CHEMICAL SENSORS COMPREHENSIVE SENSORS TECHNOLOGIES ELECTROCHEMICAL AND OPTICAL SENSORS VOLUME 5: GHENADII KOROTCENKOV GWANGJU, REPUBLIC OF KOREA

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1 CHEMICAL SENSORS COMPREHENSIVE SENSORS TECHNOLOGIES VOLUME 5: ELECTROCHEMICAL AND OPTICAL SENSORS EDITED BY GHENADII KOROTCENKOV GWANGJU INSTITUTE OF SCIENCE AND TECHNOLOGY GWANGJU, REPUBLIC OF KOREA MOMENTUM PRESS, LLC, NEW YORK

2 Contents Preface to Chemical Sensors: Comprehensive Sensors Technologies Preface to Volume 5: Electrochemical and Optical Sensors About the Editor Contributors xv xix xxi xxiii Electrochemical Gas Sensors: Fundamentals, Fabrication, and Parameters 1 J. R. Stetter G. Korotcenkov X. Zeng Y. Tang Y. Liu 1 Introduction 1 2 Fundamentals of Electrochemistry for Gas Sensors Potential and Potentiometry Current, Charge, and Amperometry Conductivity/Resistance and Conductometry 7 3 Types of Gaseous Interactions in Sensing Gas/Electrolyte Interactions Gas/Electrode Interactions 12 4 Fundamentals of Electrochemical Gas Sensors Amperometric Gas Sensors Potentiometric Gas Sensors Conductometric Gas Sensors 22 5 Analytes 23 6 Electrochemical Gas Sensor Designs and Materials Electrolytes Membranes Electrodes 38 v

3 vi. CONTENTS 7 Analytical Characteristics of Electrochemical Sensors Sensitivity (Lower Detection Limit) Selectivity Precision and Accuracy Stability 48 8 Examples of Electrochemical Gas Sensors Electrochemical Hi Sensors with Liquid Electrolytes Characteristics of Electrochemical H: Sensors Fabricated Using Polymer Electrolytes High-Temperature H, Sensors 62 9 MEMS and Nanotechnology in Electrochemical Gas Sensor Fabrication Electrochemical Sensor Applications Parameters in Gas Sensor Application Temperature Humidity Pressure Calibration Sensor Failure Mechanisms Sensor Life Market for Electrochemical Gas Sensors Outlook and Future Trends 76 References 78 2 Stabilized Zirconia-Based Gas Sensors 91 S. Zhuiykov 1 Introduction 91 2 Fundamentals of Sensor Operation Nernstian Behavior Non-Nernstian Behavior 'otentiomettic Non-Nernstian Gas Sensors Mixed-Potential Gas Sensors Differential Electrode Equilibria Gas Sensors Amperometric Gas Sensors Impedance-Based Gas Sensors Use of Nanostructured Oxides for Sensing Electrodes Zirconia Sensors Operating in Real Industrial Applications Inaccuracy of the Oxygen Probe Resulting from Catalyzed SE/Gas Reactions 113

4 CONTENTS vii 7.2 Sensor Errors Caused by Improper Operating Conditions and Probe Deterioration Markets for Zirconia-Based Sensors Summary and Outlook Acknowledgments 118 References Electrochemical Sensors for Liquid Environments 125 V. K. Gupta L. P. Singh 1 Introduction Sensors for Liquid Environments Potentiometric Sensors Conductometric Sensors Voltammetric and Amperometric Sensors FET-Based Sensors Chronological Progress in Design of Sensors for Liquid Environments Design of Ion-Selective Electrodes The Role of the Membrane in Sensors for Liquid Environments Classification of Ion-Selective Electrodes Liquid Membrane Electrodes Solid-State Electrodes Polymeric Membranes The Ionophore The Polymeric Matrix The Plasticizer The Lipophilic Additive Theory and Methodology Potential of an Ion-Exchange Membrane Selectivity of Electrodes Experimental Aspects Pre-Starting Procedure Methodology of Measurements Maintenance and Storage of Ion-Selective Electrodes Sources of Error Precautions Literature on Ion-Selective Electrodes Glass Electrodes 144

5 viii. CONTENTS 9.2 Homogeneous 9.3 Heterogeneous Solid-State Electrodes 145 Solid-State Electrodes Electrodes for Alkali Metal Ions Electrodes for Alkaline Earth Metals Electrodes for Heavy Metals Conclusion Nomenclature 159 References Ion-Sensitive Field-Effect Transistor (ISFET)-Based Chemical Sensors 171 V. K. Khanna 1 Introduction Different Structural Versions of the ISFET Concept, and a Historical Survey Front-Side and Back-Side Connected ISFETs The Extended-Gate Field-Effect Transistor (EGFET) Use of Macroporous Silicon for Field-Effect ph Sensor Fabrication Layer-by-Layer Nano Self-Assembly ISFET Light-Addressable Potentiometric Sensor (LAPS) Region Ion-Sensitive Field-Effect Transistor (RISFET) Organic-Based Field-Effect Transistors and New Materials for ISFETs Fundamentals of MOSFET Operation MOS Capacitor with Zero Gate Voltage MOS Capacitor with Applied Gate Voltage Capacitance of the MOS Capacitor Channel Conductance Flat-Band and Threshold Voltages Depletion- and Enhancement-Mode MOSFETs Static Characteristics of the MOS Transistor Theory of ph Sensitivity of the ISFET Site Binding Model Gouy-Chapman-Stern Model ph Sensitivity 4.4 Mathematical Formulation in Terms of the ph at the Point of Zero of the ISFET 200 Charge for the Relation between V / and ph ISFET Circuit Models ISFET/EGFET Gate Dielectric Materials Silicon Dioxide Silicon Nitride and Silicon Oxynitrides Aluminum Oxide Tantalum Pentoxide 207

6 CONTENTS ix 5.5 Tertiary Amines Other Dielectrics Dielectrics for the EGFET ISFET Design Considerations Design Parameters and Design Procedure ISFET Design Specifications Fabrication of the ISFET Chip Fabrication ISFET Encapsulation Materials O-Ring Packaging: The State of the Art ISFET Biasing/Readout Circuit and Instrumentation Source Follower Circuit Circuit with Buffer Amplifier Stages EGFET Readout Circuit Readout Circuits in CMOS Technology Influence of Ion-Selective Membranes and Other Coatings on ISFET Gate Dielectrics The Need for Membranes, and Membrane Materials Membrane Potential Membrane Selectivity Membranes of ISFET-Based Biosensors Problems with Membranes ISFET-Based Sensors for Positive Ions Ammonium Ion, NH4+Sensor Cadmium Ion, Cd2+ Sensor Calcium Ion, Ca2+ Sensor Cationic Surfactant Sensor Chromium Ion, Cr6+ Sensor Cupric Ion, Cu2+ Sensor Heavy-Metal Ion (Cd2+, Pb2t) Sensor Iron (Fe3+) Ion Biosensor Mercuric Ion, Hg2t Biosensor Potassium Ion, K'Sensor Silver Ion, Ag+ Sensor Sodium Ion, Na* Sensor ISFET-Based Sensors for Negative Ions Chloride ISFET Cyanide Ion, CN_ Sensor Fluoride (F-) ISFET Nitrate (N03-) Sensor 245

7 x CONTENTS 11.5 Organic Anion Sensor Phosphate (H2P04") Sensor Sulfate (S042~) Sensor ISFET-Based Sensors for Biomolecules Acetylcholine Biosensor Adenosine Sensor Adenosine Triphosphate (ATP) Sensor Creatinine Biosensor DNA Sensor Dopamine Sensor Glucose Biosensor Glutamate Biosensor Lactate Biosensor Penicillin Biosensor Triglyceride Trypsin Biosensor 250 Biosensor Urea Biosensor ISFET-Based Gas Sensors Ammonia Sensor H2 Gas Sensor Sensor for Dissolved Oxygen Transcutaneous C02 Sensor Flow-Through-Type ph/c02 Sensor System 14 Temperature Based on thiz ISFET 252 Effects on the ISFET Light Effects on the ISFET Reference Electrode-Related Problems ISFET-REFET Combinations Deviations, Repeatability, and Variability in Ta20, Gate ISFET--Reference Electrode Assemblies and Calibration of ph-standard Buffers 256 Effects ISFET Storage-Time 18.2 ISFET Storage in Air Estimation of ISFET Deviation Rate Adverse Storage Environment Effects ph Changes of Buffer Solutions in Ambient Atmosphere Measurements by the Same or Different ISFETs Identification of ISFET Malfunctions ISFET Applications and Market Water Analysis and Environmental Monitoring 263

8 CONTENTS xi 20.2 Diagnostic and Health-Care Applications Biotechnological Process Monitoring Soil Analysis, Evaluation, and Agriculture Conclusions and Outlook Dedication Acknowledgments Nomenclature 265 References Microfluidic Chips as New Platforms for Electrochemical Sensing 275 M. Hervds M. Angel Lopez A. Escarp a 1 Introduction General Outlines of Microfabrication of Microfluidic Platforms Microfabrication of Glass Microfluidic Platforms Microfabrication of Polymer Microfluidic Platforms Microfluidic Platforms for Electrochemical Sensing: Designs and Applications Voltammetric Microfluidic Sensors Potentiometric Microfluidic Sensors Conductometric Microfluidic Sensors Strengths, Weaknesses, and Future Trends 306 References Optical and Fiber Optic Chemical Sensors 311 G. Korotcenkov B. K. Cho R. Namyanaswamy F. Sevilla III 1 Introduction Optical Transduction Principles Absorption Fluorescence Chemiluminescence Scattering Reflection and Refraction Instrumentation Molecular Recognition Element 320

9 xii. CONTENTS 5 Sensor Configurations Absorption-Based Sensors Infrared and Near-Infrared Absorption UV Absorption Gas Analyzers of Absorption Type Global Remote Control Using Absorption Spectroscopy Luminescence (Fluorescence)-Based Sensors Chemiluminescence-Based Sensors Surface Plasmon Resonance Sensors Raman Scattering in Optical Chemical Sensing Ellipsometry Optical 12.1 Optical Fiber Chemical Sensors 356 Fibers Classification of Fiber Optic Sensors Advantages and Disadvantages of Fiber Optic Chemical Sensors Planar Waveguide-Based Sensor Platforms Fluorescence-Based PWCS Absorption-Based PWCS Refractometric PWCS Interferometric PWCS Integrated Optical Sensors Design and Fabrication of Optical Sensors General Comments Reasons for Uncontrolled Intensity Modulation in Optical Sensors Sensing Materials Fiber Selection and Features of Fiber Preparation Immobilization Techniques Sensors lor Flowing Systems Optical Multiple-Chemical Sensing The Optoelectronic Nose: Sensor Arrays Optical Sensors for Portable Instruments Acceptable in Field Applications Examples of Optical Chemical Sensors Fields of Optical Chemical Sensor Applications ph Sensors Metal-Ion Sensing Anion Sensing 438

10 CONTENTS xiii 19.5 Gas Sensors Humidity Sensors Vapor Sensors Other Molecular Sensors Optical Biosensors Biomedical Sensors Conclusions and Prospects 455 References Chemiluminescence Chemical Sensing: Fundamentals of Operation and Application for Water Pollutants Control 477 J.-M. Lin L. Zhao 1 Introduction Fundamentals of Chemiluminescence Sensing Principle of CL Analysis Classical Chemiluminescence Reagents Methodology of Chemical Analysis Using Chemiluminescence Sensing Application of Chemiluminescence Sensors for Water Pollutants Control Metals Hydrogen Peroxide Chemical Oxygen Demand Pesticides and Herbicides Phenols Nitrogen Compounds Estrogens Fungoids Outlook 494 References 495

ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY VOLUME 2

ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY VOLUME 2 MODERN ANALYTICAL CHEMISTRY Series Editor: David Hercules University of Pittsburgh ANALYTICAL ATOMIC SPECTROSCOPY By William G. Schrenk PHOTOELECTRON