMS Technology 4 CMU CMOS MEMS Technology 4.1 CMU CMOS MEMS Fabrication Technology Overview 4.2 Resonant Microbeam Gas Sensor Fabricated Using CMU CMOS MEMS Technology 5 Jazz SiGe BiCMOS Technology 5.1 Jazz SiGe BiCMOS Technology Overview 5.2 Gas Sensor Fabricated Using Jazz SiGe BiCMOS Technology 6 Other Types of MEMS Gas Sensors Integrated in CMOS Technology 6.1 SAW Resonator as Chemical Gas Sensor Integrated in Industrial CMOS Technology 6.2 Optical Chemical Sensors in CMOS Technology 7 Conclusions References INDEX
471 473 475 475 485
485 486 486 487 489 492 494 495 497 498 500 503 504 505 505 507 508 509 511 511 515
PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES

In spite of their century-long history, chemical sensors appeared on the commercial market only 50 years ago. In recent years, however, the field of chemical sensors has broadened and expanded greatly. At present, chemical sensors are being used in medicine, agriculture, industry, transport, environmental control, and other fields. However, the process of developing new sensors as well as improving older types of chemical sensors is still ongoing. New technologies and the toughening of ecological standards require more sensitive instruments with faster response times, better selectivity, and improved stability. The second half of this six-volume series on chemical sensors, devoted to comprehensive sensor technologies, describes these developments and the new processes and applications. These volumes are intended to be a primary source for both fundamental and practical information about where sensor technologies are now and where they are headed for the future. We are sure that Volumes 46 in this series will be a useful addition to the first three volumes, on fundamentals of sensing materials, in which various sensing materials that can be used in chemical sensors are discussed in detail. Analysis of chemical sensor design, fabrication, and functioning requires other approaches to description in comparison with materials science problems, and therefore we decided that consideration of materials and devices should be carried out separately. From our point of view, dividing the series into two parts as we have done results in more logical narration and more utility for readers who are interested in different aspects of chemical sensor design. In this series we provide readers with a thorough understanding of the concepts behind chemical sensors, presenting the information necessary to develop such sensors, covering all aspects including fundamental theories, fabrication, functionalization, characterization, and real-world applications, so as to enable them to pursue their research and development requirements. Therefore, we hope that this series will help readers understand the present status of chemical sensors and will also act as an introduction, which may encourage further study, as well as an estimate of the roles that chemical sensors may play in the future. Chemical Sensors: Comprehensive Sensor Technologies is a three-volume series, comprising Volumes4, 5, and 6 in our series, Chemical Sensors. Volume 4 deals with solid-state devices, Volume 5 with electrochemical and optical sensors, and Volume 6 with applications of chemical sensors. The chapters included in the volumes consist of review and overview papers written by experts in the field. The authors
xv
xvi PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES
of each of the chapters were chosen very carefully and are all well known throughout the world in their fields of study. Therefore, these books provide an up-to-date account of the present status of chemical sensors, from fundamental science and processing to applications. Specifically, Volume 4 includes descriptions of solid-state sensors such as conductometric or resistive gas sensors, Schottky-, FET-, capacitance-, and pyroelectric-type chemical sensors. Pellistors, masssensitive, and acoustic wave sensors are described as well. Integrated chemical sensors are also discussed in Volume 4. Volume 5 provides information related to electrochemical and optical sensors. Fundamentals of operation, methods of fabrication, and operating characteristics of electrochemical gas sensors, solid electrolytebased gas sensors, ion-selective electrodes, CHEMFETs, and different types of optical, fiber optical, and chemoluminescence chemical sensors are discussed. Volume 6 is dedicated to detailed examination of opportunities for applications of chemical sensors in various areas of our lives, including medicine, industry, environmental control, agriculture, and transportation. It is the editors wish that theses volume will provide the reader with a detailed understanding of the many applications of chemical sensors in both todays world and that of the future. In these chapters one can also find descriptions of architecture and fundamentals of electronic noses and electronic tongues, principles of wireless chemical sensor design, and possibilities for remote chemical sensing for atmospheric monitoring. In this three-volume series, the authors present sensors that utilize various sensing materials and phenomena. The terminology and concepts associated with sensors are presented, including some of the relevant physical and chemical phenomena applied in the sensor signal transduction system. As is well known, chemical sensing is multidisciplinary by nature. The role of sensing materials in such phenomena is also detailed. We need to note that the number of disciplines involved in the research and design of chemical sensors has increased dramatically. New knowledge and approaches are needed to achieve miniaturization, lower power consumption, and the ability to operate in complex environments for more selective, sensitive, and rapid determination of chemical and biological species. Compact analytical systems that have a sensor as one of the system components are becoming more important than individual sensors. Thus, in addition to traditional sensor approaches, a variety of new themes have been introduced to achieve the attractive goal of analyzing chemical species on the micro and nano scales. Therefore, throughout these books, numerous strategies for the fabrication and characterization of sensing materials and sensing structures which are employed in sensing applications are provided, and current approaches for chemical sensing are described. This series can be utilized as a text for researchers and engineers as well as graduate students who are either entering the field for the first time, or who are already conducting research in these areas but are willing to extend their knowledge of the field of chemical sensors. We hope that these volumes will also be of interest to undergraduate students in chemical engineering, electronics, environmental control, and medicine. These books have been written in a way that final-year and graduate university students in the fields of chemistry, physics, electronics, biology, biotechnology, mechanics, and bioengineering can easily comprehend. We believe that practicing engineers or project managers which would like to use chemical sensors but dont know how to do so, and how to select optimal chemical sensors for specific applications, also will find useful information. It is necessary here to comment briefly on the coverage of the literature. During our work on this series we tried to cover the field more or less completely. However, we need to acknowledge that an
PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES xvii
appreciable number of relevant papers may remain unknown to the authors. Regarding these, the editors and contributing authors express regret, not only to the authors of such works, but also to the readers of our books. Finally, we wish to thank all those who participated in the preparation of this series, including the contributing authors and copyright owners in Europe, the United States, Asia, and the rest of the world. We also wish to express our gratitude to the staff of Momentum Press, and in particular Joel Stein, for his kind assistance in bringing these volumes to fruition. Ghenadii Korotcenkov
PREFACE TO VOLUME 4: SOLID-STATE DEVICES

The field of solid-state chemical sensor design is a research field of increasing interest as a result of the demands for reliable, inexpensive, and portable systems for environmental monitoring, assessing indoor air quality, food quality control, military, and many other applications. Solid-state chemical sensors, because they can be microfabricated using modern technologies of mass production, may be able to realize those requirements in practice. Solid-state sensor technology has advanced remarkably during the past few decades and is rapidly becoming an essential technology. As a result, many solid-state chemical sensors are now commercially available, and researchers are working to develop next-generation solidstate sensors that have all the necessary requirements, including small size, low production costs, and low power consumption. The goal of this volume is to provide a critical assessment of the new trends in the field of solidstate chemical sensors, by describing the working principle and the applications related to the different types of solid-state sensors. In this volume the reader will find detailed descriptions of solid-state chemical sensors such as conductometric gas sensors, Schottky, FET, and work-function chemical sensors. Capacitance, pyroelectric, calorimetric, mass-sensitive, and acoustic wave chemical sensors are also analyzed in detail. Reduction in size from bulk to polycrystalline and nanostructured sensing materials, from micro- to nano-sized transducers, while promising high sensitivity, small size, high speed, low cost, and increased selectivity, requires new design considerations that should consider factors such as integration with other devices and device lifetime. At present, microfabrication has reached a stage of serious application and is accepted as a good alternative to classical macroscopic technologies. Therefore, approaches to microfabrication of chemical sensors and to integration are discussed in this volume as well. Future trends in solid-state sensors design are also described. So, the volume gives a survey of the latest state of technology and contributes to preparing the ground for future achievements in both solidstate sensor research and development of solid-state sensor technologies. We believe that this book covers all topics of solid-state chemical sensors from fundamentals of operation and construction of devices to optimal materials for those sensors and approaches to achieving better operating characteristics. The reader will find a strong emphasis not only on what and how, but also on why. Specialists and newcomers to the field will find this book easy to use. Each chapter has its own introduction and list of references, in order to make it accessible to any reader notwithstanding his or her background in related subjects. Since the last decade has seen an enormous amount of activity
xix
xx PREFACE TO VOLUME 4: SOLID-STATE DEVICES
in the field of solid-state sensor systems, this book represents a valuable and accessible guide and reference for researchers with up-to-date examples and state-of-the-art results. We need to admit that a number of edited surveys and monographs related to solid-state chemical sensors have been published during recent decades. However, the present volume analyzes this field of science and technology both fully and in detail. In addition, the majority of published books were written more than 10 years ago, which is a long period of time for such a rapidly developing field as chemical sensors. Since then many new technologies and new ideas have appeared and been realized. This book is intended for scientists, engineers, and manufacturers involved in the development, design, and application of solid-state chemical sensors. Undergraduate and graduate students can use this book to extend their knowledge in the field of chemical sensors. Ghenadii Korotcenkov
ABOUT THE EDITOR
Ghenadii Korotcenkov received his Ph.D. in Physics and Technology of Semiconductor Materials and Devices in 1976, and his Habilitate Degree (Dr.Sci.) in Physics and Mathematics of Semiconductors and Dielectrics in 1990. For a long time he was a leader of the scientific Gas Sensor Group and manager of various national and international scientific and engineering projects carried out in the Laboratory of Micro- and Optoelectronics, Technical University of Moldova. Currently, he is a research professor at Gwangju Institute of Science and Technology, Gwangju, Republic of Korea. Specialists from the former Soviet Union know G. Korotcenkovs research results in the study of Schottky barriers, MOS structures, native oxides, and photoreceivers based on Group IIIV compounds very well. His current research interests include materials science and surface science, focused on metal oxides and solid-state gas sensor design. He is the author of eight books and special publications, 11 review papers, 10 book chapters, and more than 180 peer-reviewed articles. He holds 18 patents. He has presented more than 200 reports at national and international conferences. His articles are cited more than 150 times per year. His research activities have been honored by the Award of the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004), The Prize of the Presidents of Academies of Sciences of Ukraine, Belarus and Moldova (2003), the Senior Research Excellence Award of Technical University of Moldova (2001, 2003, 2005), a Fellowship from the International Research Exchange Board (1998), and the National Youth Prize of the Republic of Moldova (1980), among others.
xxi
CONTRIBUTORS
Adeel Afzal (Chapter 10) Department of Analytical Chemistry University of Vienna Vienna A-1090, Austria Massood Zandi Atashbar (Chapter 2) Department of Electrical and Computer Engineering Western Michigan University Kalamazoo, Michigan 49008-5066, USA Richard E. Cavicchi (Chapter 7) Chemical Science and Technology Laboratory National Institute of Technology Gaithersburg, Maryland 20899, USA Stavros Chatzandroulis (Chapter 5) Institute of Microelectronics NCSR Demokritos Aghia Paraskevi 15310, Greece Beongki Cho (Chapter 1) Department of Material Science and Engineering Gwangju Institute of Science and Technology Gwangju 500-712, Republic of Korea Franz L. Dickert (Chapter 10) Department of Analytical Chemistry University of Vienna Vienna A-1090, Austria Ignaz Eisele (Chapter 4) Fraunhofer-Gesellschaft Munich Munich 80686, Germany
xxiii
xxiv CONTRIBUTORS
Dimitrios Goustouridis (Chapter 5) Institute of Microelectronics NCSR Demokritos Aghia Paraskevi 15310, Greece Walter Hansch (Chapter 4) University of the Federal Armed Forces of Germany Neubiberg 85579, Germany Mats Jonson (Chapter 9) Department of Physics University of Gothenburg SE-412 96 Goteborg, Sweden and Division of Quantum Phases and Devices School of Physics Konkuk University Seoul 143-701, Republic of Korea and SUPA, Department of Physics Heriot-Watt University Edinburgh EH14 4AS, Scotland, UK Peter Iskra (Chapter 4) University of the Federal Armed Forces of Germany Neubiberg 85579, Germany Ghenadii Korotcenkov (Chapters 1, 3, and 8) Department of Material Science and Engineering Gwangju Institute of Science and Technology Gwangju 500-712, Republic of Korea and Technical University of Moldova Chisinau, Republic of Moldova Sridevi Krishnamurthy (Chapter 2) Department of Electrical and Computer Engineering Western Michigan University Kalamazoo, Michigan 49008-5066, USA Ichiro Matsubara (Chapter 6) National Institute of Advanced Industrial Science and Technology (AIST) Nagoya 463-8560, Japan
CONTRIBUTORS xxv
Maiko Nishibori (Chapter 6) National Institute of Advanced Industrial Science and Technology (AIST) Nagoya 463-8560, Japan Ioannis Raptis (Chapter 5) Institute of Microelectronics NCSR Demokritos Aghia Paraskevi 15310, Greece Christoph Senft (Chapter 4) University of the Federal Armed Forces of Germany Neubiberg 85579, Germany Woosuck Shin (Chapter 6) Advanced Manufacturing Research Institute AIST Shimo-shidami Moriyama-ku, Nagoya 463-8560, Japan Victor Sysoev (Chapter 3) Department of Physics Saratov State Technical University Saratov 410054, Russia Vasiliki Tsouti (Chapter 5) Department of Applied Sciences National Technical University of Athens Zografou 15780, Greece and Institute of Microelectronics NCSR Demokritos Aghia Paraskevi 15310, Greece Sandeep Kumar Vashist (Chapter 8) Centre for Bioanalytical Sciences National Centre for Sensor Research Dublin City University Dublin 9, Ireland and National University of Singapore Singapore 117580
xxvi CONTRIBUTORS
Ioana Voiculescu (Chapter 11) Mechanical Engineering Department City College of New York New York, New York 10031, USA Marina Voinova (Chapter 9) BionanoSystems Laboratory Department of Applied Physics Chalmers University of Technology Gteborg S-412 96, Sweden Mona E. Zaghloul (Chapter 11) Electrical Engineering and Computer Science Department George Washington University Washington, DC 20052, USA
CHAPTER 1
INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES
G. Korotcenkov B. K. Cho 1. DEFINITIONS AND CLASSIFICATIONS

The Oxford English Dictionary defines a sensor as a device which detects or measures some condition or property, and records, indicates, or otherwise responds to the information received. Accordingly, sensors have the function of converting a stimulus into a measurable signal (Figure 1.1). The stimulus can be a physical stimulus such as temperature, pressure, or acceleration; alternatively, the stimulus can be a concentration of specific chemical or biological materials. While the measured signal is typically electrical, it may alternatively be pneumatic, hydraulic, or optical. Sensors are based on a broad range of underlying physical operating principles. One can usually separate three basic components of a sensor: (1) a sensor element; (2) sensor packaging and connections; and (3) sensor signal processing hardware. While they can be used in all three phases of matter, sensors for gas and liquid environments are the most common (Shieh et al. 2001). Generally, sensors can be divided into three major categories: (1) physical sensors; (2) chemical sensors; and (3) biosensors. In this volume we consider chemical sensors. Chemical sensors are widely used in many different applications, and chemical sensing technology has become a basic enabling technology in many fields (see Table 1.1). As will be shown here, interest in chemical sensors has grown as production applications, such as intelligent manufacturing processing, have proliferated. Sensors are also of great importance in safety-related areas, with applications ranging from assessing the integrity of
2 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES
Figure 1.1. (a) Basic functioning of a sensor. (b) Evolution of the stimulus (sensor input) p over time. A stimulus is applied at time t1 (response process) and removed at time t2 (recovery process). (c) Evolution of sensor response x = f(t) over time. The changes in the stimulus determine correlated changes in the sensor response (sensor output). Changes in the sensor response need some time before an equilibrated sensor response value is achieved during response and recovery processes (response and recovery times, correspondingly).
Table 1.1. Example applications and markets for chemical sensors MARKET/APPLICATION Automotive Indoor air quality Food Agriculture Medical Water treatment Environmental Industrial safety Utilities (gas, electric) Petrochemical Steel Military Aerospace EXAMPLES OF DETECTED CHEMICAL COMPOUNDS AND CLASSES O2, H2, CO, NOx, HCs CO, CH4, humidity, CO2, VOCs Bacteria, biologicals, chemicals, fungal toxins, humidity, pH, CO2 NH3, amines, humidity, CO2, pesticides, herbicides O2, glucose, urea, CO2, pH, Na+, K+, Ca2+, Cl, biomolecules, H2S, infectious disease, ketones, anesthesia gases pH, Cl2, CO2, O2, O3, H2S SOx, CO2, NOx, HCs, NH3, H2S, pH, heavy metal ions Indoor air quality, toxic gases, combustible gases, O2 O2, CO, HCs, NOx, SOx, CO2 HCs, conventional pollutants O2, H2, CO, conventional pollutants Agents, explosives, propellants H2, O2, CO2, humidity
HCs, hydrocarbons; VOCs, volatile organic compounds. Source: Reprinted with permission from Stetter et al., 2003. Copyright 2003 ECS.
INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 3
aircraft to monitoring the environment for hazardous chemicals. Chemical sensors have proven to be useful in many other domestic and military applications as well, such as the remote sensing of various chemical vapors and chemical warfare agents. The literature provides many different definitions of chemical sensors (IEC-draft 65/84 1982; Madou and Morrison 1989; Janata 1989; Moseley and Tofield 1989; Hulanicki et al. 1991; Stetter et al. 2003). Most often, chemical sensors are considered to be devices that are designed to detect and quantify a specific chemical analyte or event. For example, according to the International Union of Pure and Applied Chemistry (IUPAC), a chemical sensor is a device that can detect and signal the presence and/or quantify the concentration of a family of chemicals or a specific chemical exposed to the sensor. According to Hulanicki et al. (1991), a chemical sensor is a device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. Such chemical information may originate from a chemical reaction of the analyte or from a physical property of the system under investigation. Gpel and Schierbaum (1991), define chemical sensors as devices which convert a chemical state into an electrical signal. This simple definition is probably the one that best fits the purposes of the present work. Chemical state here must be understood to mean different concentrations or partial pressures of molecules or ions in a gas, liquid, or solid phase. Unless otherwise specified, it is usually assumed that these chemical sensors are just the primary link of the measuring chainin other words, an interface between the chemical world and the electronics. Chemical sensors differ from physical sensors, which measure physical parameters. It is necessary to note that chemical sensors are more complex extensions of physical sensors. However, in many cases the transducer technologies developed and commercialized for physical sensors are the basis for chemical sensors and biosensors. A chemical sensor is an essential component of an analyzer. In addition to the sensor, the analyzer may contain devices that perform the following functions: sampling, sample transport, signal processing, and data processing. An analyzer may be an essential part of an automated system. The analyzer, which works according to a time-dependent sampling plan, acts as a monitor. The distinction between chemical sensors and biosensors is more complex. Many authors attempt to define a sensor based on the nature of the analyte detected. In this text, we distinguish between chemical sensors and biosensors according to the nature of their reactive surface. By this definition, biosensors are devices which contain a biomolecule (such as an enzyme, antibody, or receptor) or a cell as the active detection component. Again, the nature of the analyte and the reaction which leads to detection are not limited in this definition. Some typical properties associated with chemical sensors, according to Stetter and Penrose (2002), are as follows: A sensitive layer is in chemical contact with the analyte. A change in the chemistry of the sensitive layer (a reaction) is produced after exposure to the analyte. The sensitive layer is on a platform that allows transduction of the change to electric signals. The sensors are physically small. They operate in real time. They do not necessarily measure a single or simple physical or chemical property. They are typically less expensive and more convenient than an equivalent instrument for the same chemical measurements.
It follows from these definitions that every chemical sensor can be divided into two domains: the physical transducer and the chemical interface layer (receptor) (see Figure 1.2). Some sensors may include a separator which is, for example, a membrane. At the chemical interface, the analyte interacts chemically with a surface, producing a change in physical/chemical properties. Within the receptor part of a sensor, the chemical information is transformed into a form of energy that may be measured by the transducer. Receptor layers can respond selectively to particular substances or to a group of substances. The term molecular recognition is used to describe this behavior. The transducer part of a sensor is a device capable of transforming the energy carrying the chemical information about the sample into a useful analytical signal. The transducer itself does not show selectivity. The receptor part of chemical sensors is based on the following principles (Hulanicki et al. 1991): A physical basis in which no chemical reaction takes place (Optical receptors, for example, are based on measurement of absorbance, refractive index, conductivity, temperature, or mass change.) A chemical basis in which a chemical reaction with participation of the analyte gives rise to the analytical signal A biochemical basis in which a biochemical process is the source of the analytical signal
Note that in some cases it is not possible to determine unequivocally whether a sensor operates on a chemical or on a physical principle. This is the case, for example, when the signal is due to an adsorption process. The types of reactions that may occur at the surface of chemical sensors are summarized in Table 1.2. This classification is important because chemical parameters (such as the type of chemical reaction, the equilibrium constant, and kinetic parameters) will determine a sensors performance, including sensitivity and selectivity (Stetter and Penrose 2002). Among the processes of interaction, those most important for chemical sensors are adsorption (chemisorption), ion exchange, and liquidliquid extraction (partition equilibrium). These phenomena occur primarily at the interface between the analyte and the receptor surface, where both are in an equilibrium state. Instead of equilibrium, a chemical reaction may also become the source of information. We find this, for example, in receptors in which a catalyst accelerates the rate of an analyte reaction so much that the heat released by the reaction creates a temperature change that can be transduced into an electrical signal (Grendler 2007). Transducers transfer the results of interactions between the chemical analyte and sensing materials into a measurable signal; some examples are described in Table 1.3. The change in the transducer due to
Figure 1.2. Schematic presentation of a chemical sensor. (Idea from Rahman et al. 2008.)
Table 1.2. Possible reactions at the chemical interface of chemical sensors CHEMICAL REACTION AT THE INTERFACE Adsorption Physisorption Chemisorption Partitioning Acidbase Precipitation Ion exchange Oxidation/reduction EXAMPLE A[gas] + S[surface site] = AS[surface]; Kads Vads = Ae
dG/kT
K = Cm/Cs + HA + KOH = H2O + K + A ; Ka or Kb + + Ag [aq] + NaCl[aq] = AgCl[s] + Na [aq]; Ksp + + + + H [aq] + Na [surface] = H [surface] + Na [aq]; Ki CO + O2 = CO2; Kr n
Source: Data from Stetter and Penrose 2002. the active surface event is expressed as a specific signal which may record changes in impedance, voltage, light intensity, reflectance, weight, color, or temperature. That signal is then detected, amplified, and processed by the electronics/software module. Taking into account transduction mechanisms, we can distinguish five general categories of sensors: (1) electrochemical sensors; (2) mass sensitive sensors; (3) calorimetric sensors; (4) magnetic sensors; and (5) optical sensors (see Figure 1.3). These sensors are differentiated on the basis of their underlying physical principles and operating mechanisms. For example, electrochemical sensors include sensors that detect signal changes (e.g., resistance) caused by an electrical current having passed through electrodes due to interaction with Table 1.3. Major sensor transducer technologies TRANSDUCTION MECHANISM Electrochemical OUTPUT CHANGE Current, voltage, capacitance/ impedance EXAMPLES
Photometric (radiant)
Acoustical/mechanical Magnetic Calorimetric (thermal)
Gas sensors, ISEs, FETs, CHEMFETs, conductimeters, pH sensors, interdigitated electrode capacitors Light intensity, color, or Optical sensors, fiber optic sensors, emission spectra infrared sensors, ellipsometry, internal reflectometry, laser light scattering, surface plasmon resonance Weight, amplitude, phase or SAW devices, QCM-based sensors, frequency, size, shape, position cantilevers Field strength, field detection Biosensors Temperature, heat flow, heat Thermoelectric sensors, pyroelectric content sensors, pellistors
FETs, field-effect transistors; ISEs, ion selective electrodes; SAW, surface acoustic wave; QCM, quartz crystal microbalance.
CHEMICAL SENSORS
ElectroChemical Magnetic Solid-state (electronic)
Conductometric Potentiometric FET Conductometric Culonometric CHEMFET Ion-selective electrodes Schottky diodes Work function Spectrophotometric Fluorescence Surface Plasmon Photoacoustic Thermoelectric
Optical
Calorimetric
Masssensitive
Amperometric
Fiber-optic Chemiluminescence
Catalytic (Pellistors)
Surface acoustic wave Quartz crystal microbalance
Pyroelectric
Thermal conductivity
Cantilever
Capacitance
Figure 1.3. Types of chemical sensors which can be fabricated and applied.
chemicals. Such effects may be stimulated electrically or they may result from a spontaneous interaction at the zero-current condition. Mass-sensitive sensors rely on disturbances and changes to the mass of the sensor surface during interaction with chemicals. Mass-sensitive devices transform the mass change at a specially modified surface into a change in some property of the support material. The mass change is caused by accumulation of the analyte during interaction with the sensing layer. Magnetic sensors are based on the change of paramagnetic properties of the analyte being analyzed. These are represented by certain types of oxygen monitors. (We will not examine magnetic sensors.) Optical sensors transform changes in optical phenomena that result from an interaction of the analyte with the receptor part. This category may be further subdivided according to the type of optical properties relevant to a particular sensor, for example, absorbance, reflectance, refractive index; optothermal effect, or light scattering. More generally, optical sensors detect changes in visible light or other electromagnetic waves during interactions with chemicals. The use of optical fibers in various configurations has enabled applications of optical sensors. Of course, sensors may exhibit characteristics that fall into more than one of these five broad categories. For example, some mass sensors may rely on electrical excitation or optical settings. Even so, our five categories of sensors are sufficiently distinct for the purposes of this review. We need to point out that our classification represents but one of the possible alternatives. One alternative scheme classifies sensors, not according to the primary effect, but by the method used for measuring
that effect (an example is provided by the so-called catalytic devices, in which the heat effect evolved in the primary process is measured by the change in the conductivity of a thermistor). Another alternative scheme classifies sensors according to the application to detect or determine a given analyte (examples are sensors for pH, for metal ions, or for determining oxygen or other gases). Yet another basis for the classification of chemical sensors might be by the mode of application (for example, sensors intended for use in vivo, sensors for process monitoring, and so on). Of course, it is possible to use various classifications as long as they are based on clearly defined and logically arranged principles (Hulanicki et al. 1991). Finally, we note that there is no single sensing class or sensing technology that can effectively detect everything of possible interest in every possible environment. As we will show, every type of sensor has both advantages and disadvantages.
2. A BRIEF HISTORY OF CHEMICAL SENSORS

Chemical sensors are relatively new measurement devices. Until about 45 years ago, the glass pH electrode could be considered the only portable chemical sensor sufficiently reliable for measuring a chemical parameter (Schultz and Taylor 1996; Vlasov and Legin 1998). Even that sensor, which has been under continuous development since it invention in 1922 (Table 1.4), needs to be recalibrated on a daily basis and is limited to measurements in solutions or on wet surfaces. Other sensing technologies based on oxidationreduction reactions at electrodes were extensively pursued in the 1940s and 1950s and provided analytical methods for the detection of metallic ions and some organic compounds. The first application of these electrochemical techniques to make a sensor was Table 1.4. Historical landmarks in the development of chemical sensors YEAR 1904 1909 1922 1925 1931 1936 1937 1937 1953 1954 1954 1959 1961 1962 1962 1963 DEVELOPER Kohlraush F. and Nernst W. Haber F. and Klemensiewicz Z. Hughes W.S. Kerridge P.T. Kautsky H. and Hirsch A. Beckman Corp. Kolthoff J.M. Nikolsky B.P. Brattain W. and Bardeen J. Clark L.C. Jr. Stow R.W. and Randall B.F. Baker A. Pungor E. Clark L.C. Jr. and Lyons C. Seiyama T. and Taguchi N. Goto K. and St. Pierre G.R. EVENT Thermal conductivitybased gas sensor Development of glass electrode First glass pH electrode First blood pH electrode First oxygen sensor (nonfiber optic) Commercial production of pH meter Crystalline electrode Crystalline membrane Gas adsorption influence on semiconductor conductance Invention of the oxygen electrode Invention of the pCO2 electrode Catalytic bead gas sensor (pellistor) Heterogeneous solid ion-selective electrode First amperometric biosensor Semiconductor (ZnO) gas sensor Solid electrolyte gas sensor (continued on following page)
Table 1.4. (continued) YEAR 1964 DEVELOPER King W.H. Jr. EVENT
Coated piezoelectric quartz crystals as sensors for water, hydrocarbons, polar molecules, and hydrogen sulfide 1966 Simon W. Liquid ion-selective electrode with neutral carrier 1967 Ross J.W. Ion-exchange membrane 1969 Guilbault G.G. and Montalvo J.G. First potentiometric biosensor 1969 Baker C.T. and Trachtenberg I. Chalcogenide glass membrane for ion-selective electrode 1970 Bergveld P. IS-FET 1970 Taguchi N. SnO2-based gas sensor 1972 Shone C. Piezoelectric biosensor 1974 Hesse H.H. First fiber optic sensor 1974 Chiang C.K. et al. First polymer-based conductometric gas sensor 1975 Lundstrom I. et al. Gas-FET 1975 Lubbers D.W. and Opitz N. Invention of the pCO2/pO2 opt(r)ode 1976 Schoen F.J. ImmunoFET 1976 Matsusite Electric Industrial Co. Commercialization of ceramic humidity sensor 1978 Freeman T.M. and Seitz M.R. First chemiluminescence sensors 1979 Wohltjen H. and Dessey R. Surface acoustic wave (SAW) sensors for gases 1980 Peterson J.I. et al. Fiber optic pH sensor for in vivo blood gases 1982 Schultz J.S. et al. Fiber-opticbased biosensor for glucose 1982 Persaud K.C. and Dodd G. Electronic nose 1984 Hall J.P. et al. Thermoelectric (pyroelectric effect) gas sensor 1984 Peterson J.I. et al. Fiber optic oxygen in vivo sensor 1985 Mc Aleer J.F. et al. Thermoelectric (Seebeck effect) gas sensor 1986 Thorn EMI Microsensor First commercial production of IS-FETs 1989 Wenzel S.W. and White R.M. Flexural plate wave (FPW) or Lamb wave sensor 1992 Toko T. et al. Taste sensor 1993 Abraham M.H. et al. Fullerenes application in gas sensors (SAW, QCM) 1995 Klimant I. et al. Microsensors 1995 Vlasov Y. et al. Electronic tongue 1996 Wang L.G. et al. Fullerenes application in electrochemical sensors 1996 Dresselhaus M.S. et al. Carbon nanotubes in sensor applications 1997 Russell S.D. et al. Monolithic integrated chemical sensor 2002 Comini E. et al. 1-D metal oxidebased conductometric gas sensor 2008 Javey A. et al. First integrated nanowire sensor circuit Source: Data from Schultz and Taylor 1996; Vlasov et al. 2005; http://en.wikipedia.org; etc. for the measurement of oxygen content in tissues and physiological fluids (Clark 1956). Ion-selective electrodes have provided new measurement capabilities, but they face the same limitations as the pH electrode (and are less selective). The key concept for the adaptation of those electroanalytical techniques was Clarks idea of encapsulating the electrodes and supporting chemical components by a semipermeable membrane. The membrane allows the analyte to diffuse freely within the sensor without the loss
of critical components. The concept of interposing membrane layers between the solution and the electrode also provided the basis for the first biosensor, invented by Clark and Lyons (1962). The first resistive gas sensor using an oxide semiconductor was reported in 1962 by Seiyama et al. and Taguchi. As is well known, the oxygen sensor which uses a stabilized zirconia electrolyte has been most important for the control of automobile emissions. Probably the first attempt to apply an electrochemical cell with a solid electrolyte to the gas phase was made in 1963 by Goto and St. Pierre. A thinfilm conductometric sensor was first introduced in the early 1970s. Perhaps the most important promise of these thin-film sensors for the development of viable chemical microsystems is their compatibility with processes for fabricating standard integrated circuits. The early 1970s also saw the development of the ion-selective field-effect transistor (ISFET). An ISFET is simply a metaloxidesemiconductor fieldeffect transwistor (MOSFET) without a gate. The oxide layer of the FET is replaced by an insulating, chemically sensitive membrane. Charges from sensitive chemicals accumulate on top of this insulating membrane and are amplified through the operation of the FET. Modifications and hybrids of the ChemFET and the ISFET (such as the surface-accessible FET, or SAFET, and the suspended-gate FET, or SGFET) were also introduced into research in the 1970s. Humidity sensors have also been used popularly for various aspects of domestic life ranging from air conditioning to the protection of electronic instruments from condensation. Unlike classic hydrometers, the history of such humidity sensors is rather short. In 1976, Matsusita Electric Industrial Co. commercialized electronic ovens equipped with ceramic humidity sensors for automated cooking. Notable among recent achievements in the field of chemical sensors are the contributions of Persaud and Dodd (1992), Toko et al. (1992), and Vlasov et al. (1995), which resulted in the creation of the electronic nose, the taste sensor, and the electronic tongue (Vlasov et al. 2005). Sensor technology has been further advanced by new discoveries in one-dimensional materials, conductive polymers, nanocomposites, and many other sensing materials. We hope that these advances will result in the commercialization of a variety of chemical sensors in coming years.
3. MOTIVATIONS FOR DESIGN OF CHEMICAL SENSORS

Many industries have a need to use and analyze process gases (see Table 1.5). The breadth of such uses can be illustrated by listing the key market sectors that either produce, use, or analyze process gases, namely (Cleaver 2001): Chemical and petrochemical Environmental, including both ambient air and stack emissions monitoring Scientific and engineering research organizations, including universities and national laboratories Medical institutions, including hospitals Food and drinks processing, which use gases such as nitrogen to enhance the shelf life of products by reducing oxidation and use carbon dioxide to carbonate soft drinks and alcoholic beverages Microelectronics, including semiconductor manufacturing and telecommunications Agriculture
Table 1.5. Current and potential applications for chemical sensors and biosensors
MARKET Medical/clinical APPLICATIONS Diagnostics; point-of-care patient monitoring; drug monitoring; artificial organs and prostheses; new drug discovery Process monitoring and control; quality control; workplace monitoring; waste stream monitoring; leakage alarms Detection/monitoring of pollutants, toxic chemicals, waste water, and waste streams Intelligent refrigerator or oven; fire alarm; natural gas heating; air quality control Detection of bad breath; blood alcohol City traffic control and management; air quality monitoring in tunnels or underground parking garages Plant/animal diagnostics; soil and water testing; meat/poultry inspection; waste/sewage monitoring Detection of chemical, biological, and toxin warfare agents; treaty verification Robotic controls; hybrid silicone/ organic computing components COMPETITIVE ADVANTAGES (A) Real-time analysis, immediate/ continuous monitoring, high specificity and selectivity (B) Diverse applications, taste, smell, and other sensory capabilities, combined detection and alarm capabilities, ease of use (C) Portability, cost effectiveness, designed to be smart sensors, low energy demands and low heat generation, analog/digital computing capabilities
Processing/industrial
Environmental
Household application
Lifestyle Traffic
Agriculture/veterinary
Defense/military Robotics/computers
Source: Data from Taylor 1996.
Fabrication industries, including the motor, ship, and aircraft industries Power generation, particularly the nuclear industry, which uses, for example, advanced gas reactors.
Chemical sensors may be used to detect toxic gases in monitoring and alarm systems (such as the detection of harmful gases in the workplace), or to characterize the aroma of a food as part of a quality control process. As chemical sensor technology advances in the next decade, such sensors will become routine on chemical and food processing lines, and more sophisticated sensors will be incorporated into automated process monitoring and control systems. One can estimate how many gases it is necessary to control from the list of hazardous gases typically monitored in semiconductor facilities (see Table 1.6). The results presented in Table 1.7 indicate how important it is to control the presence of toxic gases in the atmosphere. Even at very low concentration, toxic gases are already very dangerous to human
Table 1.6. Hazardous gases typically monitored in the semiconductor industry HAZARDOUS GAS Ammonia Arsine Boron dichloride Boron trifluoride Carbon monoxide Chlorine Chlorine trifluoride Diborane Dichlorosilane Germane Hydrogen Hydrogen bromide Hydrogen chloride Hydrogen fluoride Hydrogen sulfide Hydrogen selenide Phosgene Phospine Silane
a
FORMULA NH3 AsH3 BCl3 BF3 CO Cl2 ClF3 B2H6 SiH2Cl2 GeH4 H2 NBr HCl HF H2S H2Se COCl2 PH3 SiH4
PEL (ppm)a 35 0.05 5 1.5 35 0.5 0.1 0.1 5 0.2 500 3 5 3 10 0.05 0.1 0.3 5
PEL, permissible exposure limitconcentration deemed safe for 8-h time-weighted average. Source: Data from White 2000.
Table 1.7. Long- and short-term exposure limits of some typical toxic gases GAS H2S CO NOX SO2 PH3 CH3OH Cl2 NH3 HCl LONG-TERM EXPOSURE LIMIT, 8 H (ppm) 10 50 3 2 200 0.5 25 SHORT-TERM EXPOSURE LIMIT, 10 MIN (ppm) 15 300 5 5 0.3 250 1 35 5
Source: Data from www.inspectapedia.com.
health. That means that the portability and real-time output of chemical sensors and biosensors will be key advantages to their success in environmental applications. In agriculture, chemical sensors can be used for animal and plant disease diagnostics, detection of contaminants such as pesticides, drugs, and pathogens in milk, meat, and other foods, and in the determination of product quality, such as the ripeness and flavors of fruits and vegetables in the field (Taylor 1996). Pharmaceutics is other important field for chemical sensor applications. Drug discovery is critical in the development and commercialization of new pharmaceuticals, providing the basis for new drugs and new therapies. Emerging requirements for sensors in the medical and health care sector are being driven by the movement toward the continuous (and ideally non- to minimally invasive) monitoring of patients (see Tables 1.8 and 1.9). Under these conditions, feedback on the state of the patient and the results of therapy can be obtained without the delays associated with conventional intermittent measurement and the use of central laboratories for chemical and biochemical analysis (Moskalenko et al. 1996; Kharitonov and Barnes 2000; Cao and Duan 2006). The primary market needs can be categorized as economic, regulatory, and unique government requirements. Economic motivations for improved sensor materials and chemical sensing technology include reducing the cost of product manufacture, increasing a products functionality at low additional cost, and improving the quality of the product. These motivations also improve product competitiveness. For example, the quality, safety, and comfort of automobiles have been greatly enhanced by the many sensors incorporated into modern vehicles. An equally important economic driver is the development and incorporation of sensors into products that aid in extending the useful lifetimes of vehicles. Table 1.8. Principal clinical conditions for which in vivo chemical sensors are considered to be helpful CLINICAL CONDITION Diabetes mellitus Vital function monitoring in intensive care/anaesthetics/prolonged surgery Inflammation and oxidative stress Asthma Cystic fibrosis Pulmonary allograft dysfuction Lung cancer Chronic bronchitis/chest medicine Bronchial epithelial infection Respiratory monitoring Renal failure/monitoring, dialysis ANALYTE AND BREATH MARKERS Glucose, ketones, K+, insulin, lactate, pH, vapor of acetone pH, K+, electrolytes (unclassified), gases (NOx, O2, halothane, CO2, etc.), Na+ glucose, hemoglobin, osmolality, lactate NO, CO NO, CO, H2O2, isoprostanes, nitrite/nitrate NO O2, CO2, pH NO2 CO2/O2 ratio Urea, creatinine, K+, atrial natriuretic peptide, pH
Source: Data from Marczin et al. 2005; Cao and Duan 2006; etc.
Table 1.9. Traces of gases in human breath: physiological ranges GAS Ethane, pentane Isoprene Methanol CO CO (smoker) NO PHYSIOLOGICAL RANGE IN HUMAN BREATH 111 ppb 121,000 ppb 1602,000 ppb 0.42.0 ppm 120 ppm 19 ppb (lower respiratory tract) 2001,000 ppb (upper respiratory tract) 1,00030,000 ppb (nasal level) 131,000 ppb 420 ppm 2,5003,000 ppm 1302,400 ppb
Ethanol Methane CO2 Ammonia/urea
Source: Data from Moskalenko et al. 1996; Smith et al. 1999; etc. Examples include sensors to monitor the integrity of motor oil in an engine, allowing a user to change the engine oil only when it is necessary due to lubricant degradation. Other vehicle sensors might be used in lieu of more expensive externally applied inspection procedures. Chemical sensors have been essential in satisfying a profusion of government-mandated regulatory requirements, including such applications as measuring chemical effluent from factories and exhaust gases from automobiles (see Table 1.10). Water quality is also one of the objectives for control (see Table 1.11). In sum, chemical sensors have significant economic impacts and effects on the quality of life. Government agencies have many singular needs for chemical sensors across a wide range of applications. The military has been on the leading edge of applying sensor technologies to improve its Table 1.10. Air pollutants: prescribed substances Oxides of sulfur and other sulfur compounds (SO2, etc.) Oxides of nitrogen and other nitrogen compounds (NO, NO2, peroxyacetyl nitrate, NH3, etc.) Oxides of carbon (CO, CO2) Oxidizing agents (O3, Cl2, etc.) Organic compounds and partial oxidation compounds (rubber and plastics, organic solvents, chlorinated hydrocarbons and fluorocarbons, volatile organic compounds, CH4, etc.) Metals, metalloids, and their compounds (metal carbonyls, Hg, Cd, Cr, Zn, Cu, organometallic compounds, alkali metals and their oxides, and alkaline earth metals and their oxides Asbestos (suspended particulate matter and fibers), glass fibers and mineral fibers Halogens and their compounds (As, etc.) Phosphorus and its compounds (P, P2O5, etc.) Particulate matter
Table 1.11. Prescribed substances under the EC drinking water directive PARAMETER Hydrogen ion Sulfate (SO4) Magnesium (Mg) Sodium (Na) Potassium (K) Dry residues Nitrate (NO3) Nitrite (NO2) Ammonium (ammonium and ammonia ions (NH4) Kjeldahl nitrogen (N) Oxidizability (permanganate value) (O2) Dissolved or emulsified hydrocarbons Phenols (C6H5OH) Surfactants (as lauryl sulfate) Aluminum (Al) Iron (Fe) Manganese (Mn) Copper (Cu) Zinc (Zn) Phosphorus (P) Fluoride (F) Silver (Ag) UNITS pH value mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 g/1 g/1 g/1 g/1 g/1 g/1 g/1 g/1 g/1 g/1 g/1 MAXIMUM CONCENTRATION OR VALUE 5.59.5 250 50 150 12 1500 50 0.1 0.5 1 5 10 0.5 200 200 200 50 3000 5000 2200 1500 10
Source: Data from Gangolli 1999; Ho et al. 2005.
operational capability. Sensors have been used to develop necessary information about the target, and once the weapons are launched, they are guided to the target in real time by other types of on-board sensors. A great demand for new sensors stems from the National Aeronautics and Space Administrations Earth Orbiting Satellite program, which attempts to monitor changes in the chemical composition and temperature of the earths atmosphere. In this case, new materials and new sensor technologies will be required to provide sensors that possess the needed sensitivity in the important spectral regions. Reductions in the size of military forces and the resulting closings of military bases have led to a demand for sensors capable of monitoring the clean-up and disposal of numerous toxic organic compounds, chemical warfare agents, and obsolete munitions. Sensors will also be required for online control in the manufacture of low-volume specialty components or ultra-high-performance military aircraft. Without sensor-based control for these specialized needs, the unit costs of production will very likely be prohibitive. The required sensitivity of chemical sensors is indicated in the results presented in Table 1.12. Interestingly, the detection threshold of different flavor compounds in water varies considerably, with a grapefruit compound having an astonishingly low threshold value of 2 parts in 1014. That means
Table 1.12. Detection thresholds of human nose for some typical odorants in air COMPOUND Ether Limonene Benzaldehyde Butyric acid Citral Musk xylene ODOR TYPE Ether Lemon Bitter almond Rancid butter Lemon Musky THRESHOLD 5.8 mg/ml 0.1 mg/ml 3.0 g/ml 9.0 g/ml 3.0 ng/ml 0.8 pg/ml
Source: Data from Gardner and Dartlett 1999. that chemical sensors must be extremely sensitive in order to recognize odors as well as the human sensory system does.
4. WHAT DETERMINES SUCCESS IN CHEMICAL SENSOR DESIGN?

Despite the large number of chemical sensors already on the market, selection and design of a suitable sensor for a new application is a difficult task for the design engineer. Careful selection of the sensing material, the surface platform, and the sampling system is very important because those decisions can determine the specificity, sensitivity, response time, and stability of the final device. Selective functionalization of the sensor is also critical to achieving the required operating parameters. Therefore, in designing a chemical sensor, developers have to answer the following questions: (1) Does the application require high sensitivity or a broader range of detection? (2) Can the applications needs be met by careful choice of the operating parameters of the sensors, or will a combination of technologies be needed to sort out the contributions of various similar analytes? (3) Does the applications operating environment require special materials or fabrication procedures? Designing a new sensor requires good understanding of the functioning of various chemical sensors, their design, features of exploitation, and modern trends in their development. Multidisciplinary knowledge and very careful multidisciplinary approaches are also needed to achieve good results (see Figure 1.4). Among the sciences needed for the design of chemical sensors, knowledge of materials science is necessary for elaboration of effective technologies. It is required for fabricating appropriate coatings and membranes, synthesis or deposition of sensitive materials, as well as for conducting surface functionalization and materials modification. In addition, chemical sciences such as interfacial and interphase chemistry, electrochemistry, molecular chemistry, analytical chemistry, and so on, are necessary for precise understanding of the processes which are the basis on which sensors function. Without knowledge of the biological sciences, including microbiology and molecular biology, protein chemistry, immunology/ enzymology, bioprocessing, etc., it is impossible to understand the main principles of biosensor function and design. The physical sciences provide spectroscopic detection methods (optical, mass, etc.), as well as knowledge necessary for understanding the mechanisms of interaction at gassolid or liquidsolid interfaces which determine the sensors signal.
Biological Sciences Chemical Sciences Physical Sciences
Sensing Mechanism
Material Sciences
Production Engineering
Sensor Device
Electrical Engineering
Signal Processing Engineering
Design Engineering
Figure 1.4. Scheme illustrating the correlation of different sciences in chemical sensor design.
There is also no doubt that the role of engineers in this process is as important as the role of scientists. Certainly, during the initial stages of research, interest is generally focused on exploring and proving the principles by which a new technology can be applied to measure a chemical substance. However, at the following stages of elaboration the impact of engineers is significantly increased, especially when they are close to completing a design (Figure 1.5). Sometimes, design of a device that will be suitable for commercial marketing requires resolving a number of complex engineering problems that do not necessarily rely on elaboration of basic principles. Modern progress in the field of chemical sensors in many aspects has been determined by the successes of engineers working in such areas as microfabrication, microfluidics, and signal processing.
Sensing Mechanism Sensor Devices Smart Sensors Sensor Systems Measurement and Control Systems
Figure 1.5. From idea to devicesfrom science to engineering.
Designing versatile chemical sensors suitable for measurements in any environment and under any conditions is an even harder task. The environment determines appropriate materials and the transducing principle that can be utilized in a sensor. Thus the very first step in sensor design is to determine the required working conditions, measurement range, response time, resolution of measurements, lifetime, etc. Expected temperature changes, possible chemical interferences, and electromagnetic interactions should also be considered, as well as the size of the sensor, its weight, cost, safety of operation, and reliability. In addition, commercialization of designed sensors actually influences the process of their elaboration. Every step of development must pass a difficult set of criteria and questions. These questions are aimed at measuring present and future technical and market performance for the sensor and include (Taylor 1996): 1. 2. 3. 4. 5. 6. 7. 8. 9. How specific is the sensor? Can it match competing, nonsensor assays? How sensitive is it? Can it meet the needs of the market? How reliable and accurate is it? Can it be manufactured with high reproducibility? How stable is it? What is its shelf life? What restrictions must be placed on storage (e.g., refrigeration, desiccation, etc.)? How much will it cost? Who owns it? Is the technology protected? What is (are) its target market(s)?
It seems that there are many ready solutions for given problems, and therefore the careful study of results of previous research may reveal shortages that should still be solved in the future.
5. MATERIALS FOR CHEMICAL SENSORS

Research on fundamentals as reported in Volumes 13 of this series has shown that practically all known categories of materials could be used for chemical sensor elaboration. Some could be used as sensitive elements; others could be used as construction materials, or in membranes and filters. Some could be used to create contacts, and some (as additives) to promote optimization of working characteristics. At present, however, the materials that are most commonly used as sensing materials are metal oxides and polymers, which can be referred to as traditional or conventional sensing materials.
5.1. METAL OXIDES

Metal oxides are the class of materials which have seen the widest application in chemical sensors (Park and Akbar 2003; Korotcenkov 2007). As can be seen in Table 1.13 and was shown in Volume 1 of this series, they can be used in every type of chemical sensor. For example, in conductometric sensors,
Table 1.13. Metal oxides preferred for applications in various types of chemical sensors
SENSOR TYPE AND (SENSOR ELEMENTS) Chemiresistor (semiconductor) DETECTED GAS Reducing gases (CO, H2, CH4) Oxidizing gases (O3, NOx, Cl2) H2S, SO2 NH3 CO2 Alcohol Oxygen Humidity Oxygen H2 METAL OXIDES PREFERRED FOR APPLICATION SnO2; CTO; Ga2O3; In2O3 In2O3; WO3; ZnO; TiO2 SnO2/CuO; SnO2/Ag2O WO3; MoO3; In2O3 SnO2/La2O3; Al2O3/V2O5 La2O3/In2O3; La2O3/SnO2; In2O3/Fe2O3 Ga2O3, SrTiO3, SrTiFeO3; TiO2; Nb2O5; ZnO In2O3/SiO2; TiO2/MgCr2O4; SrTiO3; LaFeO3 ZrO2:Y; Bi2O3/MoO3 Sb2O5; BaCeO3; ZrO2:Y
Electrochemical (amperometric)
Surface acoustic wave Humidity; NO2; H2; ethanol; O3 ZnO; InOx; LiNbO3; SiO2; WO3 Quartz crystal balance Hg vapor; NH3, NOx, SOx, H2S SiO2 Work function (RT) Capacitance CH4, CO, Cl2 H2; NH3; C2H5OH Humidity CO2 NOx Pelistor Pyroelectric Heterostructural Schottky diode Optochemical (fiber optic) Surface plasmon resonance Cataluminescence Combustible gases and vapors H2; CH4 CO H2S H2 H2, CO, alcohol NO2; H2S; NH3 Organic vapors Ethanol NiO; Fe2O3; Co3O4 (Pd, Pt, Ir)/SiO2 Al2O3 CuO/BaTiO3; CeO2/BaCO2/CuO; Co3O4/BaTiO3; NiO/BaTiO3 CoO/In2O3; NiO/ZnO Al2O3; SiO2 ZnO; LiTaO3; LiTiO3 ZnO/Zn2SnO4; SnO2/TiO2; SnO2/Zn2SnO4 ZnO/CuO; SnO2/CuO/SnO2 ZnO; TiO2 WO3; Mn2O3; Co3O4; NiO; CuO Ta2O5; SiOxNy; TiO2 MgO; TiO2; Y2O3; LaCoO3:Sr ZnO
semiconducting metal oxides are typically used as gas-sensing materials that change their electrical resistance upon exposure to oxidizing or reducing gases. Specific properties of the metal oxides, such as the wide variety of materials with different electrophysical, optical, and chemical characteristics, their high thermal and temporal stability, and their ability to function in harsh environments, make metal oxides very suitable materials for use in chemical sensors. Further, their role in chemical sensors is not limited to being used just as sensing materials. They
Table 1.14. Functions of metal oxides in chemical sensors FUNCTION Sensing layer Substrate TYPE OF SENSOR Conductometric, SAW, QCM, optical, calorimetric Conductometric SAW, QCM Electrochemical EXAMPLES SnO2, In2O3, WO3, TiO2, ZrO2, etc.
Al2O3, SiO2, BeO; LiNbO3; ZrO2:Y ZnO Electrode In2O3, ZnO, NiO/Ni; PdO/Pd; Al2O3/Pt; MgAl2O3/Pt; Au/Ga2O3 Membrane, filter Electrochemical, gas sensors Al2O3, SiO2, zeolites Fiber Fiber optic SiO2, GeO2Sb2O3 Promoter Conductometric, SAW, QCM, PdO; RhO; Ag2O; CuO; Fe2O3; P2O5; Co3O4; optical, calorimetric NiO; MnO Structure modifier Conductometric, calorimetric Al2O3; SiO2; CaO; MgO; BaO; Y2O3; La2O3; (stabilizer) Ta2O5; CeO2 QCM, quartz crystal microbalance; SAW, surface acoustic wave. are also being used successfully as substrates, electrodes, promoters, and structure modifiers, and as membranes and filters (Table 1.14). On the other hand, low selectivity is the main shortcoming of sensors based on metal oxides.
5.2. POLYMERS
Polymers constitute another class of materials which are also very promising for application in chemical sensors (Skotheim et al. 1998; Dai et al. 2002; Thomas et al. 2006; Rahman et al. 2008). These materials, discussed in detail in Volume 3 of this series, are inexpensive to manufacture and can be prepared as films, which is very important for device application. Moreover, conducting polymers can be deposited over defined areas of electrodes. In general, polymers could be used in all types of sensors (chemiresistors, work function, optical, mass-sensitive, electrochemical, CHEMFETs, capacitance) as long as they can function at room termperature. The great advantage of conducting polymerbased sensors over other available technologies is that the conducting polymers have the potential for improved response properties and are sensitive to small perturbations. Earlier inert polymers were used only to provide mechanical strength to membranes; however, conducting polymers improve the sensitivity of the sensors due to their electrical conductivity or charge-transport properties. Conducting polymers are also known for their ability to be compatible with biological molecules in neutral aqueous solutions (Chaubey and Malhotra 2002). Moreover, the polymer itself can be modified to bind biomolecules to a biosensor (Mulchandani and Wang 1996). A large number of chemical sensors use polymers because they offer great design flexibility (McQuade et al. 2000; Gerard et al. 2002). The flexibility of polymers properties, however, is attained at the expense of doping and the introduction of functional additives. The primary dopants (anions)
introduced during chemical or electrochemical polymerization maintain charge neutrality and generally increase the electrical conductivity. Doping generates charge carriers in the polymer chain through chemical modification of the polymer structure and involves charge exchange between the polymer and the dopant species. Since every repeat unit is a potential redox site, conjugated polymers can be doped n-type (reduced) or p-type (oxidized) to a relatively high density of charge carriers (Persaud 2005). The neutral chain can be partially oxidized or reduced, i.e., doped, by inducing an excess or deficiency of electrons into the polymer lattice. This effect can be reversed by de-doping through the removal or chemical compensation of charge carriers. The nature of the anion also strongly influences the morphology of the polymer (Pron and Rannou 2002). In addition, anions can serve as specific binding sites for interaction of the conducting polymer with the analyte gas (Cabala et al. 1997). Conducting polymers can be used as the selective layer in a sensor or as the transducer itself. Polymers can form selective layers in which the interaction between the analyte and the sensing matrix generates a primary change in a physical parameter in the transduction mechanism. They are relatively open materials that allow ingress of gases into their interior. Thus, for example, a change of conductance of a conducting polymer upon exposure to a gas is the sensing mechanism in a chemiresistor. Common classes of organic conducting polymers acceptable for conductometric gas sensor application include poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, polynaphthalenes, poly(p-phenylene sulfide), poly (para-phenylene vinylene)s, etc. (Nalwa 1997). Polymers can also form different membranes, providing selectivity of chemical reactions in electrochemical sensors. On the other hand, their performance in devices that form circuit elements such as transistors has been less than ideal (Dimitrakopoulos and Malenfant 2002; Dimitrakopoulos and Mascaro 2001). Janata and Josowicz (2003) noted that the abundant literature dealing with various applications of polymers can be divided into two groups: polymers in electronic, optoelectronic and electromechanical devices (Angelopoulos 2001) on the one hand, and polymers in chemical sensors based on electronic, optical, or mechanical mechanism (Osada and De Rossi 2000). Acceptable operation of the first group relies on their chemical stability in the ambient environment, whereas the sensor applications take advantage of the physical changes that take place in the polymers when they are exposed to different chemicals. This property has its origin in the molecular and macroscopic structure of polymers. Thus the tunability is an important bonus of polymers that aids the preparation of a variety of sensing layers, but it can be troublesome where performance independent of ambient factors is desired. Because they can be readily incorporated into microfabricated structures, conducting polymers are inherently compatible with solid-state integrated chemical sensors. Consequently, they have considerable potential for fabrication of multisensing arrays, an aspect that makes sensors based on conducting polymers particularly suitable for commercialization (Janata and Huber 1985). According to Persaud (2005), polymer-based sensors have the following advantages: 1. The sensors have rapid adsorption and desorption kinetics at room temperature. 2. The sensor elements feature low power consumption (of the order of microwatts), because no heater element is required. 3. The polymer structure can be correlated to specificity toward particular classes of chemical compounds.
4. The sensors are resilient to poisoning by compounds that would normally inactivate some inorganic semiconductor-type sensors. It is apparent that polymers display promising analytical results. However, there are still concerns that many of them are unable to achieve the desired selectivity and sensitivity in real samples. Some polymers undergo degradation or an irreversible swelling process when exposed to certain environments, while others adsorb and respond to water vapor (Pejcic et al. 2007).
5.3. NEW TRENDS IN SENSING MATERIALS

As we mentioned earlier, there are no ideal sensors which meet all requirements. Nor are there any ideal sensor materials. That is why research is continually being conducted to search for new sensing materials having new properties which might be used in elaboration of chemical sensors with new and unusual functional characteristics. Detailed fundamental information about these materials is provided in Volume 2 of this series.
5.3.1. Fullerenes: Present and Future

Fullerenes are closed-cage carbon molecules containing pentagonal and hexagonal rings arranged in such a way that they have the formula C20+m, with m being an integer number (Dresselhaus et al. 1996; Mauter and Elimelech 2008) (see Figure 1.6). They are the third allotropic form of carbon, the others being graphite and diamond. Fullerenes comprise a wide range of isomers and homologous series, from the most studied C60 or C70 to the so-called higher fullerenes, C240, C540, and C720. The first of these compounds were discovered in 1985 through spectrometric measurements on interstellar dust, and their structure was confirmed later in the laboratory (Kroto et al. 1985). Kroto, Smalley, and Curl received the Nobel Prize in 1996 for their work.
Figure 1.6. Schematic view of fullerenes. (Reprinted from http://commons.wikipedia.org.)
Physicists, chemists, and material scientists or engineers, among others, have found unusual potential in these new spherical carbon structures for use as superconductor materials, sources of new compounds, self-assembling nanostructures, and several optical devices (Dresselhaus et al. 1996). This initial attention led to an increasing number of investigations that showed the special properties of fullerenes, some of which might lead to practical applications (Mauter and Elimelech 2008). Although a wide range of uses has been explored and several applications developed, fullerenes are not so far fulfilling their initial spectacular promise (Baena et al. 2002). Research on the application of fullerenes has proved to be slower than expected, but it must not be considered unsuccessful when one considers the great advances in the knowledge of the physical and chemical characteristics of fullerenes. Thanks to the additional information obtained during recent years, they have been found to be really useful in several fields, especially in solid-state applications. According to Baena et al. (2002), in analytical chemistry, fullerenes can be approached from two different points of view. The first sees fullerenes as analytes, which involves their determination in various samples such as biological tissues. The second sees fullerenes as analytical tools, including their use as chromatographic stationary phases, as electrochemical sensors based on their activity as electron mediators, and in the exploitation of their unique superficial characteristics as sorbent materials in continuous-flow systems. Initially, to establish the analytical features of fullerenes as sensors, adsorption studies were carried out on organic molecules bound onto fullerenes. For this purpose, the adsorption of gases and organic vapors was studied with fullerene-coated devices sensitive enough to detect changes in mass or pressure related to the adsorption of gas molecules to the fullerene layersuch as surface acoustic wave (SAW) sensors or quartz microbalances (QMBs). Through these first investigations, the retention of certain monomeric gas molecules was demonstrated, and consideration was given to the possible use of C60 films as analytical sensors for volatile polar gases such as NH3 (Synowczyk and Heinze 1993). Gas adsorption onto the fullerene film reduces the film resistance, resulting in a charge transfer to the electronic system. Sensitivity levels of a few milligrams per liter of NH3 in air were achieved, but there were still some problems, such as the lack of selectivity versus other gas vapors (which were also adsorbed, leading to the same electrical signal), response times of the order of seconds, the influence of humidity level on the calibration, or instability of the sensor when exposed to air several times. Nevertheless, the use of fullerenes as modifiers was found to be a promising research topic in several fields, especially as coatings in QMBs and SAW sensores, since it is well known that the presence of fullerene improves the electrochemical characteristics of the film or membrane by reducing the resistivity. In recent decades, various reusable and sensitive piezoelectric (PZ) quartz-crystal membrane sensors have been developed to detect organic/inorganic vapors and organic/inorganic biological species in solutions. Fullerene C60, and fullerene derivatives, among others, were synthesized and applied as coating materials on quartz crystals of PZ crystal sensors (Chao and Shin 1998). Thus, chemisorption on C60 fullerene was observed for amines, diamines, dithiols, dienes, and alkynes, and only physical adsorption was found for carboxylic acids, aldehydes, alcohols, ketones, alkenes, and alkanes. This seems to imply that the nucleophilic addition to fullerene by polar electron-donor groups, as in amines and thiols, is easier than electrophilic addition. Furthermore, diamines and dithiols showed greater interactions than those for the monodentate form, behavior attributed to the formation of stable cyclic compounds between fullerene and the bidentate ligand.
In independent studies, fullerene has been widely used as an electron mediator in electrodes, since the incorporation of C60 significantly reduces the electrical resistance of the coating membrane. By way of example, an iodide-sensitive sensor was reported (Wang et al. 1996) in which the bilayer lipid membrane supported on a copper wirewhich acted as a modified electrodealso contained C60 fullerene. The resulting electrode was further used in a three-electrode system for the determination of iodide in solution, obtaining a detection limit of 10 nM. Recently, the optical properties of C60 have also been applied to the development of a sensitive oxygen-sensing system based on the quenching of the photo-excited triplet state of the fullerene molecules (Bouchtalla et al. 2002; Nagl et al. 2007). Although the amperometric oxygen electrode has been the most popular sensing system for this element, the instability of the electrode surface itself, and in the oxygen diffusion barrier, demand a practical alternative. For this, much attention has been given to optical sensing systems based on luminescence quenching of an indicator [organic dye, polyamide hydrazide (PAH)transition metal complex]. The C60 fullerene can also be used as indicator, because it can easily form thermally stable films with polymers, such as polystyrene, and possesses useful electronic and photochemical properties, such as a fairly long lifetime for the photo-excited triplet state (100 s). This lifetime is effectively quenched by oxygen, and decreases with increasing oxygen concentration. By using time-resolved spectroscopy with laser-flash photolysis, a highly sensitive oxygen sensor is obtained. Probably the unavailability and high cost of fullerenes have deterred their use in analytical chemistry. Now, many firms supply fullerenes at reasonable prices. Therefore, it is optimistically forecase (Baena et al. 2002) that the advantages of fullerenes as sorbent materials, chromatographic stationary phases, and active microzones in sensors, based on their unique characteristics, will be consolidated and extended in the near future. One of the foreseeable trends is the use of synthetic fullerene derivatives that exhibit better properties than the original fullerenes. The introduction of radicals into the fullerene spheres can lead to an increase in the reversible sorption of organic molecules, as well as to direct retention and elution of metal traces by covalent binding of typical ligands such as EDTA and DDC. The unusual electrical properties of fullerenes can be fully exploited by progressively substituting the conventional carbon forms in building macro- and microelectrodes.
5.3.2. Carbon NanotubesA New Material for Chemical Sensors

Carbon nanotubes (CNTs), which have high mechanical and chemical stability, were first fabricated in 1991. There are two types of CNT morphology (Saito et al. 1998; Dresselhaus et al. 1996; Varghese et al. 2001; Terrones et al. 2004). On the one hand, single-walled nanotubes (SWCNTs) consist of a honeycomb network of carbon atoms and can be visualized as a cylinder rolled from a graphitic sheet. On the other hand, multiwalled nanotubes (MWCNTs) are a coaxial assembly of graphitic cylinders generally separated by a plane space of graphite (Dresselhaus et al. 1996) (see Figure 1.7). CNTs seem to be ideal for adsorption and detection of gases due to their hollow center, nanometer size, and large surface area. Gas adsorption on CNTs is today the focus of intense experimental and theoretical studies. Synthesis methods for SWCNTs and MWCNTs include arc discharge, laser ablation, pyrolysis, chemical vapor deposition (CVD), and gas-phase catalytic growth (Terrones et al. 2004). However, these methods do not produce a monodisperse product with controlled physical and chemical properties.
Figure 1.7. Schematic diagrams of (a) a single-wall carbon nanotube (SWNT), (b) a multiwall carbon nanotube (MWNT), (c) a double-wall carbon nanotube (DWNT), and (d) a peapod nanotube consisting of a SWNT lled with fullerenes (e.g., C60). (Reprinted with permission from Dresselhaus et al. 2003. Copyright 2003 Elsevier.)
The electronic structure of SWCNTs can be either metallic or semiconducting, depending on their diameter and chirality (Dresselhaus et al. 1996). Combining metallic and semiconducting nanotube elements with different electronic properties (Varghese et al. 2001) can create MWCNTs. It is supposed (Valentini et al. 2003) that these diverse electronic properties allow the possibility of developing nanoelectronic devices as nanowires, or as metal/semiconductor heterojunctions by combining metallic and semiconducting nanotubes. A possible approach is the modification of different parts of a single nanotube to have different electronic properties using controlled mechanical or chemical processes (e.g., nanotube bending or gas molecule adsorption). Carbon nanotubes have the same developed surface as fullerenes, and therefore their applications lie in the same general area (Mauter and Elimelech 2008). In particular, the results of recent research have shown that CNTs may find successful applications in design of room-temperature sensors, where their peculiar structural features could be realized. It has in fact been established that such sensors can be extremely sensitive. For example, research conducted by Penza et al. (2004) showed that at room temperature, CNT-based SAW sensors were up to 34 orders of magnitude more sensitive than existing organic layercoated SAW sensors. They had a very low limit of detection, and 1 ppm of ethanol or toluene was easily sensed. It was established that the selectivity to volatile organic compounds (VOCs) can be affected by the type of organic solvent used to disperse the carbon nanotubes as sensing materials onto SAW sensors (Penza et al. 2004). The interaction between the CNTs surface and VOCs plays a main role in the sensing mechanism. Mass spectrometry measurements indicated that the interaction between the CNTs and solvents used becomes stronger with solvents that form hydrogen bonds (e.g., ethanol), suggesting a possible role for the chemisorbed oxygen on CNTs as chemical mediators between the CNTs and the dispersing agents. This means that the sensing effects are strongly dependent on the chemical affinity between the analytes to be detected and the solvent used. Also, CNTs form a net supporting adsorbed molecules, producing a sensing structure that is stable at room temperature. CNT-based sensors have shown good electrical response as well (Valentini et al. 2003, 2004). These authors established that NO2 exposure drastically decreases the electrical resistance of CNT-based sensors; NH3, H2O, C6H6, and ethanol exposure increases the electrical resistance; and CO exposure does not
affect the resistance. The threshold of NO2 detection was less than 10 ppb. Further, the sensitivity achieved was pretty good, and also, removing the gas totally restored the initial resistance. Such CNT behavior indicates that charge transfer due to the interaction of carbon nanotubes with adsorbates is an important mechanism in changing conductivity in the CNTs upon adsorption of NO2, water vapor, NH3, C3H6, and ethanol gases. The nanotube sensors exhibited fast response and substantially higher sensitivity than existing solid-state sensors at room temperature. Sensor reversibility was characterized by fast recovery at 165C. The experimental findings revealed that p-type semiconductor behavior is present in analyzed CNTs. The carbon nanotube thin films studied by Valentini et al. (2003, 2004) were prepared by plasmaenhanced chemical vapor deposition. Valentini et al. (2003, 2004) also found that modification of the sensing material by noble metals could be used to improve the parameters of CNT-based sensors. It has been established that bulk doping of CNTs also plays an important role in sensing effects. For example, Terrones et al. (2004) pointed out that theoretical ab initio calculations have demonstrated that CO and H2O molecules do not react with the surface of pure-carbon SWCNTs. If the surface of the tube is doped with a donor or an acceptor, drastic changes in the electronic properties are observed as a result of the binding of the molecules to the doped locationsbecause of the presence of holes (B-doped tubes) or donors (N-doped tubes), the surfaces became more reactive. So, a brief analysis of results obtained indicates that CNTs are really promising materials for sensor applications (Li et al. 2008; Kalcher et al. 2009; Bondavalli et al. 2009). Other interesting results connected with CNT preparation and study have also been reported in the literature (Dresselhaus 1996; Harris 1999; Poulin et al. 2002; Valentini et al. 2003; Cantalini et al. 2003; Penza et al. 2004; Mauter and Elimelech 2008).
5.3.3. Metal Oxide One-Dimensional Nanomaterials

As research on carbon fullerenes and nanotubes has shown, the dimensionality is a very important factor in determining the properties of nanomaterials. Therefore, control of the size and shape of metal oxide crystallites is of great interest with regard to applications of such materials in chemical sensors. Results obtained during study of one-dimensional metal oxide nanomaterials have great importance due to their potential for fundamental studies as well as for application in low-cost, small-sized, and low-powerconsumption devices. One-dimensional metal oxide nanomaterials have excellent crystallinity and clear facets. It is expected that these nanomaterials will have less concentration of point defects and specific adsorption and catalytic properties, conditioned by a particular combination of crystallographic planes. In addition, one-dimensional metal oxide nanomaterials should be more thermodynamically stable in comparison to nanograins, promoting stable operation of chemical sensors at higher temperatures. Development of nanotechnology gives hope for realizing chemical sensors based on one-dimensional metal oxide nanowires, which optimizes their parameters even more in comparison with devices based on polycrystalline materials. To date, various kinds of one-dimensional nanomaterials, such as Si, Ge, silica, MgO, CaO, GaN, SiC, In2O3, TiO2, Fe2O3, ZnO, etc., have been synthesized as nanowires, nanotubes, nanospheres, nanorods, and nanobelts (Guha et al. 2004; Li et al. 2002; Kam et al. 2004) (see Figure 1.8). A number of methods, such as physical evaporation, silica-assisted Fe-catalytic growth, thermal reaction between
Figure 1.8. Morphology of as-made ZnO nanowires. (a)(d) show long (1015 m) and thin (3060 nm) nanowires grown in the higher-temperature region of the furnace. (e)(h) show short (12 m) and thick (60100 nm) nanowires grown in the lower-temperature region of the furnace. The scale bar for (a) is 10 m, for (b), (c), (e), (f), and (g) 1 m, and for (d) and (h) 200 nm. (Reprinted with permission from Banerjee et al. 2004. Copyright 2004 IOP.)
powders and active carbon, alumina-assisted catalytic growth, carbon-assisted synthesis, etc., have been tried for fabricating these materials. However, there is much more research on synthesis of nanoribbons, nanobelts, and nanowires than on attempts to apply these materials in chemical sensors. Therefore, we now know more about regularities of nanowires growth (Kam et al. 2004; Jung et al. 2003; Varghese et al. 2003) than about their electrophysical, surface, catalytic, and sensor characteristics. It is necessary to admit, however, that research in this area has recently become much more intensive (HernandezRamrez et al. 2007; Liu 2008; Comini et al. 2009). Therefore, one may hope that practical application of one-dimensional metal oxide nanomaterials in chemical sensors may not be very long in coming. The basis of this optimism is the progress achieved in the synthesis of one-dimensional metal oxide
nanomaterials, which now allows synthesis of high-quality nanomaterials with the length of individual nanowires equaling up to 10500 m (Li et al. 2002; Zhang et al. 2004).
5.3.4. Nanocomposites
Development of nanocomposites is another promising direction in the design of materials for chemical sensors. Nanocomposite materials have recently attracted increased interest because of the possibilities of synthesizing materials with unique physical-chemical properties (Gaskov et al. 2001; Zhang et al. 2003). Highly sophisticated surface-related properties, such as optical, electronic, catalytic, mechanical, and chemical properties, can be obtained by advanced nanocomposites, making them attractive for chemical sensor applications. At present, research on elaboration of nanocomposite materials is being carried out in various directions, such as composites based on carbon nanotubes and fullerenes, metal oxide nanocomposites, and organicnonorganic nanocomposites. Materials obtained as a result of this elaboration have their own specific advantages. For example, the addition of CNTs to a polymer matrix leads to a very low electrical percolation threshold and allows one to obtain, with only very small amounts of CNTs, an electrical conductivity sufficient to provide an electrostatic discharge (Flahaut et al. 2000). Transitioning to nanocomposites could improve mechanical properties and promote stabilization of the parameters of the basic material (Konig 1987). For example, in carbonpolymer composites, the presence of carbon nanotubes inside the polymeric matrix can provide mechanical support to the conformational rearrangement of the polymeric chains. Nanocomposites also provide more possibilities for control of the catalytic activity of the sensing matrix. For example, the introduction of TiO2 nanoparticles into the polymer matrix of poly(pphenylenevinylene) (PPV) changes the adsorption properties: Adsorption of oxygen is stronger on the nanocomposite than on PPV (Baraton et al. 1997). A full description of possible methods of fabricating nanocomposites with particular properties is not possible in this brief review. Interested readers may refer to the literature for details. It is necessary to remember that design of nanostructured composites for chemical sensors requires consideration of many factors, e.g., the interface volume, crystallite size, interphase interactions, thickness, surface and interfacial energy, texture, stress and strain, etc., all of which depend significantly on materials selection, deposition methods, and process parameters (Gaskov et al. 2001; Zhang et al. 2003). Some aspects of the use of metal oxide nanocomposites in the elaboration of solid-state gas sensors were considered in detail by Gaskov and Rumyantseva (2001, 2009). For example, Gaskov and Rumyantseva (2001) give the following explanation of the advantages of nanocomposites for gas sensor applications. The nanocomposite materials can be represented as M1O/ M2O, where M1O is the nanocrystalline matrix and M2O is the doping oxide distributed between the surface and the bulk of the M1O nanocrystalline grain. The advantage of nanocomposites over simple nanocrystalline oxides, when used in gas sensors, is associated with the redistribution of M2 between the bulk and the surface of the M1O grains, depending on the redox properties of the gas phase. Low oxidation levels of M2 cation, corresponding to larger ionic radius and predominant distribution of M2 over the surface of the M1O grains, occur in a reducing atmosphere. By contrast, cations in higher oxidation
Table 1.15. M1O/M2O nanocomposites with promise for gas-sensitive materials IONIC RADII r(M2), nm M1O/M2O Cr2O3/SnO2 SnO2/CuO SnO2/MoO3 Ga2O3/Fe2O3 In2O3/NiO In2O3/Fe2O3 WO3/TiO2 r(M1), nm Cr3+ Sn4+ Sn4+ Ga3+ In3+ In3+ W6+ 0.061 0.069 0.069 0.062 0.079 0.079 0.058 OXIDIZED FORM Sn4+ Cu2+ Mo6+ Fe3+ Ni3+ Fe3+ Ti4+ 0.069 0.073 0.042 0.064 0.060 0.064 0.060 REDUCED FORM Sn2+ Cu1+ Mo5+ Fe2+ Ni2+ Fe2+ Ti3+ 0.093 0.096 0.063 0.077 0.070 0.077 0.067
Source: Data from Gaskov and Rumyantseva 2001. states are formed in an oxidizing atmosphere, with increasing probability that M2 cations will occupy regular cationic positions in M1O. The liability of the chemical state of the M2 cation in the nanocrystalline system may result in a dramatic change in the state of grain boundaries and in modification of the electronic properties of the material in the presence of even trace amounts (0.110 ppm) of reducing or oxidizing gas molecules in the gas phase. Table 1.15 lists examples of nanocomposites that are of interest for creating gas-sensitive materials.
5.3.5. Other Materials

There are also other approaches to the elaboration of new sensing materials, based on using ionic liquids (Hardacre et al. 2004), new mesoporous materials (Melde et al. 2008), new wide-band-gap semiconductors (Chaniotakis and Sofikiti 2008), porous semiconductors (Korotcenkov and Cho 2010), and metal nanoparticles (Luo et al. 2006). These materials were discussed in detail in Volumes 2 and 3 of this series. For example, as metal particles are reduced in size, the collective oscillation of electrons in the conduction band causes changes in the electrical, optical, and magnetic properties. Such phenomena in nanomaterials may play an important role in sensor technology. By exploiting these nanoscale properties, a highly efficient chemical sensor can be designed and fabricated (Riu et al. 2006). Nanoparticles, nanoclusters, and nanoarrays of nanoparticles have been used in VOC sensors (Ahn et al. 2004). The main problem with metal nanoparticles is related to their low stability. However, metallic nanoparticles can be stabilized in an organic medium using surface functionalization. These materials are known as coreshell nanoparticles. Coreshell metal nanoparticles are being incorporated into various chemiresistor sensor applications, particularly in VOC detection. In all of these sensors, nanocrystalline metals are embedded into a polymer matrix. One of the major driving forces for using polymer matrixes is to make the sensor chemically resistant to corrosive gases and VOCs. The nanoparticles are chemically susceptible to corrosive analytes and can adversely affect any unprotected sensing system. The chemical susceptibility of the nanoparticles and the type of polymer matrix used can cause issues for long-term reliability of the sensor (Drake et al. 2007).
Zeolites are another group of compounds that have generated some interest (Rolison 1990; Walcarius 1999). This is not surprising considering that they comprise a microporous open framework structure which is accessible to certain guest molecules. Further, their surface and structural properties can be easily modified, which makes them ideal candidates for the selective adsorption of various volatile hydrocarbons and small organic molecules (Pejcic et al. 2007). However, zeolites do have a strong tendency to preferentially adsord water relative to analyte, and this appears to be hindering their application in environments with elevated moisture levels. These materials will not be discussed in this chapter, due to their lesser importance in comparison with the materials mentioned above. Zeolites are discussed in detail in Volume 2 of this series.
6. SOME USEFUL DEFINITIONS

In conclusion, in Table 1.16 we provide some definitions which will help the reader to understand better the materials discussed in this volume (White 2000; http://en.wikipedia.org). We would like to note that the development of smart sensors is one of the most promising directions in chemical sensor design. A smart sensor is made with the same technology as integrated circuits. This means that a smart sensor utilizes the transduction properties of one class of sensing materials and the electronic properties of silicon (GaAs). Integrated sensors provide significant advantages in terms of overall size and the ability to use small signals from the transduction element. Potential advantages of the smart sensor concept include: Table 1.16. Denitions used in chemical sensor technologies
Analyte Analytical chemistry Chemometrics A substance or chemical constituent that is determined in an analytical procedure. The study of the chemical composition of natural and artificial materials. The science of extracting information from chemical systems by data-driven means. It is a highly interfacial discipline, using methods frequently employed in core data-analytic disciplines such as multivariate statistics, applied mathematics, and computer science, used to investigate and address problems in chemistry, biochemistry, and chemical engineering. A field of applied mathematics that deals with operations on or analysis of signals, in either discrete or continuous time, to perform useful operations on those signals. The surroundings of a physical system that may interact with the system by exchanging mass, energy, or other properties. Physical and biophysical factors along with their chemical interactions that affect an organism. Processes and activities that characterize and monitor the quality of the environment. (continued on following page)
Signal processing
Environment Environment (biophysical) Environment monitoring
Table 1.16. (continued)

Pollution Contaminants in an environment that cause instability, disorder, harm, or discomfort to the ecosystem, i.e., physical systems or living organisms. Air (water) pollution is the release of chemicals and particulates into the atmosphere (water). Chemicals or substances which are physical hazards or health hazards. The specific gas that is intended to be monitored. Gas with toxic properties that shuts down the central nervous system. Gas that will be burn when mixed with air (or oxygen) and ignited. Rapid oxidation of a substance, involving heat and light. Gas that at ambient temperature and pressure forms a flammable mixture with air at concentrations of 12% (or less) by volume. Gases in an atmosphere that absorb and emit radiation within the thermal infrared range. The main greenhouse gases in the Earths atmosphere are water vapor, carbon dioxide, methane, nitrous oxide, and ozone. A substance that oxidizes something, especially chemically. Chemisorption of oxidizing gases is accompanied by electron transfer on adsorbed species. The element or compound in a redox (reduction/reoxidation) reaction that reduces another species. In doing so, it becomes oxidized, and is therefore the electron donor in the redox. Chemisorption of reducing gas is accompanied by electron transfer from adsorbed species on the substrate. Exposure levels are based on concentration in air, which can be measured in percent by volume or in parts per million (ppm) (equivalent to mg/kg) or parts per billion (ppb). To convert percent concentration to ppm, move the decimal point four places to the right. Gas monitoring code requirements usually refer to permissible exposure level (PEL). Concentration deemed safe for 8-h time-weighted average. A concentration of airborne contaminants, normally expressed in parts per million or milligrams per cubic meter, which represents the maximum level from which one could escape within 30 min without any escape-impairing symptoms or irreversible health effects. The lowest gas concentration that a sensor can reliably and repeatably detect.
Hazardous materials Target gas Toxic gas Combustible gas Combustion Flammable gas Greenhouse gases
Oxidizing agent Reducing agent (reductant or reducer)
Concentration
Permissible exposure limit (PEL) Immediately dangerous to life and health (IDLH)
Lower detectable limit (LDL)
Lower explosive limit (LEL) The concentration of a gas below which the concentration of vapors is or lower flammable limit insufficient to support an explosive. This concentration is always referred to (LFL) as 100% LEL or LFL for that gas. Upper explosive limit (UEL) The maximum concentration of gas in air that will combust. or upper flammable limit (UFL) Odor threshold A concentration level that is detectable by the olfactory senses. (continued on following page)

Sensing/interaction mechanisms Fundamental mechanisms and interactions that allow the detection and quantification of chemicals (e.g., optical absorption, specific affinity of a material for a chemical, frequency shift). A sensing/interaction mechanism is also known as a transduction mechanism that converts the chemical presence to some form of usable signal. A structure that recognizes external stimuli. The process of acquiring and interpreting sensory information. A gas sensor exposed to very high levels of target gas (more than 20 times the designed operating range) becomes saturated and made inoperative. Poisoning also occurs when compounds react and form strong bonds with a sensors catalyst surface, thereby tieing up reaction sites for the target gas. This action diminishes the sensitivity of the sensor to the target gas. Requires an external AC or DC electrical source. Provides its own energy or derives it from the phenomenon being measured. Typically, a sensor with associated components (frequently electronics and user input/output devices) that can convert the sensors raw signal to usable information on a single target chemical (e.g., chemical concentration). It may be a stand-alone instrument or a sensor module for incorporation in a more comprehensive system. A combination of approved compatible devices with the necessary electrical interconnection and energy to produce an alarm signal in the event of system activation. A gas detection system in which the analytical instrument is maintained in continuous operation and sampling is performed without interruption. A gas monitoring method utilizing an air pump to draw air samples through tubing from the sampling location to a remote-mounted gas sensor. Integrated systems developed to meet specific client application requirements that can include the following: single or multiple sensors, signal processing and data analysis functions, data monitoring and recording, and control functions. The definition of smart and intelligent sensing can be debated. In general, it is difficult to identify any features in a smart sensor that parallel intelligence in natural systems; however, the terms have become cemented in the technical jargon. Usually, smart sensors are defined as sensors with integrated electronics that can perform one or more of the following functions: (1) logic functions, (2) two-way communication, (3) make decisions (Giachino 1986). Micromachining, microelectromechanical (MEMs), and nanoelectromechanical (NEMs) systems belong to the same class of miniaturized sensor devices. Physically, a smart sensor consists of a transduction element, signal conditioning electronics, and a controller/ processor that support some intelligence in a single package. (continued on following page)
Sensory receptor Sensory perception Poisoning
Passive sensor Active sensor Sensor system
Alarm system
Continuous gas-detection system Extractive sampling Measurement and control systems
Smart sensor

Microelectromechanical system (MEMs) Nanoelectromechanical systems (NEMs) Bulk micromachining Surface micromachining Cantilever Remote sensing The technology of the very small, which merges at the nanoscale into nanoelectromechanical systems and nanotechnology. Similar to MEMs but smaller. A process used to produce micromachinery or MEMs systems. Bulk micromachining creates structures by selectively etching inside a substrate. Deposition and etching of different structural layers on top of the substrate; i.e., this process creates structure on top of the substrate. A beam supported on only one end. Small- or large-scale acquisition of information of an object or phenomenon by the use of either recording or real-time sensing devices that are wireless, or not in physical or intimate contact with the object of control. A network consisting of spatially distributed devices using sensors to cooperatively monitor physical or environmental conditions.
Sensor network
Packaging or assembling of sensing and actuating, or signal processing devices, in the proximity of the analyte Lower maintenance Reduced downtime Better reliability Improved resolution and sensitivity, and superior functionality Fault-tolerant systems Adaptability for self-calibration and compensation Lower cost due to batch fabrication Lower weight Wireless data transfer Fewer interconnections between multiple sensors and control systems Less complex system architecture
These advantages of smart sensors are application-specific. There is certainly justification for many applications in distributing the signal processing throughout a large sensor system so that each sensor has its own calibration, fault diagnostics, signal processing, and communication, thereby creating a hierarchical system. Innovations in sensor technology have generally allowed a greater number of sensors to be networked, more accurate sensors to be developed, and on-chip calibration to be included. In general, new technology has contributed to better performance by increasing the efficiency and accuracy of information distribution and by reducing overall costs. However, these performance enhancements have been achieved at the expense of increased complexity of individual sensor systems. In closing, some definitions of sensor characteristics are summarized in Table 1.17. Most of these characteristics are given in manufacturers data sheets. However, information on the reliability and robustness of a sensor is rarely given in a quantitative manner.
Table 1.17. Summary of the main sensor characteristics

PARAMETER Sensitivity Sensitivity error Range Dynamic range Full-scale output Resolution Detection limit DEFINITION The slope of the output characteristic curve (y/x). A departure from the ideal slope of the characteristic curve. Maximum minus minimum value of the measured stimulus. Total range of the sensor from minimum to maximum. The algebraic difference between the electrical output with maximum and minimum input stimulus. Smallest measurable increment in measured stimulus. The lowest concentration value which can be detected by the sensor in question, under definite conditions. Whether or not the analyte can be quantified at the detection limit is not determined. Maximum frequency of the stimulus which can be detected. Time required for a sensor output to change from its previous state to a final settled value within an error tolerance band of the correct new value. Time required for recovery initial state of sensors after interaction with analyte. Error of measurement, in percent full-scale deflection. Capability to follow the changes in the input parameter regardless of the direction. Long-term stability (deviation of measurement over a time period). The percentage change in the zero point or baseline of a gas sensor or gas detection system over a specific period of time. The degree of reproducibility of a measurement (repeatability, reproducibility) Extent to which the actual measured curve of a sensor departs from the ideal curve. Ability to follow rapid changes in the input parameter; amplitude and phase distortion characteristics, response time. The dependent variable always either increases or decreases as the independent variable increases. No desirable output with further increase in stimuli (span-end nonlinearity). Output exists when it should be zero. Insensitivity of a sensor in a specific range of input signals. Leading dimension of sensors. Weight of sensors. Operating temperature and environment conditions. Service life in hours or number of cycles of operation. Purchase cost of the sensors. The length of time over which the sensor will operate. The maximum storage time (shelf life) must be distinguished from the maximum operating life. The latter can be specified either for continuous operation or for repeated onoff cycles.
Sensing frequency Response time Recovery time Accuracy Hysteresis Drift Zero drift Precision Linearity Dynamic linearity Monotonicity Saturation Offset Dead band Size Weight Optimal environment Reliability Cost Life cycle
7. ACKNOWLEDGMENTS
This work was supported by the World Class University (WCU) Program at the Gwangju Institute of Science and Technology (GIST) through a grant (Project No. R31-20008-000-10026-0) provided by the Ministry of Education, Science and Technology (MEST) of Korea, for the project titled Development of Maritime Environmental Sensor Using Nano and Photonic Technology, funded by the Ministry of Land, Transport and Maritime Affairs, Korea, and by the Korean Science and Engineering Foundation (KOSEF) NCRC grant funded by the Korean government (MEST) (No. R15-2008-006-01002-0).
REFERENCES
Ahn H., Chandekar A., Kang B., Sung C., and Whitten J.E. (2004) Electrical conductivity and vapor-sensing properties of -(3-thienyl)alkanethiol-protected gold nanoparticle films. Chem. Mater. 16, 32743278. Angelopoulos M. (2001) Conducting polymers in microelectronics. IBM J. Res. Dev. 45, 5775. Baena J.R., Gallego M., and Valcarcel M. (2002) Fullerenes in the analytical sciences. Trends Anal. Chem. 21(3), 187198. Banerjee D., Lao J.Y., Wang D.Z., Huang J.Y., Steeves D., Kimball B., and Ren Z.F. (2004) Synthesis and photoluminescence studies on ZnO nanowires. Nanotechnology 15, 404409. Baraton M.I., Merhari L., Wang J., and Gonsalves K.E. (1997) Dispersion of metal oxide nanoparticles in conjugated polymers: Investigation of the TiO2/PPV nanocomposite. MRS Symp. Proc. 501, 5964. Bondavalli P., Legagneux P., and Pribat D. (2009) Carbon nanotubes based transistors as gas sensors: State of the art and critical review. Sens. Actuators B 140, 304318. Bouchtalla S.L., Janot J.M., Deronzier A., Moutet J.C., and Seta P. (2002) [60]Fullerene immobilized in a thin functionalized polypyrrole film: Basic principles for the elaboration of an oxygen sensor. Mater. Sci. Eng. C 21, 125129. Cabala R., Meister V., and Potje-Kamloth K. (1997) Effect of composite doping on sensing properties of polypyrrole. J. Chem. Soc., Faraday Trans. 93, 131137. Cantalini C., Valentini L., Lozzi L., Armentano I., Kenny J.M., and Santucci S. (2003) NO2 gas sensitivity of carbon nanotubes obtained by plasma enhanced chemical vapor deposition. Sens. Actuators B 93, 333337. Cao W. and Duan Y. (2006) Breath analysis: Potential for clinical diagnosis and exposure assessment. Clinical Chem. 52(5), 800811. Chao Y.C. and Shih J.S. (1998) Adsorption study of organic molecules on fullerene with piezoelectric crystal detection system. Anal. Chim. Acta 374, 3946. Chaniotakis N. and Sofikiti N. (2008) Novel semiconductor materials for the development of chemical sensors and biosensors: A review. Anal. Chim. Acta 6(15), 19. Chaubey A. and Malhotra B.D. (2002) Mediated biosensors. Biosens. Bioelectron. 17, 441456. Clark L.C. Jr. (1956) Monitor and control of blood tissue O2 tensions. Trans. Am. Soc. Artif. Intern. Organs 2, 4148. Clark L.C. Jr. and Lyons C. (1962) Electrode system for continuous monitoring in cardiovascular surgery. Ann. N.Y. Acad. Sci. 148, 133153. Cleaver K.D. (2001) The analysis of process gases: A review. Accred. Qual. Assur. 6(1), 815. Comini E., Baratto C., Faglia G., Ferroni M., Vomiero A., and Sberveglieri G. (2009) Quasi-one dimensional metal oxide semiconductors: Preparation, characterization and application as chemical sensors. Prog. Mater. Sci. 54, 167.
INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 35 Dai L., Soundarrajan P., and Kim T. (2002) Sensors and sensor arrays based on conjugated polymers and carbon nanotubes. Pure Appl. Chem. 74(9), 17531772. Dimitrakopoulos C.D. and Mascaro D.J. (2001) Organic thin-film transistors: A review of recent advances. IBM J. Res. Dev. 45, 1127. Dimitrakopoulos Ch.D.and Malenfant P.R.L. (2002) Organic thin film transistors for large area electronics. Adv. Mater. 14, 99117. Drake C., Deshpande S., Bera D., and Seal S. (2007) Metallic nanostructured materials based sensors. Int. Mater. Rev. 52(5), 289317. Dresselhaus M.S., Dresselhaus G., and Eklund P.C. (1996) Science of Fullerenes and Carbon Nanotubes. Academic Press, San Diego, CA. Dresselhaus M.S., Lin Y.M., Rabin O., Jorio A., Souza Filho A.G., Pimenta M.A., Saito R., Samsonidze Ge.G., and Dresselhaus G. (2003) Nanowires and nanotubes. Mater. Sci. Eng. C 23, 129140. Flahaut E., Peigney A., Laurent Ch., Marliere Ch., Chastel F., and Rousset A. (2000) Carbon nanotubemetal oxide nanocomposites: Microstructure, electrical conductivity and mechanical properties. Acta Mater. 48, 38033812. Freeman T.M. and Seitz W.R. (1978) Chemiluminescence fiber optical probe for hydrogen peroxide based on the luminol reaction. Anal. Chem. 50, 12421246. Gangolli S. (ed.) (1999) The Dictionary of Substances and Their Effects. The Royal Society of Chemistry, Cambridge, UK. Gardner J.W. and Dartlett P.N. (1999) Electronic Noses: Principles and Applications. Oxford University Press, Oxford, UK. Gaskov A.M. and Rumyantseva M.N. (2001) Nature of gas sensitivity in nanocrystalline metal oxides. Russ. J. Appl. Chem. 74(3), 440444. Gaskov A. and Rumyantseva M. (2009) Metal oxide nanocomposites: Synthesis and characterization in relation with gas sensing phenimena. In: Baraton M.I. (ed.), Sensors for Environment, Health and Security. Springer Science + Business Media, Dordrecht, The Netherlands, 329. Gerard M., Chaubey A., and Malhotra B.D. (2002) Application of conducting polymers to biosensors. Biosens. Bioelectron.17, 345359. Giachino J.M. (1986) Smart sensors. Sens. Actuators 10, 239248. Gpel W. and Schierbaum K.-D. (1991) Definition and typical examples. In: Gpel W., Hesse J., and Zemel J.N. (eds.), Sensors. A Comprehensive Survey, Vol. 2, Part I. VCH, Weinheim, Germany, 2. Grendler P. (2007) Chemical Sensors: An Introduction for Scientists and Engineers. Springer-Verlag, BerlinHeidelberg. Guha P., Chakrabarti S., and Chaudhuri S. (2004) Synthesis of -Ga2O3 nanowire from elemental Ga metal and its photoluminescence study. Physica E 23, 8185. Hardacre C., Compton R.C., and Buzzeo M.C. (2004) Use of room temperature ionic liquids in gas sensor design. Anal. Chem. 15, 45834588. Harris P.J.E. (1999) Carbon Nanotubes and Related Structures. Cambridge University Press, Cambridge UK. Hernandez-Ramrez F., Tarancon A., Casals O., Arbiol J., Romano-Rodrguez A., and Morante J.R. (2007) High response and stability in CO and humidity measures using a single SnO2 nanowire. Sens. Actuators B 121, 317. Ho C.K., Robinson A., Miller D.R., and Davis M.J. (2005) Overview of sensors and needs for environmental monitoring. Sensors 5, 4-37. Hulanicki A., Geab S., and Ingman F. (1991) Chemical sensors definitions and classification. Pure Appl. Chem. 63(9), 12471250. IEC-draft 65/84 (1982) Terms and Definitions in Industrial Process Measurement and Control. International Electrotechnical Committee, Geneva.
36 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES Janata J. and Huber R.J. (eds.) (1985) Solid State Chemical Sensors. Academic Press, New York. Janata J. (1989) Principles of Chemical Sensors. Plenum Press, New York and London. Janata J. and Josowicz M. (2003) Conducting polymers in electronic chemical sensors. Nature 2(January), 1924. Jung S.W., Park W.I., Yi G.C., and Kim M. (2003) Fabrication and controlled magnetic properties of Ni/ZnO nanorod heterostructures. Adv. Mater. 15(15), 13581361. Kalcher K., Svancara I., Buzuk M., Vytras K., and Walcarius A. (2009) Electrochemical sensors and biosensors based on heterogeneous carbon materials. Monatsh . Chem. 140, 861889. Kam K.C., Deepak F.L., Cheetham A.K., and Rao C.N.R. (2004) In2O3 nanowires, nanobouquets and nanotrees. Chem. Phys. Lett. 397, 329334. Kharitonov S.A. and Barnes P.J. (2000) Clinical sapects of exhaled nitric oxide. Eur. Respir. J. 16, 781792. Konig U. (1987) Deposition and properties of multicomponent hard coating. Surf. Coat. Technol. 33, 91103. Korotcenkov G. (2007) Metal oxides for solid state gas sensors. What determines our choice? Mater. Sci. Eng. B 139, 123. Korotcenkov G. and Cho B.K. (2010) Porous semiconductors: Advanced material for gas sensor applications. Crit. Rev. Solid State Mater. Sci. 35(1), 137. Kroto H.W., Heath J.R., OBrien S.C., Curl R.F., and Smalley R.E. (1985) C60: Buckminsterfullerene. Nature 318, 162163. Li Z.J., Li H.J., Chen X.L., Li L., Xu Y.P., and Li K.Z. (2002) -Ga2O3 nanowires on unpatterned and patterned MgO single crystal substrates. J. Alloys Comp. 345, 275279. Li C., Thostenson E.T., and Chou T.W. (2008) Sensors and actuators based on carbon nanotubes and their composites: A review. Compos. Sci. Technol. 68, 12271249. Liu A. (2008) Towards development of chemosensors and biosensors with metal-oxide-based nanowires or nanotubes. Biosens. Bioelectron. 24, 167177. Luo X., Morrin A., Killard A.J., and Smyth M.R. (2006) Application of nanoparticles in electrochemical sensors and biosensors. Electroanalysis 18(4), 319326. Madou M. and Morrison S. (1989) Chemical Sensing with Solid State Devices. Academic Press, San Diego, CA. Marczin N., Kharitonov S.A., Yacoub M.H., and Barnes P.J. (eds.) (2005) Disease Markers in Exhaled Breath. Taylor & Francies, Oxford, UK. Mauter M.S. and Elimelech M. (2008) Environmental applications of carbon-based nanomaterials. Environ. Sci. Technol. 42(16), 58435859. McQuade D.T., Pullen A.E., and Swager T.M. (2000) Conjugated polymer-based chemical sensors. Chem. Rev. 100, 25372574. Melde B.J., Johnson B.J., and Charles P.T. (2008) Mesoporous silicate materials in sensing. Sensors 8, 52025228. Moseley P. and Tofield B. (1989) Solid State Gas Sensors. Adam Hilger, Bristol, UK. Moskalenko K.L., Nadezhdinskii A.I., and Adamovskaya I.A. (1996) Human breath trace gas content study by tuneable diode laser spectroscopy. Infrared Phys. Technol. 37, 181192. Mulchandani A.K. and Wang C.L. (1996) Bienzyme sensors based modified electrodes. Electroanalysis 8, 414419. Nagl S., Baleizjo C., Borisov S.M., Schferling M., Berberan-Santos M.N., and Wolfbeis O.S. (2007) Optical sensing and imaging of trace oxygen with record response. Angew. Chem. Int. Ed. 46, 23172319. Nalwa H.S. (ed.) (1997) Handbook of Organic Conductive Molecules and Polymers, Vol. 4. John Wiley, Chichester, UK. OsadaY. and De Rossi D.E. (eds.) (2000) Polymer Sensors and Actuators. Springer-Verlag, Berlin. Park C.O. and Akbar S.A. (2003) Ceramics for chemical sensing. J. Mater. Sci. 38, 46114637. Pejcic B., Eadington P., and Ross A. (2007) Environmental monitoring of hydrocarbons: A chemical sensor perspective. Environ. Sci. Technol. 41(18), 63336342.
INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 37 Penza M., Antolini F., and Vittori-Antisari M. (2004) Carbon nanotubes as SAW chemical sensors materials. Sens. Actuators B 100, 4759. Persaud K.C. (2005) Polymers for chemical sensing. Mater.Today April, 2844. Poulin P., Vigolo B., and Launois P. (2002) Films and fibers of oriented single wall nanotubes. Carbon 40, 17411749. Pron A. and Rannou P. (2002) Processible conjugated polymers: From organic semiconductors to organic metals and superconductors. Prog. Polym. Sci. 27, 135190. Rahman Md. A., Kumar P., Park D.-S., and Shim Y.-B. (2008) Electrochemical sensors based on organic conjugated polymers. Sensors 8, 118141. Riu J., Maroto A., and Xavier Rius F. (2006) Nanosensors in environmental analysis. Talanta 69(2), 288301. Rolison D.R. (1990) Zeolite-modified electrodes and electrode-modified zeolites. Chem. Rev. 90(5), 867878. Saito R., Dresselhaus G., and Dresselhaus M.S. (1998) Physical Properties of Carbon Nanotubes. Imperial College Press, London. Schultz J.S. and Taylor R.F. (1996) Introduction to chemical and biological sensors. In: Taylor R.F. and Schultz J.S. (eds.), Handbook of Chemical Sensors and Biosensors. IOP Publishing, Bristol and Philadelphia. Shieh J., Huber J.E., Fleck N.A., and Ashby M.F. (2001) The selection of sensors. Prog. Mater. Sci. 46, 461504. Skotheim T.A., Elsenbaumer R., and Reynolds J.R. (eds.) (1998) Handbook of Conducting Polymers, 2nd ed. Marcel Dekker, New York. Smith D., Spanel P., and Davies S. (1999) Trace gases in breath of healthy volunteers when fasting and after a protein-calorie meal: A preliminary study. J. Appl. Physiol. 87, 15841588. Stetter J. and Penrose W. (2002) Understanding chemical sensors and chemical sensor arrays (electronic noses): Past, present, and future. Sensors Update 10, 189229. Stetter J.R., Penrose W.R., and Yao S. (2003) Sensors, chemical sensors, electrochemical sensors, and ECS. J.Electrochem. Soc. 150(2), S11S16. Synowczyk A.W. and Heinze J. (1993) Application of fullerenes as sensor materials. In: Kuzmany H., Mehring N., and Fink J. (eds.), Electronic Properties of Fullerenes. Springer Series in Solid State Sciences, 117, 7377. Springer-Verlag, Berlin. Taylor R.F. (1996) Chemical and biological sensors: Markets and commercialization. In: Taylor R.F. and Schultz J.S. (eds.), Handbook of Chemical Sensors and Biosensors. IOP Publishing, Bristol and Philadelphia. Terrones M., Jorio A., Endo M., Rao A.M., Kim Y., Hayashi T., Terrones H., Charlier J.C., Dresselhaus G., and Dresselhaus M.S. (2004) New direction in nanotube science. Mater. Today October, 3045. Thomas S.W. III, Joly G.D., and Swager T.M. (2006) Chemical sensors based on amplifying fluorescent conjugated polymers. Mater. Sci. Eng. R 52, 4991. Valentini L., Cantalini C., Lozzi L., Armentano I., Kenny J.M., and Santucci S. (2003) Reversible oxidation effects on carbon nanotubes thin films for gas sensing applications. Mater. Sci. Eng. C 23, 523529. Valentini L., Cantalini C., Armentano I., Kenny J.M., Lozzi L., and Santucci S. (2004) Highly sensitive and selective sensors based on carbon nanotubes thin films for molecular detection. Diamond Rel. Mater. 13, 13011305. Varghese O.K., Kichambre P.D., Gong D., Ong K.G., Dickey E.C., and Grimes C.A. (2001) Gas sensing characteristics of multi-wall carbon nanotubes. Sens. Actuators B 81, 3241. Varghese O.K., Gong D., Paulose M., Grimes C.A., and Dickey E.C. (2003) Crystallization and high-temperature structural stability of titanium oxide nanotube arrays. J. Mater. Res. 18(1), 156165. Vlasov Yu. and Legin A. (1998) Non-selective chemical sensors in analytical chemistry: From electronic nose to electronic tongue. Fresenius. J. Anal. Chem. 361, 255260. Vlasov Yu., Legin A., Rudnitskaua A., Di Natale C., and DAmico A. (2005) Nonspecific sensor arrays (electronic tongue) for chemical analysis of liquids. Pure Appl. Chem. 77(11), 19651983.
38 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES Walcarius A. (1999) Zeolite-modified electrodes in electrochemical chemistry. Anal. Chim. Acta 384, 116. Wang L.G., Wang X., Ottova A.L., and Tien H.T. (1996) Iodide sensitive sensor based on a supported bilayer lipid membrane containing a cluster form of carbon (fullerene C60). Electro-Analysis 8, 10201022. White L.T. (2000) Hazardous Gas Monitoring: A Guide for Semiconductor and Other Hazardous Occupancies. Logan T. White Engineering, Tucson, AZ. Zhang S., Yongqing D.S., and Du F.H. (2003) Recent advances of superhard nanocomposite coatings: A review. Surf. Coat. Technol. 167, 13119. Zhang Y., Ago H., Liu J., Yumura M., Uchida K., Ohshima S., Iijima S., Zhu J., and Zhang X. (2004) The synthesis of In, In2O3 nanowires and In2O3 nanoparticles with shape-controlled. J. Crystal Growth 264, 363368.

Chemical Sensors: Comprehensive Sensor Technologies, Vol. 4: Solid State Sensors

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemical Sensors: Comprehensive Sensor Technologies, Vol. 4: Solid State Sensors

Uploaded by

Copyright:

Available Formats

CHEMICAL SENSORS

COMPREHENSIVE SENSORS TECHNOLOGIES

MOMENTUM PRESS, LLC, NEW YORK

2.2 2.3 2.4 2.5 2.6

Selectivity Response and Recovery Rates Saturation Resolution Noise

4.3 4.4 4.5 4.6 4.7 4.8

214 214 218 219 221 222 223 223 229

261 261 262 262 263 264

471 473 475 475 485

PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES

xvi PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES

PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSORS TECHNOLOGIES xvii

PREFACE TO VOLUME 4: SOLID-STATE DEVICES

xx PREFACE TO VOLUME 4: SOLID-STATE DEVICES

ABOUT THE EDITOR

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES

G. Korotcenkov B. K. Cho 1. DEFINITIONS AND CLASSIFICATIONS

2 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 3

4 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 5

Acoustical/mechanical Magnetic Calorimetric (thermal)

6 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

Surface acoustic wave Quartz crystal microbalance

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 7

2. A BRIEF HISTORY OF CHEMICAL SENSORS

8 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 9

3. MOTIVATIONS FOR DESIGN OF CHEMICAL SENSORS

10 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

Source: Data from Taylor 1996.

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 11

Source: Data from www.inspectapedia.com.

12 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 13

Ethanol Methane CO2 Ammonia/urea

14 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

Source: Data from Gangolli 1999; Ho et al. 2005.

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 15

4. WHAT DETERMINES SUCCESS IN CHEMICAL SENSOR DESIGN?

16 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

Biological Sciences Chemical Sciences Physical Sciences

Signal Processing Engineering

Figure 1.5. From idea to devicesfrom science to engineering.

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 17

5. MATERIALS FOR CHEMICAL SENSORS

5.1. METAL OXIDES

18 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 19

20 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 21

5.3. NEW TRENDS IN SENSING MATERIALS

5.3.1. Fullerenes: Present and Future

Figure 1.6. Schematic view of fullerenes. (Reprinted from http://commons.wikipedia.org.)

22 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 23

5.3.2. Carbon NanotubesA New Material for Chemical Sensors

24 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 25

5.3.3. Metal Oxide One-Dimensional Nanomaterials

26 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

INTRODUCTION TO CHEMICAL SENSOR TECHNOLOGIES 27

28 CHEMICAL SENSORS: TECHNOLOGIES. VOLUME 4: SOLID-STATE DEVICES

5.3.5. Other Materials