CMOS and SOI CMOS FET-based Gas Sensors

by

James A. Covington School of Engineering University of Warwick

A thesis submitted to the University of Warwick for the degree of Doctor of Philosophy September 2001

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Contents
Heading Contents List of Figures List of Tables Summary Acknowledgements Declaration Selected Abbreviations and Acronyms CHAPER 1: Introduction 1.1 Electronic noses 1.2 The concept of electronic noses 1.2.1 Mammalian olfactory system 1.2.2 Gas sensors 1.2.3 Signal processing, identification and recognition 1.2.4 Smart gas sensors 1.3 Commercial electronic noses 1.3.1 Application of electronic noses 1.4 Aims of the project 1.5 Outline of thesis 1.6 References CHAPTER 2: MOS processes, materials and resistive sensors technologies employing catalytic metals and conducting polymers 2.1 Introduction 2.2 GasFET and MIS capacitor devices 2.3 Polymer based FET sensors 2.4 Resistive conducing polymer sensors 2.4.1 Electrochemically deposited conducting polymers 2.4.2 Spun or drip cast polymers 2.4.3 Carbon-black composite polymers 2.5 Metal oxide sensing films 2.6 Conclusions 17 17 26 29 29 33 34 37 39 Page iii ix xiv xviii xixx xx xxii 1 1 1 2 3 6 7 8 10 11 12 13 17

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2.7 References CHAPTER 3: Design of CMOS compatible devices for gas sensing 3.1 Introduction 3.1.1 MOS technology 3.1.2 Silicon-on-insulator technology 3.1.3 Development of resistive gas sensors utilising SOI technology 3.2 Design of a room temperature chemFET sensor 3.2.1 Mode of operation 3.2.2 Dimension and configuration of the gate structure 3.2.3 Sensor electrode material 3.3 Final room temperature chemFET sensor design 3.3.1 Fabrication process 3.4 Design of gas sensors using SOI technology 3.4.1 Design of a micro-hot plate 3.5 Design of a MOSFET heater 3.5.1 Interdigitated heater structures 3.5.2 Square heater structure 3.5.3 Electro-thermal simulation of heater structures 3.5.4. Thermal-mechanical simulation of heater structures 3.6 SOI Sensor structures 3.6.1 Chemoresistive electrodes 3.6.2 The chemFET sensor 3.6.3 Temperature sensors 3.7 Cell dimensions and final layout 3.7.1 SUMC final layout 3.8 Conclusions 3.9 References CHAPTER 4: Device fabrication and deposition of vapour sensitive layers 4.1 Introduction 4.2 Device realisation

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4.2.1 ChemFET array device 4.3 Deposition of polymer sensing materials 4.3.1 Spun-coated polymers 4.3.2 Carbon-black composite polymers 4.3.3 Electrochemically prepared polymers 4.4 Thickness profiling of conducting polymer films 4.4.1 Thickness profiles of Spun-coated/drip-cast polymers 4.4.2 Thickness profiles of composite polymers 4.4.3 Thickness profiles of electrochemically deposited polymers 4.5 Realisation of the SOI heater/sensor 4.5.1 Back-etching of SOI sensor array 4.5.2 Deposition of metal oxide films 4.6 Additional devices for resistive and work function measurements 4.6.1 Resistive sensor 4.6.2 Polymer substrate 4.7 Conclusions 4.8 References CHAPTER 5: Flow injection analysis test station and measurement instrumentation 5.1 Introduction 5.2 Flow injection analysis test station 5.3 Chemical hardware 5.4 Electronic interface 5.4.1 Electronic controller cards 5.5 Virtual instrumentation 5.5.1 Control software 5.6 Testing protocols 5.6.1 Leak testing diagnostics 5.6.2 Pre/post clean and sample preparation 5.7 I-V characterisation instrument 5.7.1 Electronic interface and associated hardware

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5.7.2 Software control program for I-V instrument 5.7.3 Commissioning of I-V instrument 5.8 Constant current measurement instrument 5.8.1 Electronic interface of the constant current measurement instrument 5.8.2 Control software for constant current instrument 5.8.3 Commissioning of constant current measurement instrument 5.9 Testing protocols for I-V characterisation and constant current measurements instruments 5.10 Conclusions 5.11 References CHAPTER 6: Room temperature chemFET sensors employing conducting polymer films: results, theory and analysis 6.1 Introduction 6.2 Response of chemFET sensors to different organic vapours 6.2.1 UMIST chemFET sensors employing a conducting polymer 6.2.2 ChemFET sensors employing composite polymers 6.2.3 ChemFET sensors employing electrochemically deposited polymers 6.3 Dynamic modelling of n-channel chemFET sensors 6.3.1 Response time 6.4 Static modelling of chemFET sensor 6.4.1 Static response of the UMIST sensor 6.4.2 ChemFET sensors employing composite polymers 6.4.3 ChemFET sensors employing electrochemically deposited polymers 6.5 Modelling of chemFET sensor response to organic vapours 6.5.1 Modelling of static response of chemFET sensors 6.5.2 Workfunction measurements of polymer materials

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6.6 Dependence of n-channel chemFET sensor response to film thickness 6.7 Detection limits of room temperature chemFET sensors employing conducting polymer films 6.7.1 ChemFET sensors with a composite polymer gate 6.7.2 ChemFET sensors with a electrochemically deposited polymer gate 6.8 Conclusions 6.9 References CHAPTER 7: The affect of water concentration and temperature on static response of chemFET sensors 7.1 Introduction 7.2 The affect of water concentration on the static response of room temperature chemFET sensors 7.2.1 ChemFET sensors employing composite polymer films as the gate 7.2.2 ChemFET sensors employing electrochemically deposited polymer films as the gate 7.3 The affect of temperature on the static response of room temperature chemFET sensors 7.3.1 ChemFET sensors employing composite polymer films as the gate 7.3.2 ChemFET sensors employing electrochemically deposited polymer films as the gate 7.4 Response and comparison to chemFET sensors of resistive composite sensors to analyte concentration, water concentration and temperature 7.4.1 The affect of analyte concentration on resistive sensor response 7.4.2 The affect of water concentration on the static response of a resistive sensor 7.4.3 The affect of temperature on the static response of resistive

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composite polymer sensors 7.5 Conclusions 7.6 References CHAPTER 8: Electrical and thermal characterisation of MOSFET heaters and gas sensors based on SOI technology 8.1 Introduction 8.2 Electrical characterisation of SOI devices 8.2.1 I-V and C-V characterisation before SOI membrane formation 8.2.2 Characterisation of the diode and resistive temperature sensors 8.3 Thermal characterisation of SOI devices 8.3.1 I-V analysis of the MOSFET heater after membrane formation 8.3.2 Temperature measurements of the MOSFET heaters and membrane 8.3.3 Thermal imaging of SOI device 8.4 Response of SOI sensors to organic vapours 8.5 Conclusions 8.6 References CHAPTER 9: Aims and conclusions 9.1 Research procedure and objectives 9.1.1 Room temperature chemFET sensors with a conducting polymer films 9.1.2 Static and dynamic analysis of room temperature chemFET sensors response to organic vapours 9.1.3 The affect of water concentration on the response and relative baseline of room temperature chemFET sensors 9.1.4 The affect of temperature on the response and relative baseline of room temperature chemFET sensors 9.1.5 The development of micro-hot plate gas sensors based in SOI technology 9.1.6 Thermal electrical characterisation of SOI heaters 9.1.7 Project objectives 267 269 265 263 262 260 249 252 254 256 257 257 258 244 231 231 232 234 238 238 226 230 231

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9.2 Application of CMOS sensors 9.3 Smart CMOS gas sensors 9.4 Future work 9.5 References APPENDIX A: Circuit diagrams APPENDIX B: LabVIEW programs and flow diagrams

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List of Figures
Heading Figure 1.1: A simplified schematic of an electronic nose instrument and biological olfactory system Figure 2.1: Schematic of (a) GasFET and (b) MISCAP Figure 2.2: Dipole formation of a Pd-MOS device Figure 2.3: Interaction sites for analyte on a polymer chemoresistor Figure 3.1: Examples of (a) SIMOX and (b) wafer bonding process in forming SOI wafers Figure 3.2: SOI sensor configuration with FET heater and associated electronics Figure 3.3: Schematic of a sensor and reference with integrated circuitry Figure 3.4: Schematic overview of a single chemFET sensor with channel dimensions of 385 m 10 m Figure 3.5: Drawing of final chemFET sensor array Figure 3.6: Fabrication process for the room temperature chemFET sensor Figure 3.7: SOI micro-hot plate Figure 3.8: Interdigitated heater designs Figure 3.9: Square FET heater design Figure 3.10: (a) I-V characteristics of SOI FET heater and (b) lattice temperature Figure 3.11: 3D Thermo-simulation of a FET heater on a SOI Membrane Figure 3.12: 3D Simulations of square and interdigitated with gap FET heaters Figure 3.13: Mechanical simulation of a SOI device showing upward deformation of the membrane Figure 3.14: Mechanical simulation of the tensile stress within the buried oxide layer Figure 3.15: Electrode structures for Matra and SUMC processes Figure 3.16: SOI chemFET sensor structures Figure 3.17: Layout of a spreading and a channel resistive temperature sensors Figure 3.18: Diode temperature sensors Figure 3.19: Bipolar temperature sensors (Matra only) Figure 3.20: Final design for Matra process Figure 3.21: Final design for SUMC process Page 2 18 18 31 48 50 52 55 56 58 60 63 64 65 67 67 69 70 72 73 75 76 77 79 81

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Figure 4.1: Schematic and photograph of the UMIST chemFET sensor Figure 4.2: Photograph of fabricated chemFET sensor Figure 4.3: (a) Photograph of the sensing area and (b) photograph of the packaged device Figure 4.4: SEM of chemically prepared CVD deposited poly(pyrrole) Figure 4.5: AFM plot of composite polymer material Figure 4.6: Photograph of composite polymer deposition system Figure 4.7: Schematic of electrochemically grown polymer deposition unit (not to scale) Figure 4.8: Potential growth transients for poly(pyrrole)/BSA (PPY/BSA) and poly(bithiophene)/TBATFB (PBT/TBATFB). Figure 4.9: SEMs of (a) poly(pyrrole)/BSA and (b) poly(bithiophene)/TBATFB Figure 4.10: Photograph of electrochemically grown conducting polymers after deposition Figure 4.11: 3D profile of poly(pyrrole) deposited by CVD Figure 4.12: 3D profile of poly(styrene-co-butadiene) Figure 4.13: 3D profile of poly(pyrrole)/BSA Figure 4.14: Photograph of fabricated SOI device Figure 4.15: Photograph of the underside of a SOI device, with zoomed in section after removal of most of the handle silicon. Figure 4.16: A photograph of the etching jig used for the SUMC devices Figure 4.17: Schematic of SnO2 deposition system Figure 4.18: Schematic and photograph of SRL127 Figure 4.19: Schematic and photograph of SRL170 Figure 5.1: Schematic overview of FIA test station Figure 5.2: Schematic of chemical hardware Figure 5.3: Photograph of the FIA test station Figure 5.4: Schematic of the sensor chamber Figure 5.5: Simplified circuit diagram of MFC electronics hardware Figure 5.6: Front panel of FIA control software Figure 5.7: Flow diagram of testing protocols Figure 5.8: I-V characterisation instrument Figure 5.9: Schematic of I-V characterisation hardware Figure 5.10: (a) Typical noise values and (b) characterisation of BSS88 transistors Figure 5.11: Constant current measurement instrument Figure 5.12: Simplified circuit diagram of electronic hardware Figure 5.13: Noise and response measurements for constant current measurement instrument Figure 5.14: Testing protocols for I-V and constant current measurement instruments Figure 6.1: Typical shift in I-V characteristics of a p-channel (MISFET) chemFET sensor employing poly(pyrrole) to ethanol vapour in air, at a fixed gate voltage of 0.6 volts Figure 6.2: Typical responses of n-channel (MOSFET) chemFET sensors employing composite polymer films as the gate to toluene vapour in air Figure 6.3: Typical responses of n-channel (MOSFET) chemFET sensors employing composite polymer films as the gate to ethanol vapour in

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air Figure 6.4: Response of n-channel (MOSFET) chemFET sensors employing a composite polymer films deposited onto a solid gold gate to toluene vapour in air Figure 6.5: Typical responses of n-channel (MOSFET) chemFET sensors employing electrochemically deposited polymer films as the gate to ethanol vapour in air Figure 6.6: Typical responses of n-channel (MOSFET) chemFET sensors employing electrochemically deposited polymer films as the gate to toluene vapour in air Figure 6.7: Response of n-channel (MOSFET) chemFET sensors employing electrochemically deposited polymer films deposited onto a solid gold gate to toluene vapour in air Figure 6.8: Transient response of chemFET sensors with composite polymer films to toluene vapour in air modelled to a double exponential expression Figure 6.9: Transient recovery of chemFET sensors with composite polymer films to toluene vapour in air modelled to a double exponential expression Figure 6.10: Transient response of chemFET sensors with electrochemically deposited polymer films to ethanol vapour in air modelled to a double exponential expression Figure 6.11: Transient recovery of chemFET sensors with electrochemically deposited polymer films to ethanol vapour in air modelled to a double exponential expression Figure 6.12: on (left) and off (right) transients for chemFET sensors employing composite polymer films to toluene vapour in air at 30 oC. Figure 6.13: on (left) and off (right) transients for chemFET sensors employing composite polymer films to ethanol vapour in air at 30 oC. Figure 6.14: on1 (left) and on2 (right) transients for chemFET sensors employing electrochemically deposited polymer films to toluene vapour in air at 30 oC. Figure 6.15: off1 (left) and off (right) transients for chemFET sensors employing electrochemically deposited polymer films to toluene vapour in air at 30 oC. Figure 6.16: on1 (left) and on2 (right) transients for chemFET sensors employing electrochemically deposited polymer films to ethanol vapour in air at 30 oC. Figure 6.17: off1 (left) and off2 (right) transients for chemFET sensors employing electrochemically deposited polymer films to ethanol vapour in air at 30 oC. Figure 6.18: The affect of ethanol vapour in air on drain source current of UMIST chemFET sensors employing a chemically prepared polymer films at 30 oC. Figure 6.19: Broad range static response of chemFET sensor employing composite polymer films to toluene vapour in air Figure 6.20: Broad range static response of chemFET sensor employing composite polymer films to ethanol vapour in air

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Figure 6.21: Broad range static response of chemFET sensor employing electrochemically deposited polymer films to ethanol vapour in air Figure 6.22: Broad range static response of chemFET sensor employing electrochemically deposited polymer films to toluene vapour in air Figure 6.23: The response of chemFET sensors with three different thicknesses of poly(styrene-co-butadiene) to toluene and ethanol vapour in air. Figure 6.24: The response of chemFET sensors with three different thicknesses of poly(9-vinylcarbazole) to toluene and ethanol vapour in air. Figure 6.25: The affect of toluene and ethanol vapour in air on n-channel chemFET sensors employing composite polymer films at constant water concentration and temperature (4500 PPM, 30 oC). Figure 6.26: The affect of toluene vapour on chemFET sensors employing an electrochemically deposited polymer films at constant water concentration and temperature (4500 PPM, 30 oC). Figure 7.1: The affect of water concentration on the relative baseline of chemFET sensors employing poly(ethylene-co-vinyl acetate) and poly(styrene-co-butadiene) at 30 oC Figure 7.2: The affect of water concentration on chemFET sensors employing composite polymer films to toluene vapour in air at 30 oC Figure 7.3: The affect of water concentration on chemFET sensors employing composite polymer films to ethanol vapour in air at 30 oC Figure 7.4: The affect of water concentration on the relative baseline of chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films at 30 oC Figure 7.5: The affect of water concentration on the response of chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films to ethanol vapour in air at 30 oC Figure 7.6: The affect of water concentration on the response of chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films to toluene vapour in air at 30 oC Figure 7.7: The shift in VGDS for a chemFET sensor with an open and solid gate to temperature between 30 60 oC at constant water concentration (4500 PPM) Figure 7.8: The affect of temperature on chemFET sensors employing composite polymer films on the response at fixed water concentration on 4500 PPM to toluene vapour in air Figure 7.9: The affect of temperature on chemFET sensors employing composite polymer films on the response at fixed water concentration on 4500 PPM to toluene vapour in air Figure 7.10: Modularised log plot of the effect of temperature on chemFET sensors employing composite polymer films at fixed toluene (left) and ethanol (right) vapour in air Figure 7.11: The affect of temperature on the water dependency on the relative baseline of chemFET sensors employing poly(ethylene-co-vinyl acetate) and poly(styrene-co-butadiene) polymer films Figure 7.12: The shift in VGDS for an open and solid gate chemFET sensor with

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electrochemically deposited polymer films to temperature at fixed water concentration Figure 7.13: The affect of temperature chemFET sensors employing electrochemically deposited polymer films to ethanol vapour in air at fixed water concentration (4500 PPM). Figure 7.14: The response of chemFET sensors employing electrochemically deposited polymer films to toluene vapour in air at constant water concentration (4500 PPM) at 40 oC (left) and 50 oC (right) Figure 7.15: The affect of temperature on the water dependency of the baseline of chemFET sensors employing electrochemically deposited polymer films Figure 7.16: Dynamic response of resistive composite sensors to ethanol and toluene vapour in air at constant temperature and water concentration (30 oC and 4500 PPM) Figure 7.17: Static response of resistive devices to toluene and ethanol vapour in air at constant temperature and water concentration (30 oC / 4500 PPM) Figure 7.18: The affect of water concentration on resistive composite polymer sensors at 30 oC Figure 7.19: The affect of temperature on resistive composite sensors at fixed water concentration (4500 PPM) Figure 7.20: The affect of temperature on the static response of resistive composite polymer sensors to toluene and ethanol vapour in air Figure 8.1: MOSFET characteristics in the subthreshold, linear and saturated regions for FET1, FET2 and FET3 Figure 8.2: C-V analysis of the gate oxide of the MOSFET heaters Figure 8.3: Forward I-V characteristics for the temperature diodes and the affect of temperature on the diodes operated at a constant current of 10 A Figure 8.4: The affect of temperature on the resistance of a spreading resistor Figure 8.5: Long term measurement of the temperature sensors Figure 8.6: The I-V characteristics of FET 1 for devices with and without a membrane Figure 8.7: The I-V characteristics of FET 2 for devices with and without a membrane Figure 8.8: The I-V characteristics of FET 3 for devices with and without a membrane Figure 8.9: Dynamic characteristics of two MOSFET heaters Figure 8.10: Temperature measurement of the membrane Figure 8.11: The dynamic output characteristics of a diode temperature sensor to a modulated MOSFET heater input. Figure 8.12: The dynamic output characteristics of a diode temperature sensor to a modulated MOSFET heater input at a fixed bias Figure 8.13: Layout of the SOI structure and an equivalent circuit of the lumped model Figure 8.14: Thermal image of SOI device with two MOSFET heaters in operation Figure 8.15: Thermal images of powering up of two SOI MOSFET heaters Figure 8.16: Dynamic characteristics of SOI chemoresistors to toluene and

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ethanol vapour in air Figure 8.17: Static characteristics of SOI chemoresistors with poly(styrene-cobutadiene) coating to toluene and ethanol vapour in air Figure 9.1: Design of a new SOI device for high temperature applications with integrated transducer circuitry Figure 9.2: Diagrams of the op-amp transducer circuit with a fixed gain of 40 implemented in the latest SOI design

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List of Tables
Heading Table 1.1: Popular gas sensor technologies Table 1.2: Commercially available electronic nose instruments Table 1.3: A typical specification for a cabin monitor for the automotive industry Table 3.1: Room temperature chemFET sensors, open and closed gate combinations Table 3.2: Room temperature chemFET device fabrication parameters Table 3.3: Physical properties of the materials used in the SOI heater simulations Table 3.4: The physical constants used by the SOLIDIS-ISE simulator Table 3.5: Evaluation of SOI heater structures with differing membrane dimensions Table 3.6: Typical resistance values for spreading resistors over the operating temperature range Table 3.7: Typical diode saturation values Table 3.8: Material thickness values for Matra and SUMC processes Table 4.1: A comparison of different deposition techniques for conducting polymers (CP = chemically prepared, CM = composite materials, ECP = electrochemically prepared) Table 4.2: Thickness measurements for composite polymer deposited by Cyrano Sciences Inc. USA Table 4.3: Thickness measurements for composite polymer deposited at Warwick University Table 4.4: Thickness measurements for electrochemically deposited polymers, with average and maximum measured thickness Table 5.1: Chemical hardware components Table 5.2: Chemical constants, with temperature ranges, for analytes used in testing. Also minimum saturated PPM available using the refrigeration unit Table 5.3: Volume and exhaust times for the chemical hardware and sensor chamber Table 5.4: Pre/post-clean procedure Table 5.5: The specification of the FIA rig and measurement equipment (*limited by drive op-amp this can be altered to increase the current, i.e. TCA0732DP has a 1A output) Table 6.1: Modelling coefficients for expression (6.11) Table 6.2: Typical time responses of chemFET sensors employing composite and electrochemically deposited polymer films to toluene and ethanol vapour in air at fixed concentrations of 5793 PPMs and 11729 PPMs respectively at constant water concentration and temperature (4500 PPM, 30 oC). (CP1 Poly(ethylene-co-vinyl acetate), CP2 Poly(styrene-co-butadiene), CP3 Poly(9vinylcarbzole), PPY Poly(pyrrole)/BSA, PBT Poly(bithiophene)/TBATFB) Table 6.3: Values of Langmuir isotherm coefficients for chemFET sensors with chemically prepared electrochemically doped film to ethanol vapour in air Page 6 9 11 57 57 66 69 71 74 76 77 97

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Table 6.4: Parameter fits to broad range static response of chemFET sensors employing a composite polymer film to toluene vapour in air, including the confidence interval r2 Table 6.5: Parameter fits to broad range static response of chemFET sensors employing a composite polymer film to ethanol vapour in air, including the confidence interval r2 Table 6.6: Typical sensitivity values for chemFET sensors employing composite polymer films to toluene and ethanol vapour in air over a broad concentration range Table 6.7: Parameter fits to broad range static response for chemFET sensors employing an electrochemically polymer film to ethanol vapour in air, including the confidence interval r2 Table 6.8: Parameter fits to broad range static response for chemFET sensors employing an electrochemically polymer film to toluene vapour in air, including the confidence interval r2 Table 6.9: Typical sensitivity values for chemFET sensors employing composite polymer films to toluene and ethanol vapour in air Table 6.10: Work function measurements of polymer materials Table 6.11: The affect of ethanol vapour in air on the work function values of three conducing polymers. Table 6.12: Detection limits for chemFET sensors employing composite polymers to toluene and ethanol vapour in air at 4500 PPM water concentration and fixed temperature 30 oC Table 6.13: Detection limits for chemFET sensors employing electrochemically deposited polymers to toluene and ethanol vapour in air at 4500 PPM water concentration and fixed temperature 30 oC Table 6.14: A summary of the best fitting models for chemFET sensors employing polymer films to toluene and ethanol vapour in air (SU - deposited at Southampton University) Table 6.15: A summary of the sensitivities, detection limits and response times of chemFET sensors employing conducting polymer films Table 7.1: Modelling coefficients fits for the affect of water concentration on the baseline of chemFET sensors employing poly(ethylene-co-vinyl acetate) and poly(styrene-co-butadiene) polymer films at 30oC Table 7.2: Modelling coefficients for the effect of water concentration on the response of chemFET sensors employing composite polymers to toluene vapour in air (CP3 poly(9-vinylcarbazole) Table 7.3: Modelling coefficients for the affect of water concentration on the response of chemFET sensors employing composite polymers to ethanol vapour in air Table 7.4: Modelling coefficients for the affect of water concentration on the baseline of chemFET sensors employing poly(pyrrole)\BSA and poly(bithiophene)/TBATFB polymer films at 30oC Table 7.5: Modelling coefficients for the affect of water concentration on chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films to ethanol vapour in air at 30 oC Table 7.6: Modelling coefficients for the affect of water concentration on chemFET sensors employing poly(pyrrole)/BSA and

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poly(bithiophene)/TBATFB polymer films to toluene vapour in air at 30 oC Table 7.7: Modelling coefficients for the affect of temperature on the baseline of a solid gate chemFET sensor with a composite polymer coating Table 7.8: Modelling coefficients for the affect of temperature on the relative baseline of chemFET sensors employing composite polymer films at a fixed water concentration Table 7.9: Modelling coefficients for the affect of temperature on the response of chemFET sensors employing composite polymer films to toluene vapour in air at fixed water concentration, from expression (7.30) Table 7.10: Modelling coefficients for the affect of temperature on the response of chemFET sensors employing composite polymer films to ethanol vapour in air at fixed water concentration, from expression (7.30) Table 7.11: Modelling coefficients for the affect of temperature on the relative baseline for chemFET sensors employing poly(ethylene-co-vinyl acetate) and poly(styrene-co-butadiene) polymer films. Table 7.12: Modelling coefficients for the affect of temperature on the relative baseline of chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films at fixed water concentration of 4500 PPM. Table 7.13: Modelling coefficients for the affect of temperature on the response chemFET sensors employing poly(pyrrole)/BSA and poly(bithiophene)/TBATFB polymer films to ethanol vapour in air. Table 7.14: Modelling coefficients for the affect of temperature and water concentration (3000 PPM 9853 PPM) on the baseline for poly(pyrrole)/BSA and poly(bithiophene)/TBATFB Table 7.15: Modelling coefficients for resistive composite polymer sensor to toluene and ethanol vapour at fixed temperature and water concentration (30 oC / 4500 PPM) Table 7.16: Sensitivity values for resistive and chemFET sensors employing poly(styrene-co-butadiene) for toluene and ethanol vapour in air Table 7.17: Modelling coefficients for the dependency of resistive sensors employing a poly(styrene-co-butadiene) polymer films to water concentration Table 7.18: Modelling coefficients for the affect of temperature on the baseline of resistive composite sensors Table 7.19: Modelling coefficients for the affect of temperature on the response of resistive polymer sensors to toluene and ethanol vapour in air Table 7.20: Summary of the effect of water concentration on chemFET sensors employing composite and electrochemically deposited polymers at fixed temperature of 30oC (CP1 poly(ethylene-co-vinyl acetate, CP2 poly(styrene-co-butadiene), CP3 poly(9-vinylcarbazole), PPY/BSA poly(pyrrole)/BSA, PBT/TBATFB poly(bithiophene)/TBATFB) Table 7.21: Summary of the affect of temperature on chemFET sensors employing composite and electrochemically deposited films at constant water concentration (4500 PPM). Table 7.22: Summary of the affect of analyte concentration and temperature on

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resistive sensors employing poly(styrene-co-butadiene) Table 8.1: MOSFET heater characteristics Table 8.2: Diode coefficients for expression (8.1) Table 8.3: Summary of temperature sensors characteristics Table 8.4: Typical time constants of the MOSFET heaters Table 8.5: Typical sensitivity values for SOI chemoresistors Table 9.1: A summary of the numbers and types of polymers employed for each of the experiments carried out in this research Table 9.2: Summary of results for chemFET and resistive sensors employing conducting polymer films. (PPY/BSA Poly(pyrrole)/BSA, PBT/TBATFB Poly(bithiophene)/TBATFB, CP1 Poly(ethyleneco-vinyl acetate), CP2 Poly(styrene-co-butadiene), CP3 Poly(9vinylcarbzole) Table 9.3: Summary of different SOI designs Table 9.4: Characteristics of the temperature sensors used in the MATRA SOI designs

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Summary In recent years, there has been considerable interest in the use of gas/vapour monitors and electronic nose instruments by the environmental, automotive and medical industries. These applications require low cost and low power sensors with high yield and high reproducibility, with an annual prospective market of 1 million pounds. Present device and sensor technologies suffer a major limitation, their incompatibility with a standard silicon CMOS process. These technologies have either operating/annealing temperatures unsuited for MOSFET operation or an inappropriate sensing mechanism. The aim of this research is the development of CMOS compatible gas/vapour sensors, with a low cost of fabrication, high device repeatability and, in the future, transducer sensor amalgamation. Two novel approaches have been applied, utilising bulk CMOS and SOI BiCMOS. The bulk CMOS designs use a MOSFET sensing structure, with an active polymeric gate material, operating at low temperatures (< 100 oC), based on an array device of four elements, with channel lengths of 10 m or 5 m. The SOI designs exploit a MOSFET heater with a chemoresistive or chemFET sensing structure, on a thin membrane formed by the epi-taxial layer. By applying SOI technology, the first use in gas sensor applications, operating temperatures of up to 300 o C can be achieved at a power cost of only 35 mW (simulated). Full characterisation of the bulk CMOS chemFET sensors has been performed using electrochemically deposited (e.g. poly(pyrrole)/BSA)) and composite polymers (e.g. poly(9-vinylcarbazole)) to ethanol and toluene vapour in air. In addition, environmental factors (humidity and temperature) on the response and baseline were investigated. This was carried out using a newly developed flow injection analysis test station, which conditions the test vapour to precise analyte (< 15 PPM of toluene) and water concentrations at a fixed temperature (RT to 105 oC 0.1), with the sensor characterised by either I-V or constant current instrumentation. N-channel chemFET sensors operated at constant current (10 A) with electrochemically deposited and composite polymers showed sensitivities of up to 1.1 V/PPM and 4.0 V/PPM to toluene vapour and to 1.1 V/PPM and 0.4 V/PPM for ethanol vapour, respectively, with detection limits of <20 PPM and <100 PPM to toluene and <20 PPM and 10+ PPM to ethanol vapour (limited by baseline noise), respectively. These responses followed either a power law (composite polymers) or a modified Langmuir isotherm model (electrochemically deposited polymers) with analyte concentration. It is proposed that this reaction-rate limited response is due to an alteration in polymers work function by either a partial charge transfer from the analyte or a swelling effect (polymer expansion). Increasing humidity caused, in nearly all cases a reduction in relative baseline, possible by dipole formation at the gate oxide surface. For the response, increasing humidity had no effect on sensors with composite polymers and an increase for sensors with electrochemically-deposited polymers. Higher temperatures caused a reduction in baseline signal, by a thermal expansion of the polymer, and a reduction in response explained by the analyte boiling point model describing a reduction in the bulk solubility of the polymer. Electrical and thermal characterisation of the SOI heaters, fabricated by the MATRA process, has been performed. I-V measurements show a reduction in drain current for a MOSFET after back-etching, by a degradation of the carrier mobility. Dynamic measurement showed a two stage thermal response (dual exponential), as the membrane reaching equilibrium (100-200 ms) followed by the bulk (1-2 s). A temperature coefficient of 8 mW/oC was measured, this was significantly higher than expected from simulations, explained by the membrane being only partially formed. Diode and resistive temperature sensors showed detection limits under 0.1 oC and shown to measure a modulated heater output of less than 1 oC at frequencies higher than 10 Hz. The principle research objectives have been achieved, although further work on the SOI device is required. The results and theories presented in this study should provide a useful contribution to this research area.

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Acknowledgements
I would like to thank my academic supervisor Prof. Julian Gardner for generously allowing me the opportunity of studying in this field, and for his constant guidance and support during my PhD. I would also like to acknowledge the Engineering and Physical Science Research Council (EPSRC) for their financial support during three years of this study. I am also grateful to all of my friends a colleagues for their constant support and encouragement during the course of this study. For practical work associated with my PhD. I would particularly like to thank the members of the Sensors Research Laboratory, School of Engineering, University of Warwick, including, Mr F. T. Courtney for his assistance in mechanical matters and to Mr G. Searle, Mr S. M. Lee, Mr I. Griffiths, Mr and to Dr M.V. Cole for there help in technical matters. Also Mr D. Chrastina, from the Department of Physics, University of Warwick, with his assistance with certain equipment and the members of the Optical Engineering Laboratory, School of Engineering, University of Warwick. I would also like to acknowledge Prof. P. N. Bartlett for his assistance in modelling and C. Seng for the deposition of electrochemically grown conducting polymers, from the Department of Chemistry, University of Southampton UK and Dr J. Li of Cyrano Sciences, USA for the deposition of composite polymers. Also Prof. N. F. de Rooji, Mr D. Braind, and the other members of the fabrication laboratory of the Insitutute of Microtechnology University of Neuchatel, Switzerland for the fabrication of devices. Furthermore, I would like to acknowledge Dr F. Udrea, Mr C.C. Lu, Dr D. Setaidi and Dr D. Togaru from the Department of Engineering, University of Cambridge, UK with whom I worked in close collaboration in a part of this research. Also Dr G. Ensell, and the other members of the Southampton University Microtecnology Centre, UK for assistance in the fabrication of devices. Lastly, I would like to acknowledge Dr J.V. Hatfield from the Department of Electrical and Electronic Engineering, UMIST, Manchester, UK, with whom I worked in collaboration for some of this study, including donation some of several the devices used in this work.

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Declaration
The work described in this thesis is entirely original and my own, except where otherwise indicated.

Parts of this work have been presented at international conferences and published in the scientific literature listed below:

1. Journal Papers /Books

[1]

J.V. Hatfield, J.A. Covington, J.W. Gardner, GasFETs incorporating conducting polymers as gate materials, Sensors and Actuators B, 65 (1-3) (2000) pp. 253-256.

[2]

J.A. Covington, J.W. Gardner, C. Toh, P.N. Bartlett and D. Briand, The Characterisation of an Electrodeposited Conducting polymer FET Array for Vapour Sensing, Published in Electronic Noses and Olfaction 2000 (Ed. J.W. Gardern, K.C. Persaud), IoP, 2000, pp. 35-42.

[3] J.A Covington, J.W. Gardner, D. Briand, A polymer gate FET sensor array for detecting organic vapours, Sensors and Actuators B, 77 (1-2) (2001) pp. 155-162.
[4]

F. Udrea, J.W. Gardner, D. Setiadi, J.A. Covington, T. Dogaru, C.C. Lu, W.I. Milne, Design and simulations of a new class of SOI CMOS micro hot-plate gas sensors, Sensors and Actuators B: Chemical, 78 (1-3) (2001) pp. 180-190.

2. Conference Papers
[1]

J.V. Hatfield, J.A. Covington, J.W. Gardner, GasFETs incorporating conducting polymers as gate materials, Technical Digest of the Seventh International Meeting on Chemical Sensors, (1998), Beijing, pp. 707-709.

[2] J. A. Covington, J.W. Gardner, J.V. Hatfield, Conducting polymer FET devices for vapour sensing, Proc. Of SPIE Smart Electronics and MEMS (1999), pp. 296-307. [3] D. Setiadi, F. Udrea, W.I. Milne, J.A. Covington, 3D Numerical Simulation of Novel SOI MOSFET Based Gas Sensors, Proceedings of ECS Chemical Sensors (1999), Hawii, pp. 416-419
[3]

J.A Covington, J.W. Gardner, D. Briand, A polymer gate FET sensor array for detecting organic vapours, 8th International Conference on Chemical Sensors, (oral presentation given) (2000), Basel, pp. 166.

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J.A. Covington, J.W. Gardner, C. Toh, P.N. Bartlett and D. Briand, The Characterisation of an Electrodeposited Conducting polymer FET Array for Vapour Sensing, International Symposium on Electronic Noses, (oral presentation), (2000), Brighton, pp. 29-30.

[5] F. Udrea, D. Setiadi, J.W. Gardner, J.A. Covington, C.C. Lu, A novel class of smart gas sensors using CMOS micro-heaters embedded in an SOI membrane. Eurosensors XIV (2000), Copenhagen, pp 707-710.
[6]

M. Cole, J.W. Gardner, J.A. Covington, D. Fife, J.W. Brignell, P.N. Bartlett, Active bridge polymeric resistive device for vapour sensing, Eurosensors XIV (2000) Copenhagen, pp. 895-898.

[7]

C.C. Lu, D. Setiadi, F. Udrea, W.I. Milne, J.A. Covington, J.W. Gardner, 3D Thermo-electro -mechanical simulations of gas sensors based on SOI membranes, Modeling and Simulation of Microsystems (2000) San Diego, pp. 297-300.

[8]

J.W. Gardner, J.A. Covington, F. Udrea, T. Dogaru, C-C Lu, W.I. Milne, SOI-based Micro-hotplate Microcalorimeter Gas Sensor with Integrated BiCMOS Transducer, Transducer 01 & Eurosensors XV, (2001) Munich, pp. 1688-1691.

[9]

C.C. Lu, F. Udrea, J.W. Gardner, D. Setiadi, T. Dogaru, T.H. Tsai, J.A. Covington, Design and Coupled-Effect Simulations of CMOS Micro Gas-Sensors Built on SOI Thin Membranes, Design, Test Integration and Packaging of MEMS/MOEMS, Proc. of SPIE, Vol. 4408 (2001), pp. 86-95.

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Selected Abbreviations and Acronyms

TERM ADC AFM ASIC ANN BAW BiCMOS BSA CCM CMOS CVD DAC DAQ DIO DSA EMC IC I.D. IVC LED LPCVD MFC MFM MOS MOSFET O.D. PARC PBT P.C PCB PPY DEFINITION Analogue to Digital Converter Atomic Force Microscope Application Specific Integrated Circuit Artificial Neural Network Bulk Acoustic Wave Bipolar Complementary Metal Oxide Semiconductor Butane Sulfonate Acid Constant Current Measurement Complementary Metal Oxide Semiconductor Chemical Vapour Deposition Digital to Analogue Converter Data Acquisition Digital Input/Output Decane Sulfonate Acid Electromagnet Compatibility Integrated Circuit Inner Diameter Current-Voltage Characterisation Light Emitting Diode Low Pressure Chemical Vapour Deposition Mass Flow Controller Mass Flow Meter Metal Oxide Semiconductor Metal Oxide Semiconductor Field Effect Transistor Outside Diameter Pattern Recognition Poly(bithiophene) Personal Computer Printed Circuit Board Poly(pyrrole)

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R.H. R.T SAD SAW SCE SEM SOI SPCO SRL TBATFB TTL UV VI VOC

Relative Humidity Room Temperature Sensor Array Device Surface Acoustic Wave Saturated Calomel Electrode Scanning Electron Microscope Silicon-On-Insulator Single Pole Change Over Sensors Research Laboratory Tetrabutyammonium Tetrafluoroborate TransistorTransistor Logic UltraViolet Virtual Instrument Volatile Organic Compound