Table Of ContentSpectroscopyfor Materials
Characterization
Spectroscopy for Materials Characterization
Edited by
Simonpietro Agnello
Department of Physics and Chemistry – Emilio Segrè
University of Palermo
Palermo
Italy
Thiseditionfirstpublished2021
©2021byJohnWiley&Sons,Inc.
PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey
PublishedsimultaneouslyinCanada.
Allrightsreserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmitted,
inanyformorbyanymeans,electronic,mechanical,photocopying,recordingorotherwise,exceptas
permittedbylaw.Adviceonhowtoobtainpermissiontoreusematerialfromthistitleisavailableat
http://www.wiley.com/go/permissions.
TherightofSimonpietroAgnellotobeidentifiedastheauthoroftheeditorialmaterialinthisworkhasbeenasserted
inaccordancewithlaw.
RegisteredOffice
JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ07030,USA
EditorialOffice
111RiverStreet,Hoboken,NJ07030,USA
Fordetailsofourglobaleditorialoffices,customerservices,andmoreinformationaboutWileyproductsvisitusat
www.wiley.com.
Wileyalsopublishesitsbooksinavarietyofelectronicformatsandbyprint-on-demand.Somecontentthatappearsin
standardprintversionsofthisbookmaynotbeavailableinotherformats.
LimitofLiability/DisclaimerofWarranty
Inviewofongoingresearch,equipmentmodifications,changesingovernmentalregulations,andtheconstantflowof
informationrelatingtotheuseofexperimentalreagents,equipment,anddevices,thereaderisurgedtoreviewand
evaluatetheinformationprovidedinthepackageinsertorinstructionsforeachchemical,pieceofequipment,reagent,
ordevicefor,amongotherthings,anychangesintheinstructionsorindicationofusageandforaddedwarningsand
precautions.Whilethepublisherandauthorshaveusedtheirbesteffortsinpreparingthisbook,theymakeno
representationsorwarrantieswithrespecttotheaccuracyorcompletenessofthecontentsofthisworkandspecifically
disclaimallwarranties,includingwithoutlimitationanyimpliedwarrantiesofmerchantabilityorfitnessfora
particularpurpose.Nowarrantymaybecreatedorextendedbysalesrepresentatives,writtensalesmaterialsor
promotionalstatementsforthiswork.Thisworkissoldwiththeunderstandingthatthepublisherisnotengagedin
renderingprofessionalservices.Theadviceandstrategiescontainedhereinmaynotbesuitableforyoursituation.You
shouldconsultwithaprofessionalwhereappropriate.Neitherthepublishernorauthorshallbeliableforanylossof
profitoranyothercommercialdamages,includingbutnotlimitedtospecial,incidental,consequential,orother
damages.Thefactthatanorganization,website,orproductisreferredtointhisworkasacitationand/orpotential
sourceoffurtherinformationdoesnotmeanthatthepublisherandauthorsendorsetheinformationorservicesthe
organization,website,orproductmayprovideorrecommendationsitmaymake.Further,readersshouldbeaware
thatwebsiteslistedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswrittenandwhenitis
read.Neitherthepublishernorauthorsshallbeliableforanylossofprofitoranyothercommercialdamages,including
butnotlimitedtospecial,incidental,consequential,orotherdamages.
Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactourCustomerCare
DepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)572-3993orfax(317)
572-4002.
Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynotbe
availableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteatww.wiley.com.
LibraryofCongressCataloging-in-PublicationDataAppliedfor
ISBN:9781119697329
CoverdesignbyWiley
Coverimage:©khalus/gettyimages
Setin9.5/12.5ptSTIXTwoTextbyStraive,Pondicherry,India
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xv
ListofContributors xvii
1 Radiation–MatterInteractionPrinciples:OpticalAbsorptionandEmissioninthe
Visible-UltravioletRegion 1
SimonpietroAgnello
1.1 EmpiricalAspectsofRadiation–MatterInteraction 1
1.1.1 OpticalAbsorption:TheLambert–BeerLaw 1
1.1.2 Emission:FluorescenceandPhosphorescence 5
1.2 MicroscopicPointofView 7
1.2.1 EinsteinCoefficients 7
1.2.2 OscillatorStrength,Lifetime,QuantumYield 11
1.2.3 VibronicStates:HomogeneousandInhomogeneousLineshape 14
1.2.4 JablonskiEnergyLevelDiagram:PermittedandForbiddenTransitions 20
1.2.5 ExcitedStatesRateEquations 22
1.3 InstrumentalSetups 23
1.3.1 TypicalBlockDiagramofSpectrometers 23
1.3.2 LightSources 24
1.3.3 DispersionElements:GratingsandResolutionPower 25
1.3.4 Detectors:Photodiode,Photomultiplier,ChargeCoupledDevice 27
1.4 CaseStudies 29
1.4.1 OpticalAbsorptioninVisible-UltravioletRange 29
1.4.1.1 ScanningDevice(BandwidthandScanningSpeedEffects) 29
1.4.1.2 CCDFiberOpticDevice 31
1.4.2 Photoluminescence 31
1.4.2.1 EmissionandExcitationSpectra:EnergyLevelsReconstruction 32
References 33
2 Time-ResolvedPhotoluminescence 35
MarcoCannasandLaviniaVaccaro
2.1 IntroductiontoPhotoluminescenceSpectroscopy 35
2.1.1 PhotoluminescencePropertiesRelatedtoPointsDefects:Electron–PhononCoupling 35
2.1.2 OpticalTransitions:TheFranck–CondonPrinciple 38
2.1.3 Zero-PhononLine 40
vi Contents
2.1.4 PhononLineStructure 43
2.1.5 VibrationalStructure 45
2.1.6 InhomogeneousEffects 48
2.2 ExperimentalMethodsandAnalysis 48
2.2.1 Time-ResolvedLuminescence 48
2.2.2 Site-SelectiveLuminescence 50
2.2.3 BasicDesignofExperimentalSetup:PulsedLaserSources;Monochromators;
Detectors 51
2.2.3.1 TunableLaser 52
2.2.3.2 Time-ResolvedDetectionSystem:SpectrographandIntensifiedCCDCamera 52
2.3 CaseStudies:LuminescentPointDefectsinAmorphousSiO 54
2
2.3.1 EmissionSpectraandLifetimeMeasurements 55
2.3.2 Zero-PhononLineProbedbySite-SelectiveLuminescence 58
References 63
3 UltrafastOpticalSpectroscopies 65
AliceSciortinoandFabrizioMessina
3.1 FemtosecondSpectroscopy:AnOverview 65
3.2 UltrafastOpticalPulses 67
3.2.1 GeneralProperties 67
3.2.1.1 DispersionEffect:GroupVelocityDispersion 67
3.2.2 NonlinearOptics:BasisandApplications 69
3.2.2.1 SecondHarmonicGenerationandSumFrequencyGeneration 69
3.2.2.2 NoncollinearOpticalParametricAmplifier 70
3.2.2.3 SupercontinuumGeneration 72
3.3 TransientAbsorptionSpectroscopy 73
3.3.1 TheExperimentalMethod 74
3.3.2 TypicalExperimentalSetups 76
3.3.3 DataAnalysisandInterpretation 78
3.4 UltrafastFluorescenceSpectroscopies 79
3.4.1 FLUC:TheExperimentalMethod 80
3.4.2 FLUC:TypicalExperimentalSetups 80
3.4.3 FLUC:DataAnalysisandInterpretation 82
3.4.4 Kerr-BasedFemtosecondFluorescenceSpectroscopy 82
3.5 FemtosecondStimulatedRamanSpectroscopy 83
3.5.1 TheExperimentalMethod 83
3.5.2 TypicalExperimentalSetups 84
3.5.3 DataAnalysisandInterpretation 87
3.6 CaseStudies 88
3.6.1 UltrafastRelaxationDynamicsofMoleculesinSolutionPhase 88
3.6.2 RelaxationofExcitedChargeCarriersandExcitonsinSemiconductorNanoparticles 89
3.6.3 UltrafastRelaxationDynamicsofCarbon-basedNanomaterials 91
References 92
4 ConfocalandTwo-PhotonSpectroscopy 97
GiuseppeSancataldoandValeriaVetri
4.1 IntroductionandHistoricalPerspectives 97
4.1.1 PointSpreadFunctionandOpticalResolution 98
Contents vii
4.1.2 OpticalSectioningandImagingof3DSamples 101
4.2 FluorescenceImaging 102
4.2.1 LaserScanningConfocalFluorescenceMicroscope 103
4.2.2 Two-PhotonMicroscope 105
4.2.3 TheImportanceofSamplePreparationfromSolidStatetoDynamicSpecimens 108
4.2.4 SettingUpaMeasurement 109
4.3 SpectroscopyUsingaMicroscope 110
4.3.1 ObservablesinFluorescenceMicroscopy 111
4.3.2 MeasuringDynamics:GainingInformationBelowResolution 113
4.4 CaseStudies 117
4.4.1 UnderstandingMicrostructuresandMechanisticAspectsinMaterials 117
4.4.2 FluctuationMethodsfortheAnalysisofNanosystems 121
References 124
5 InfraredAbsorptionSpectroscopy 129
TizianaFioreandClaudiaPellerito
5.1 Fundamentals 129
5.1.1 Introduction 130
5.1.2 BasicPrinciples 130
5.1.3 InfraredSpectra 135
5.1.4 FourierTransformInfraredSpectrometers(Interferometers) 137
5.2 SourcesandDetectors 140
5.3 TechniquesandSamplingMethods 144
5.3.1 TransmissionMethods 144
5.3.1.1 SolidSamples 144
5.3.1.2 LiquidandSolutionSamples 147
5.3.1.3 GasSamples 148
5.3.2 AttenuatedTotalReflectance(ATR)Method 148
5.3.3 FTIRMicrospectroscopy 150
5.3.4 AFM-IRSpectroscopy 150
5.3.5 HyphenatedTechniques 150
5.4 ApplicationsandCaseStudies 151
5.4.1 ChemicalCharacterizationandKinetics 151
5.4.2 Surfaces 152
5.4.3 MedicalandLifeScience(Pharmaceutical,Medical,Biological,Biotechnological) 153
5.4.4 CulturalHeritageandForensic 156
5.4.5 EnvironmentalandGeological 157
5.4.6 FoodIndustry 158
References 158
6 RamanandMicro-RamanSpectroscopy 169
GiulianaFaggio,RossellaGrillo,andGiacomoMessina
6.1 BasicTheory 169
6.1.1 Introduction 169
6.1.2 SpectroscopicUnits 169
6.1.3 MolecularVibrations 170
6.1.4 ClassicalTheoryoftheRamanScattering 171
6.1.5 SimplifiedQuantumApproachtoRamanScattering 174
viii Contents
6.1.6 RamanandIRActivities 178
6.1.7 CrystalVibrations 180
6.1.8 RamanScatteringinCrystals 183
6.1.9 Surface-EnhancedRamanScattering(SERS) 185
6.2 Instrumentation 187
6.2.1 LaserSourcesandOpticalFilters 187
6.2.2 Monochromators 188
6.2.3 Detectors 189
6.2.4 RamanMicroscopyandRamanMapping 189
6.3 CaseStudies 191
6.3.1 RamanIndicators 191
6.3.2 IdentificationofMaterialsandCrystallineQuality 191
6.3.3 GrapheneandGraphiteRamanSpectra 193
6.3.4 DopingDetection 196
6.3.5 BasicExamplesofSERS 196
References 198
7 ThermallyStimulatedLuminescence 201
FedericoMoretti
7.1 TheoryofThermallyStimulatedLuminescence 202
7.1.1 SimpleModel 205
7.1.1.1 First-OrderKinetics 207
7.1.1.2 Second-OrderKinetics 211
7.1.1.3 General-OrderKinetics 211
7.1.2 LocalizedTransitions 213
7.1.3 BeyondtheIdealBehavior 214
7.1.3.1 LuminescenceQuenching 215
7.1.3.2 TrapEnergyDistributions 216
7.2 DataAnalysisMethods 216
7.2.1 InitialRise 217
7.2.2 PeakShape 218
7.2.3 HeatingRateMethod 220
7.2.4 GlowCurveFit 221
7.3 InstrumentationandConsiderationsonSamples 221
7.4 CaseStudies 222
7.4.1 LanthanideEnergyLevelPositionintheBandgap 223
7.4.2 BandgapEngineering 224
7.4.3 CorrelationofTSLDatawithEPRResults 225
Note 225
References 226
8 SpectroscopicStudiesofRadiationEffectsonOpticalMaterials 229
SylvainGirard,VincenzoDeMichele,andAdrianaMorana
8.1 Introduction 229
8.1.1 RadiationEnvironments 229
8.1.2 ApplicationsforOpticalMaterials 230
8.2 Radiation-InducedEffectsonOpticalMaterialsandOpticalFibers 231
Contents ix
8.2.1 Radiation-InducedAttenuation–RIA 231
8.2.2 Radiation-InducedEmission–RIE 233
8.2.3 Radiation-InducedCompaction–RICandRefractiveIndexChange–RIRIC 234
8.2.4 OriginsofRadiation-InducedOpticalChanges 234
8.3 Radiation-InducedAttenuationMeasurements 235
8.3.1 PostirradiationRIAMeasurements 235
8.3.1.1 BulkGlasses 235
8.3.1.2 OpticalFibers 235
8.3.2 InSituRIAMeasurements 236
8.3.2.1 BulkGlasses 236
8.3.2.2 OpticalFibers 237
8.3.3 ExploitationofRIASpectra:PointDefectIdentification 241
8.3.3.1 SpectralDecomposition 241
8.3.3.2 PointDefectKinetics 243
8.4 Radiation-InducedLuminescence(RIL) 243
8.4.1 ArchitecturesofFiber-BasedSensors:ExtrinsicandIntrinsic 243
8.4.2 CalibrationoftheRILVersusProtonFlux 245
8.4.3 BraggPeakMeasurementsforProton-TherapyApplications 245
8.5 CaseStudies 246
8.5.1 CharacterizationofBulkGlassesforSpaceOpticalSystems 246
8.5.2 Fiber-BasedDosimetrywithPhosphorus-DopedOpticalFibers 247
8.5.3 ProtonFluxMeasurementsThroughtheRILofOpticalFibers 249
References 249
9 ElectronParamagneticResonanceSpectroscopy(EPR) 253
AntoninoAlessiandFrancoGelardi
9.1 Introduction 253
9.2 BasicPrincipleofEPR 253
9.3 AnisotropyofgandSpectralLineshape 255
9.4 TheEPRLineshapeinPowderorinAmorphous 257
9.5 HyperfineInteractions 258
9.6 ParamagneticCenterwithS=1 261
9.7 BasicsofContinuousWaveEPRSetup 263
9.8 ParametersforEPRSignalAcquisition 266
9.9 CwEPRCaseStudies 268
9.10 Time-ResolvedEPRSpectroscopy 270
9.10.1 SaturationTransients 270
9.10.2 SpinNutations 272
9.10.3 FreeInductionDecay 274
9.10.4 SpinEcho 276
References 277
10 NuclearMagneticResonanceSpectroscopy 281
AlbertoSpinellaandPellegrinoConte
10.1 Introduction 281
10.2 NMRGeneralConcepts 281
10.2.1 NuclearSpinandMagneticMoment 281
x Contents
10.2.2 SpinPrecessionandLarmorFrequency 283
10.2.3 LongitudinalMagnetization 283
10.2.4 TransverseMagnetizationandNMRSignal 284
10.2.5 SpinInteractions 285
10.2.6 FourierTransformNMR 287
10.3 Liquid-StateNMR 288
10.3.1 TheNMRSpectrometer 288
10.3.2 SamplePreparation 288
10.3.3 HowtoSetanExperiment 289
10.3.4 LongitudinalRelaxationTimeMeasurement 289
10.3.5 TransverseRelaxationTimeMeasurement 290
10.3.6 2D-Liquid-StateNMRTechniques 291
10.3.7 ConsiderationsontheMolecularDynamicsbyNMRSpectroscopy 292
10.4 Solid-StateNMR 293
10.4.1 PowderedSamples 293
10.4.2 Cross-PolarizationandHeteronuclearDecoupling 294
10.4.3 Magic-AngleSpinning 296
10.4.4 HomonuclearDipolarDecoupling 299
10.4.5 2D-SolidStateNMRTechniques 299
10.4.6 RecouplingTechniques 300
10.4.7 MolecularDynamicsbySolid-StateNMRSpectroscopy 301
10.5 NonconventionalNMRTechniques 301
10.5.1 TimeDomainNMR 302
10.5.2 FastFieldCyclingNMRRelaxometry 302
10.5.3 Earth’sMagneticFieldNMR 309
10.6 CaseStudies 309
10.6.1 PolymersandPolymer-BasedComposites 309
10.6.2 MesoporousMaterials 310
10.6.3 CulturalHeritage 311
10.6.4 Food 313
10.6.5 EnvironmentalNMR:Rocks,Soils,Waters,Air 313
10.6.6 NMRof“Exotic”Nuclei 314
References 315
11 X-RayAbsorptionSpectroscopyandX-RayRamanScatteringSpectroscopy
forEnergyApplications 319
AlessandroLongo,FrancescoGiannici,andChristophJ.Sahle
11.1 Introduction 319
11.2 TheX-RayAbsorptionCoefficientandtheEXAFSTechnique 320
11.2.1 TheEXAFSEquationandtheKeyApproximations 322
11.2.1.1 Many-BodyEffects 323
11.2.1.2 InelasticEffects 324
11.2.2 MultipleScatteringTheory:BasicInformation 325
11.2.3 XANESorNear-EdgeX-RayAbsorptionFineStructureandPre-EdgeRegion 328
11.3 EXAFS:DataAnalysisOverview 331
11.4 ExperimentalSetups 333
Contents xi
11.4.1 TransmissionGeometry 333
11.4.2 FluorescenceGeometry 334
11.5 X-RayRamanScatteringSpectroscopy 335
11.5.1 TheoreticalBackground 335
11.5.2 ExperimentalSetup 338
11.5.2.1 Instrumentation 338
11.5.2.2 DataProcessing 338
11.6 CaseStudies:ApplicationofXAFSandXRSforEnergyMaterials 339
11.6.1 COOxidationReaction:TheAu/CeO Catalyst 339
2
11.6.2 MaterialsforSolidOxideFuelCells 340
11.6.3 Oxide-IonConductors:DopantsandVacancies 342
11.6.4 Proton-ConductingOxides 343
11.6.5 TheRoleofOxygeninFuelCellCathodes 344
References 346
12 X-RayPhotoelectronSpectroscopy 351
MichelangeloScopelliti
12.1 GeneralPrinciples 351
12.2 InstrumentalSetup 352
12.2.1 VacuumandUltrahighVacuum,UHV 353
12.2.1.1 RoughingPumps 354
12.2.1.2 TurbomolecularPumps 355
12.2.1.3 IonPumps 355
12.2.1.4 TitaniumSublimationPumps 356
12.2.2 MagneticShielding 356
12.2.3 Sources 356
12.2.4 SampleManipulators 358
12.2.5 ChargeNeutralizationSystems 359
12.2.5.1 ElectronGuns 360
12.2.5.2 IonGuns 360
12.2.6 AnalyzersandDetectors 361
12.3 Applications 362
12.3.1 QuantitativeAnalysis 364
12.3.2 QualitativeAnalysis 365
12.3.3 SurfaceMaps 365
12.3.4 Profiles 367
12.3.4.1 DepthProfiles 367
12.3.4.2 Angle-ResolvedProfiles 368
12.4 DataAnalysis 368
12.4.1 ShiftCorrections 370
12.4.2 Background 371
12.4.3 LineShapes 372
12.4.4 NonlinearFitting 375
12.5 CaseStudies 376
12.5.1 HydrocarbonContamination 376
12.5.2 EnergyLoss 376
