Table Of ContentHandbook of Humidity Measurement
Methods, Materials and Technologies
Volume 3: Sensing Materials and Technologies
Handbook of Humidity Measurement: Methods, Materials
and Technologies, 3-Volume Set
(ISBN: 978-1-138-29787-6)
Handbook of Humidity Measurement,
Volume 1: Spectroscopic Methods of Humidity Measurement
(ISBN: 978-1-138-30021-7)
Handbook of Humidity Measurement,
Volume 2: Electronic and Electrical Humidity Sensors
(ISBN: 978-1-138-30022-4)
Handbook of Humidity Measurement,
Volume 3: Sensing Materials and Technologies
(ISBN: 978-1-138-48287-6)
Handbook of Humidity Measurement
Methods, Materials and Technologies
Volume 3: Sensing Materials and Technologies
Ghenadii Korotcenkov
CRC Press
Taylor & Francis Group
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Library of Congress Cataloging‑in‑Publication Data
Names: Korotcenkov, G. S. (Gennadii Sergeevich), author.
Title: Handbook of humidity measurement : methods, materials, and
technologies / Ghenadii Korotcenkov.
Other titles: Humidity measurement
Description: Boca Raton : CRC Press, Taylor & Francis Group, 2018-[2020] |
Includes bibliographical references. Contents: volume 1. Spectroscopic
methods of humidity measurement -- volume 2. Electronic and electrical
humidity sensors -- volume 3. Sensing materials and technologies.
Identifiers: LCCN 2017049880| ISBN 9781138300217 (hardback : alk. paper : v.
1) | ISBN 9781138300224 (hardback : alk. paper : v. 2) | ISBN
9781138482876 (hardback : alk. paper : v. 3)
Subjects: LCSH: Hygrometry. | Humidity. | Water vapor, Atmospheric. |
Spectrum analysis.
Classification: LCC QC915 .K825 2018 | DDC 551.57/10287--dc23
LC record available at https://lccn.loc.gov/2017049880
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Contents
Preface to the Series...................................................................................................................................................................xiii
Preface......................................................................................................................................................................................... xv
Acknowledgments.....................................................................................................................................................................xvii
Author ........................................................................................................................................................................................xix
Section i Humidity-Sensitive Materials
Chapter 1 Polymers.................................................................................................................................................................. 3
1.1 Introduction .................................................................................................................................................. 3
1.1.1 Polymers as Sensing Materials........................................................................................................ 3
1.1.2 Stability of Polymers....................................................................................................................... 5
1.2 Polymer Degradation.................................................................................................................................... 6
1.2.1 Thermal Degradation ...................................................................................................................... 7
1.2.2 Oxidative Degradation .................................................................................................................... 8
1.2.2.1 Photochemical Oxidation................................................................................................. 9
1.2.2.2 Thermal Oxidation......................................................................................................... 11
1.2.2.3 Hydrolytic Degradation.................................................................................................. 12
1.2.3 Biodegradation .............................................................................................................................. 12
1.2.4 Degradation Caused by Ionizing Radiations................................................................................. 12
1.2.5 Conducting Polymers Dedoping ................................................................................................... 13
1.3 Approaches to Polymer Stabilization ......................................................................................................... 15
References ............................................................................................................................................................. 19
Chapter 2 Metal Oxide in Humidity Sensors......................................................................................................................... 23
2.1 Main Advantages and Limitations of Metal Oxides and Their Characterization...................................... 23
2.2 Mechanisms of Humidity Sensitivity ......................................................................................................... 23
2.3 Multilayer Water Adsorption at Solid Surfaces.......................................................................................... 25
2.3.1 Brunauer-Emmett-Teller (BET) Isotherm ..................................................................................... 26
2.3.2 Water Adsorption at Solid Surfaces .............................................................................................. 26
2.4 How to Optimize Sensor Performance....................................................................................................... 28
References............................................................................................................................................................. 32
Chapter 3 Al O as a Humidity-Sensitive Material ............................................................................................................... 35
2 3
3.1 Al O -Based Humidity Sensors.................................................................................................................. 35
2 3
3.2 Features of Al Anodization ........................................................................................................................ 38
3.2.1 General Consideration................................................................................................................... 38
3.2.2 Mechanism of Pore Formation...................................................................................................... 40
3.2.3 Parameters of Anodic Porous Alumina and How to Control Them ............................................. 41
3.2.4 Two-Step Anodization................................................................................................................... 43
3.3 Limitations of Al O -Based Humidity Sensors and How Resolve This Problem...................................... 43
2 3
3.4 Al O -Based Humidity Sensors Fabricated Using Other Technologies..................................................... 45
2 3
References............................................................................................................................................................. 47
v
vi Contents
Chapter 4 Carbon-Based Materials........................................................................................................................................ 51
4.1 Introduction ................................................................................................................................................ 51
4.2 Carbon Black .............................................................................................................................................. 51
4.2.1 CB-Polymer Composites and Their Application in Humidity Sensors ........................................ 52
4.3 Fullerenes ................................................................................................................................................... 56
4.4 Carbon Nanotubes ...................................................................................................................................... 57
4.4.1 Synthesis of CNTs......................................................................................................................... 57
4.4.2 Features of CNTs and Prospects for Their Applications in Humidity Sensors ............................ 58
4.4.3 Disadvantages of CNTs Which Can Limit Their Application in Humidity Sensors.................... 60
4.4.4 CNT-Based Composites ................................................................................................................ 64
4.5 Graphene..................................................................................................................................................... 66
4.5.1 Synthesis and Deposition of Graphene Layers.............................................................................. 66
4.5.2 Graphene-Based Gas and Humidity Sensors ................................................................................ 67
4.5.3 Disadvantages of Graphene, Limiting Its Application.................................................................. 70
4.6 Nanodiamond Particles .............................................................................................................................. 71
4.7 Carbon Nitride............................................................................................................................................ 72
4.7.1 Carbon Nitride and Its Properties ................................................................................................. 72
4.7.2 Humidity-Sensing Characteristics of Carbon Nitride................................................................... 73
4.8 Surface Functionalizing of Carbon Nanotubes and Other Carbon-Based Nanomaterials ........................ 76
4.8.1 Carbon Nanotubes......................................................................................................................... 76
4.8.2 Carbon Black and Fullerenes ........................................................................................................ 78
4.8.3 Graphene ....................................................................................................................................... 79
References ............................................................................................................................................................. 81
Chapter 5 Semiconductor-Based Humidity Sensors.............................................................................................................. 91
5.1 Conventional IV and III-V Semiconductors............................................................................................... 91
5.2 Gallium and Boron Nitrides (Wide-Band Semiconductors) ...................................................................... 93
5.2.1 Gallium Nitride ............................................................................................................................. 93
5.2.2 Boron Nitride................................................................................................................................. 94
5.3 Chalcogenides............................................................................................................................................. 96
5.4 Dichalcogenides.......................................................................................................................................... 98
5.4.1 Features and Synthesis .................................................................................................................. 98
5.4.2 Dichalcogenide-Based Humidity Sensors..................................................................................... 99
5.5 Silicon Carbide (SiC)................................................................................................................................ 102
5.5.1 SiC-Based Humidity Sensors ...................................................................................................... 103
References........................................................................................................................................................... 104
Chapter 6 Porous Silicon...................................................................................................................................................... 109
6.1 Porous Silicon: General Consideration..................................................................................................... 109
6.1.1 Advantages of Porous Silicon for Humidity-Sensor Application ............................................... 109
6.2 Features of Silicon Porosification............................................................................................................. 110
6.2.1 Electrochemical Porosification.................................................................................................... 110
6.2.2 Other Methods of Silicon Porosification..................................................................................... 112
6.3 PSi Characterization ................................................................................................................................. 113
6.4 PSi-Based Humidity Sensors.................................................................................................................... 116
6.4.1 Capacitance Humidity Sensors.................................................................................................... 116
6.4.2 Resistive Humidity Sensors......................................................................................................... 118
6.4.3 Other Types of PSi-Based Humidity Sensors.............................................................................. 119
6.4.4 Micromachined PSi-Based Humidity Sensors ............................................................................ 120
6.5 Limitations of PSi-Based Humidity Sensors............................................................................................ 121
6.6 Approaches to Optimization of PSi-Based Humidity Sensors................................................................. 122
6.6.1 Sensitivity.................................................................................................................................... 122
6.6.2 Selectivity.................................................................................................................................... 124
6.6.3 The Rate of Response.................................................................................................................. 126
Contents vii
6.6.4 Hysteresis .................................................................................................................................. 127
6.6.5 Linearity .................................................................................................................................... 128
6.6.6 Stability ..................................................................................................................................... 129
6.6.6.1 Stabilization through Oxidation ................................................................................. 129
6.6.6.2 Stabilization through Thermal Carbonization and Nitridation................................... 131
6.6.6.3 Stabilization through Surface Functionalizing........................................................... 131
6.6.6.4 Temperature Stabilization .......................................................................................... 132
6.6.6.5 Drift Compensation.................................................................................................... 132
6.7 Conclusions and Future Trends............................................................................................................... 132
References .......................................................................................................................................................... 132
Chapter 7 Mesoporous Silica and Its Prospects for Humidity Sensor Application ............................................................ 139
7.1 Classification of Porous Materials .......................................................................................................... 139
7.2 Mesoporous Silica................................................................................................................................... 139
7.3 Advantages of Silica for Sensor Applications......................................................................................... 142
7.4 Silica-Based Humidity Sensors............................................................................................................... 143
7.4.1 Approaches to Humidity Sensor Design................................................................................... 143
7.4.2 Features of Humidity Sensor Fabrication ................................................................................. 147
References .......................................................................................................................................................... 148
Chapter 8 Aluminosilicate (Zeolites)-Based Humidity Sensors......................................................................................... 151
8.1 Zeolites and Features of Their Synthesis ................................................................................................ 151
8.2 Advantages for Gas-Sensor Applications................................................................................................ 154
8.3 Zeolite-Based Humidity Sensors............................................................................................................. 156
8.4 Limitations of Zeolite Application in Humidity Sensors ........................................................................ 158
References .......................................................................................................................................................... 159
Chapter 9 Metal Phosphate-Based Humidity Sensitive Materials...................................................................................... 163
9.1 Metal Phosphates .................................................................................................................................... 163
9.2 Synthesis and Mechanism of Molecular Sieve Growth .......................................................................... 163
9.3 Metal Phosphate-Based Humidity Sensors ............................................................................................. 166
9.4 Limitations .............................................................................................................................................. 168
References .......................................................................................................................................................... 168
Chapter 10 Black Phosphorus and Phosphorene-Based Humidity Sensors ......................................................................... 171
10.1 Black Phosphorus.................................................................................................................................... 171
10.2 Crystal and Electronic Structures of BP.................................................................................................. 171
10.3 Synthesis of Black Phosphorus and Phosphorene................................................................................... 173
10.3.1 Bulk Black Phosphorus............................................................................................................. 173
10.3.2 Phosphorene .............................................................................................................................. 173
10.4 Black Phosphorus-Based Humidity Sensors........................................................................................... 175
10.5 Limitations .............................................................................................................................................. 178
10.5.1 The Tunability of Black Phosphorus Properties ....................................................................... 178
10.5.2 Instability of Black Phosphorus ................................................................................................ 179
References .......................................................................................................................................................... 182
Chapter 11 Metal-Organic Framework-Based Humidity Sensors ........................................................................................ 187
11.1 Metal-Organic Frameworks .................................................................................................................... 187
11.1.1 General Consideration............................................................................................................... 187
11.1.2 MOF Synthesis and Structural Engineering.............................................................................. 187
viii Contents
11.2 Humidity-Sensor Applications................................................................................................................ 191
11.2.1 Advantages for Gas-Sensor Applications.................................................................................. 191
11.2.2 MOF-Based Humidity Sensors ................................................................................................. 191
11.2.2.1 Mass-Sensitive Sensors............................................................................................ 192
11.2.2.2 Other Types of Humidity Sensors............................................................................ 194
11.2.3 Features of MOF-Based Sensor Fabrication............................................................................. 196
11.2.4 How to Optimize the Sensor Performance? .............................................................................. 198
11.2.5 Limitations ................................................................................................................................ 200
11.3 Prospects of MOF for Structural Engineering of Humidity-Sensitive Materials.................................... 202
References.......................................................................................................................................................... 203
Chapter 12 Supramolecular Materials .................................................................................................................................. 209
12.1 Cavitands................................................................................................................................................. 209
12.1.1 Characterization ........................................................................................................................ 209
12.1.2 Cavitands as a Material for Gas and Electrochemical Sensors ................................................. 210
12.1.3 Cavitand-Based Humidity Sensors ........................................................................................... 211
12.1.4 Limitations ................................................................................................................................ 213
12.2 Metallo-Complexes ................................................................................................................................. 214
12.2.1 Characterization ........................................................................................................................ 214
12.2.2 Advantages for Gas-Sensor Applications.................................................................................. 214
12.2.3 Humidity-Sensor Applications of Metallo-Complexes............................................................. 216
12.2.4 Approaches to Improving Gas-Sensor Parameters and Limitations ......................................... 218
12.2.5 Limitations ................................................................................................................................ 218
References.......................................................................................................................................................... 218
Chapter 13 Biomaterials as Sensing Elements of Humidity Sensors ................................................................................... 223
13.1 Proteins as Humidity-Sensitive Material................................................................................................. 223
13.2 Collagen-Based Humidity Sensors ......................................................................................................... 223
13.3 Other Biomaterials .................................................................................................................................. 224
References.......................................................................................................................................................... 225
Section ii Sensor technologies and Related Materials
Chapter 14 Substrates and Electrodes in Humidity Sensors................................................................................................. 229
14.1 Conventional Substrates for Humidity Sensors....................................................................................... 229
14.2 Electrodes................................................................................................................................................ 230
14.3 Materials for Heater Fabrication ............................................................................................................. 232
References.......................................................................................................................................................... 234
Chapter 15 Fundamentals of Microfabrication Technologies............................................................................................... 237
15.1 CMOS Process and Its Use in the Manufacture of Humidity Sensors.................................................... 237
15.1.1 CMOS Process: General Consideration.................................................................................... 237
15.1.2 CMOS-Based Humidity Sensors............................................................................................... 238
15.1.3 CMOS-MEMS-Based Humidity Sensors ................................................................................. 238
15.2 Features of Micromachining Processes................................................................................................... 239
15.2.1 Bulk Micromachining ............................................................................................................... 239
15.2.1.1 Wet Etching.............................................................................................................. 240
15.2.1.2 Dry Etching.............................................................................................................. 243
15.2.1.3 Examples of the Manufacture of Membranes and Cantilevers ................................ 247
15.2.2 Surface Micromachining........................................................................................................... 247
15.2.2.1 Features of Surface Micromachining Processes ...................................................... 249
15.2.3 Processes Using Both Bulk and Surface Micromachining ....................................................... 250
Contents ix
15.2.4 Other Micromachining Techniques........................................................................................... 251
15.2.4.1 PSi-Based Micromachining ..................................................................................... 251
15.2.4.2 Lasers in Micromachining ....................................................................................... 252
15.2.4.3 LIGA Micromachining ............................................................................................ 252
15.3 Wafer Bonding ........................................................................................................................................ 254
15.3.1 Direct Bonding (High Temperature) ......................................................................................... 254
15.3.2 Anodic Bonding ........................................................................................................................ 256
15.3.3 Bonding Using Intermediate Layers ......................................................................................... 256
15.4 Summary ................................................................................................................................................. 258
References.......................................................................................................................................................... 258
Chapter 16 Micromachining Platforms for Humidity Sensors and Examples of Their Fabrication .................................... 263
16.1 Micromachining Membranes .................................................................................................................. 263
16.2 Silicon-Based Microcantilevers .............................................................................................................. 266
16.3 Functionalization of Cantilever and Membrane Surfaces ....................................................................... 269
References.......................................................................................................................................................... 270
Chapter 17 Platforms and Materials for QCM and SAW-Based Humidity Sensors............................................................. 271
17.1 Piezoelectric Materials............................................................................................................................ 271
17.2 High-Temperature AW Devices .............................................................................................................. 273
17.3 Micromachining QCM-Based Sensors ................................................................................................... 275
References.......................................................................................................................................................... 278
Chapter 18 Technologies Suitable for Fabrication of Humidity Sensing Layers: General Consideration ........................... 281
18.1 Introduction: Acceptable Technologies and Their Advantages and Limitations..................................... 281
18.2 Ceramic Technology ............................................................................................................................... 281
18.3 Planar Sensors ......................................................................................................................................... 286
18.3.1 Thick-Film Technology............................................................................................................. 287
18.3.1.1 Screen Printing......................................................................................................... 288
18.3.1.2 Other Printing Technologies .................................................................................... 293
18.3.1.3 Advantages and Disadvantages of Thick-Film Technology..................................... 294
18.3.2 Thin-Film Technology............................................................................................................... 296
18.3.2.1 Features of the Morphology of the Films Deposited Using Methods of
Thin-Film Technology ............................................................................................. 296
18.4 Summary ................................................................................................................................................. 299
References .......................................................................................................................................................... 300
Chapter 19 Polymer Technologies........................................................................................................................................ 305
19.1 Introduction............................................................................................................................................. 305
19.2 Methods of Polymer Synthesis................................................................................................................ 305
19.3 Preparation of Porous Polymers.............................................................................................................. 307
19.4 Fabrication of Polymer Films.................................................................................................................. 308
19.4.1 Solution-Based Methods ........................................................................................................... 309
19.4.2 Dry Methods.............................................................................................................................. 310
19.5 Bulk and Structure Modification of Polymers ........................................................................................ 311
19.5.1 Solvents and Their Role in the Formation of Pores .................................................................. 312
19.5.2 Cross-Linkers ............................................................................................................................ 312
19.5.3 Initiators .................................................................................................................................... 314
19.5.4 Plasticizers................................................................................................................................. 314
19.6 Approaches to Polymer Functionalizing................................................................................................. 315
19.6.1 Polymer Doping ........................................................................................................................ 315
19.6.1.1 Redox Doping (Ion Doping) .................................................................................... 315
19.6.1.2 Photo and Charge-Injection Doping ........................................................................ 316
19.6.1.3 Nonredox Doping..................................................................................................... 316
