Solid State Gas Sensing

346 Pages·2009·9.219 MB·English

by  Jan Spannhake, Andreas Helwig, Olaf Schulz, Gerhard Müller (auth.), Elisabetta Comini, Guido Faglia, Giorgio Sberveglieri (eds.)

Solid State Gas Sensing
Elisabetta Comini Guido Faglia
l l
Giorgio Sberveglieri
Editors
Solid State Gas Sensing
1 3
Editors
ElisabettaComini GuidoFaglia
SensorLaboratory SensorLaboratory
CNR-INFMandBresciaUniversity CNR-INFMandBresciaUniversity
ViaValotti,9 ViaValotti,9
25133Brescia 25133Brescia
Italy Italy
GiorgioSberveglieri
SensorLaboratory
CNR-INFMandBresciaUniversity
ViaValotti,9
25133Brescia
Italy
ISBN:978-0-387-09664-3 e-ISBN:978-0-387-09665-0
DOI:10.1007/978-0-387-09665-0
LibraryofCongressControlNumber:2008929496
#2009SpringerScienceþBusinessMedia,LLC
Allrightsreserved.Thisworkmaynotbetranslatedorcopiedinwholeorinpartwithoutthewritten
permissionofthepublisher(SpringerScienceþBusinessMedia,LLC,233SpringStreet,NewYork,
NY10013,USA),exceptforbriefexcerptsinconnectionwithreviewsorscholarlyanalysis.Usein
connectionwithanyformofinformationstorageandretrieval,electronicadaptation,computer
software,orbysimilarordissimilarmethodologynowknownorhereafterdevelopedisforbidden.
Theuseinthispublicationoftradenames,trademarks,servicemarks,andsimilarterms,evenifthey
arenotidentifiedassuch,isnottobetakenasanexpressionofopinionastowhetherornottheyare
subjecttoproprietaryrights.
Printedonacid-freepaper
springer.com
Preface
Gas sensor technology has advanced remarkably during the past few
decades and is becoming an essential technology. Many gas sensors are
now commercially available and researchers are making efforts, thanks to
pioneering novel ideas, to develop next-generation gas sensors, having all
the necessary requirements, such as small size, low production costs and
power consumption.
This book covers all gas sensor topics, a research field with an increasing
interestin the last few years due to the demands ofreliable,inexpensive and
portable systems for environmental monitoring, indoor air quality, food
quality control and many other applications. The goal of this book is to
provide a critical assessment of the new trends in the gas sensor field, by
describingtheworkingprincipleandtheapplicationsrelatedtothedifferent
typesofsensorsandpayingattentiontotherecentimpactofnanotechnology
onthefield.
Nanotechnologyisanewfieldthatwilldramaticallychangesolid-stategas
sensing. In the last few decades, the study of one-dimensional (1D) materials
has become a primary focus in nanoscience and nanotechnology. With
reductioninsize,novelelectrical,mechanical,chemicalandopticalproperties
havebeenintroduced,whicharelargelybelievedtobetheresultofsurfaceand
quantum confinement effects. For example, nanowire-like structures are the
ideal system for studying the transport process in one-dimensionally (1D)
confined objects, which are of benefit not only for understanding the
fundamental phenomena in low dimensional systems but also for developing
newgenerationnanodevicesandgassensorswithhighperformances.
Thefirstchapterisdevotedtomicro-fabricationforgassensors.Following
chapters deal with the subject on the base of the transduction principle as
electrical,permittivity,fieldeffect,electrochemical,optical,thermometricand
mass(bothquartzandcantilevertypes)based.
The book is characterized by a methodical and thorough treatment of the
subject matters. The chapters are logically related, and each has its own
introduction and bibliography, in order to make it accessible to any reader
notwithstandinghisbackgroundonrelatedsubjects.
v
vi Preface
Sincethelastyearshaveseenanenormousamountofactivityinthefieldof
gas 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.
Italy ElisabettaComini
May2008 GuidoFaglia
GiorgioSberveglieri
Contents
1 Micro-FabricationofGasSensors........................... 1
JanSpannhake,AndreasHelwig,OlafSchulz,
andGerhardMu¨ller
1.1 Introduction...................................... 1
1.2 GasSensorsandMEMSMiniaturization
Techniques ....................................... 3
1.2.1 SiliconasaSensorMaterial .................... 3
1.2.2 ThermalSensorsandActuators ................. 4
1.2.3 ThermalMicrostructures....................... 6
1.3 SpecificSensorExamples............................ 11
1.3.1 HeatConductivitySensors ..................... 12
1.3.2 Metal-Oxide-BasedGasSensors................. 16
1.3.3 Field-EffectGasSensors....................... 19
1.3.4 ThermalInfraredEmitters ..................... 21
1.4 Gas-SensingMicrosystems........................... 22
1.4.1 LowFalse-Alarm-RateFireDetection............ 23
1.4.2 AirQualityMonitoringandLeakDetection ....... 27
1.5 IndustrializationIssues.............................. 34
1.5.1 InitiatingaSystem-LevelInnovation ............. 34
1.5.2 BuildingAdded-ValueLines.................... 34
1.5.3 MasteringtheMEMSChallenge................. 36
1.5.4 CooperationAcrossTechnicalandEconomic
Interfaces................................... 37
1.5.5 CreatingHigherAddedValue................... 40
1.6 ConclusionsandOutlook............................ 40
References............................................. 41
2 Electrical-BasedGasSensing............................... 47
ElisabettaComini,GuidoFagliaandGiorgioSberveglieri
2.1 Introduction...................................... 47
2.2 MetalOxideSemiconductorSurfaces .................. 49
2.2.1 GeometricStructures.......................... 49
2.2.2 ElectronicStructures.......................... 50
vii
viii Contents
2.3 ElectricalPropertiesofMetalOxideSemiconductor
Surfaces.......................................... 50
2.3.1 SemiconductorStatistics....................... 50
2.3.2 SurfaceStates ............................... 52
2.3.3 SurfaceSpaceChargeRegion................... 54
2.3.4 SurfaceDipoles .............................. 57
2.4 ConductionModelsofMetalOxidesSemiconductor ...... 58
2.4.1 PolycrystallineMaterialswithLargeGrains........ 60
2.4.2 PolycrystallineMaterialswithSmallGrains........ 61
2.4.3 Mono-crystallineMaterials..................... 63
2.5 AdsorptionoverMetalOxideSemiconductorSurfaces..... 65
2.5.1 PhysicalandChemicalAdsorption............... 65
2.5.2 SurfaceReactionsTowardsElectricalProperties.... 67
2.5.3 CatalystsandPromoters....................... 69
2.6 DepositionTechniques.............................. 70
2.6.1 Three-DimensionalNanostructures .............. 70
2.6.2 Two-DimensionalNanostructures ............... 71
2.6.3 One-DimensionalMaterials .................... 80
2.7 ConductometricSensorFabrication ................... 84
2.7.1 SubstrateandHeater.......................... 84
2.7.2 ElectricalContacts............................ 88
2.7.3 HeatingTreatments........................... 89
2.7.4 Dopings,CatalystsandFilters .................. 90
2.8 TransductionPrinciplesandRelatedNovelDevices....... 92
2.8.1 DCResistance............................... 92
2.8.2 ACImpedance............................... 94
2.8.3 ResponsePhotoactivation...................... 95
2.9 ConclusionsandOutlook............................ 99
References............................................. 99
3 Capacitive-TypeRelativeHumiditySensorwithHydrophobic
PolymerFilms .......................................... 109
YoshihikoSadaoka
3.1 Introduction...................................... 109
3.2 FundamentalAspects............................... 110
3.2.1 SorptionIsothermsofPolymers ................. 110
3.2.2 WaterSorptionBehaviorofPolymers ............ 111
3.2.3 EffectsoftheSorbedWaterontheDielectric
Properties................................... 111
3.3 CharacterizationofPolymers......................... 113
3.3.1 SorptionIsotherms ........................... 113
3.3.2 FT–IRMeasurement.......................... 115
3.3.3 Solvatochromism............................. 117
3.3.4 CapacitanceChangeswithWaterSorption......... 120
3.3.5 Cross-LinkedPolymer......................... 124
Contents ix
3.4 Humidity-Sensors-BasedHydrophobicPolymer
ThinFilms ....................................... 130
3.4.1 Poly-Methylmethacrylate-BasedHumidity
Sensor ..................................... 131
3.4.2 CharacteristicsofCross-LinkedPMMA-Based
Sensor ..................................... 133
3.4.3 Polysulfone-basedSensor ...................... 136
3.4.4 Acetylene-TerminatedPolyimide-basedSensor ..... 138
3.4.5 Cross-LinedFluorinatedPolyimide-BasedSensor... 143
3.4.6 ImprovementsUsingMEMSTechnology ......... 145
References............................................. 149
4 FETGas-SensingMechanism,ExperimentalandTheoretical
Studies................................................ 153
AnitaLloydSpetz,MagnusSkoglundh,andLarsOjama¨e
4.1 Introduction...................................... 153
4.2 BriefSummaryoftheDetectionMechanism
ofFETDevices.................................... 154
4.3 UHVStudiesofFETSurfaceReactions ................ 157
4.4 TEMandSEMStudiesoftheNanostructure
ofFETSensingLayers.............................. 160
4.5 MassSpectrometryforAtmosphericPressureStudies...... 161
4.6 TheScanningLightPulseTechnology.................. 162
4.7 DRIFTSpectroscopyforInSituStudiesofAdsorbates.... 163
4.8 AtomisticModellingofChemicalReactions
onFETSensorSurfaces............................. 168
4.9 NanoparticlesasSensingLayersinFETDevices ......... 171
4.10 SummaryandOutlook.............................. 173
References............................................. 174
5 Solid-StateElectrochemicalGasSensing...................... 181
NorioMiura,PerumalElumalai,VladimirV.Plashnitsa,
TaroUeda,RyotaroWama,andMasahiroUtiyama
5.1 Introduction...................................... 181
5.2 Mixed-Potential-TypeSensors........................ 185
5.2.1 High-Temperature-TypeNOxSensors............ 185
5.2.2 ImprovementinNO SensitivitybyAdditives ...... 189
2
5.2.3 Hydrocarbon(C H orCH )Sensors............. 191
3 6 4
5.2.4 UseofNanostructuredNiO-BasedMaterials....... 192
5.2.5 NanosizedAuThin-LayerforSensingElectrode.... 196
5.3 AmperometricSensors.............................. 198
5.4 ImpedancemetricSensors............................ 200
5.4.1 SensingofVariousGasesinppmLevel ........... 200
5.4.2 EnvironmentalMonitoringofC H inppb
3 6
Level ...................................... 201
x Contents
5.5 Solid-StateReferenceElectrode....................... 204
5.6 ConclusionsandFutureProspective ................... 205
References............................................. 206
6 OpticalGasSensing...................................... 209
IlariaCacciariandGiancarloC.Righini
6.1 Introduction...................................... 209
6.2 SpectroscopicDetectionSchemes...................... 210
6.3 Ellipsometry...................................... 213
6.4 SurfacePlasmonResonance.......................... 216
6.5 Guided-WaveConfigurationsforGasSensing ........... 221
6.5.1 IntegratedOpticalSPRSensors ................. 223
6.5.2 FiberOpticSPRSensors....................... 223
6.5.3 ConventionalandMicrostructuredFibersforGas
Sensing..................................... 225
6.6 Conclusions ...................................... 229
References............................................. 231
7 ThermometricGasSensing................................. 237
Istva´nBa´rsony,CsabaDu¨cs}oandPe´terFu¨rjes
7.1 DetectionofCombustibleGases ...................... 237
7.1.1 Combustion................................. 237
7.1.2 ThermalConsiderationsduringCombustion ....... 238
7.1.3 Catalysis.................................... 239
7.1.4 ExplosiveMixtures ........................... 240
7.2 CatalyticSensing .................................. 241
7.2.1 Pellistors ................................... 242
7.2.2 MicrocalorimetersinEnzymaticReactions ........ 248
7.3 ThermalConductivitySensors........................ 249
7.4 CalorimetricSensorsMeasuringAdsorption/Desorption
Enthalpy......................................... 251
7.5 MEMSandSiliconComponents...................... 251
7.5.1 ThermalConsiderations ....................... 252
7.5.2 TemperatureReadout......................... 254
7.5.3 IntegratedCalorimetricSensors ................. 256
7.6 SensorArraysandElectronicNoses ................... 257
References............................................. 259
8 AcousticWaveGasandVaporSensors ....................... 261
SamuelJ.Ippolito,AdrianTrinchi,DavidA.Powell,
andWojtekWlodarski
8.1 Introduction...................................... 261
8.1.1 AcousticWavesinElasticMedia ................ 263
8.1.2 AdvantagesofAcoustic-Wave-BasedGas-Phase
Sensors..................................... 266
Contents xi
8.2 ThicknessShearMode(TSM)-BasedGasSensors ........ 267
8.2.1 QuartzCrystalMicrobalance(QCM)-BasedGas
Sensors..................................... 268
8.2.2 Thin-FilmResonator(TFR)-BasedGasSensors .... 276
8.3 SurfaceAcousticWave(SAW)-BasedGasSensors........ 282
8.3.1 ConventionalSAWGasSensors................. 285
8.3.2 Multi-LayeredSAWGasSensors................ 286
8.3.3 GasandVaporSensitivity...................... 286
8.3.4 SAWDeviceGasSensorPerformance ............ 291
8.4 ConcludingRemarks ............................... 296
References............................................. 296
9 Cantilever-BasedGasSensing .............................. 305
HansPeterLang
9.1 IntroductiontoMicrocantilever-BasedSensing........... 305
9.1.1 EarlyApproachestoMechanicalSensing.......... 305
9.1.2 CantileverSensors............................ 306
9.1.3 DeflectionMeasurement....................... 307
9.2 ModesofOperation................................ 310
9.2.1 StaticMode................................. 310
9.2.2 DynamicMode .............................. 311
9.3 Functionalization.................................. 312
9.4 ExampleofanOpticalBeam-DeflectionSetup ........... 313
9.4.1 GeneralDescription .......................... 313
9.4.2 Cantilever-BasedElectronicNoseApplication...... 314
9.5 ApplicationsofCantilever-BasedGasSensors ........... 316
9.5.1 GasSensing................................. 316
9.5.2 ChemicalVaporDetection ..................... 318
9.5.3 ExplosivesDetection.......................... 319
9.5.4 GasPressureandFlowSensing.................. 321
9.6 OtherTechniques.................................. 322
9.6.1 MetalOxideGasSensors ...................... 322
9.6.2 QuartzCrystalMicrobalance ................... 323
9.6.3 ConductingPolymerSensors.................... 323
9.6.4 SurfaceAcousticWaves ....................... 323
9.6.5 FieldEffectTransistorSensorsDevices ........... 324
References............................................. 325
Index..................................................... 329