Cluster Secondary Ion Mass Spectrometry: Principles and Applications

357 Pages·2013·10.058 MB·English

by  Dominic M. Desiderio, Nico M. M. Nibbering, Joseph A. Loo(eds.)

CLUSTER SECONDARY
ION MASS
SPECTROMETRY

CLUSTER SECONDARY
ION MASS
SPECTROMETRY
Principles and Applications
Edited by
Christine M. Mahoney
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LibraryofCongressCataloging-in-PublicationData:
Mahoney,ChristineM.,1975-
Clustersecondaryionmassspectrometry:principlesandapplications/ChristineM.Mahoney.
pagescm
Includesbibliographicalreferencesandindex.
ISBN978-0-470-88605-2(hardback)
1.Secondaryionmassspectrometry.I.Title.
QD96.S43M342013
543’.65–dc23
2012045181
PrintedinSingapore
10987654321
CONTENTS
Contributors xi
AbouttheEditor xiii
1 ANINTRODUCTIONTOCLUSTERSECONDARYIONMASS
SPECTROMETRY(CLUSTERSIMS) 1
ChristineM.MahoneyandGregGillen
1.1 SecondaryIonMassSpectrometryinaNutshell 2
1.1.1 SIMSImaging 4
1.1.2 SIMSDepthProfiling 4
1.2 BasicClusterSIMSTheory 5
1.3 ClusterSIMS:AnEarlyHistory 6
1.3.1 NonlinearSputterYieldEnhancements 6
1.3.2 MolecularDepthProfiling 7
1.4 RecentDevelopments 8
1.5 AboutthisBook 9
Acknowledgment 11
References 11
2 CLUSTERSIMSOFORGANICMATERIALS:THEORETICALINSIGHTS 13
ArnaudDelcorte,OscarA.Restrepo,andBartlomiejCzerwinski
2.1 Introduction 13
2.2 MolecularDynamics SimulationsofSputteringwithClusters 15
2.2.1 TheClusterEffect 15
2.2.2 ComputerSimulations andtheMolecularDynamics “Experiment” 18
2.2.3 LightandHeavyElementClusters,andtheImportanceofMass
Matching 20
2.2.4 StructuralEffectsinOrganicMaterials 21
2.2.4.1 AmorphousMolecularSolidsandPolymers 21
2.2.4.2 OrganicCrystals 26
2.2.4.3 ThinOrganicLayersonMetalSubstrates 28
2.2.4.4 HybridMetal–OrganicSamples 32
2.2.5 InducedChemistry 34
2.2.6 MultipleHitsandDepthProfiling 36
2.2.7 FromSmallPolyatomicProjectilestoMassiveClusters 38
2.2.7.1 Light-ElementClusters 38
2.2.7.2 LargeArgonClusters 41
2.2.7.3 MassiveGoldClusters 45
v
vi CONTENTS
2.3 OtherModels 46
2.3.1 Analytical Models:FromLinearCollisionCascades toFluidDynamics 46
2.3.2 RecentDevelopments andHybridApproaches 47
2.4 Conclusions 50
Acknowledgments 51
References 51
3 IONSOURCESUSEDFORSECONDARYIONMASSSPECTROMETRY 57
AlbertJ.Fahey
3.1 Introduction 57
3.2 ResearchNeeds thathaveInfluenced theDevelopment ofPrimaryIon
SourcesforSputtering 58
3.3 FunctionalAspectsofVarious IonSources 59
3.3.1 EnergySpreadintheBeam 59
3.3.2 Point-SourceIonization 60
3.3.3 StableEmission 60
3.3.4 IonReactivity 60
3.3.5 SourceLifetime 60
3.3.6 Penetration DepthandSurfaceEnergySpreadoftheProjectile 61
3.4 AtomicIonSources 61
3.4.1 FieldEmission 61
3.4.2 RadioFrequency(RF)Ionization 62
3.4.3 ElectronImpact 63
3.4.4 ThermalIonization 64
3.4.5 DC-GlowDischarge 65
3.4.6 Sputtering 66
3.5 MolecularIonSources 66
3.5.1 FieldEmission 66
3.5.2 RadioFrequencyDischarge 67
3.5.3 ElectronImpact 68
3.5.4 DC-GlowDischarge 69
3.5.5 Sputtering 69
3.6 ClusterIonSources 70
3.6.1 JetsandElectronImpact(MassiveGasClusters) 71
3.6.2 FieldEmission 72
3.7 Summary 73
References 74
4 SURFACEANALYSISOFORGANICMATERIALSWITHPOLYATOMIC
PRIMARYIONSOURCES 77
ChristineM.Mahoney
4.1 Introduction 77
4.2 ClusterSourcesinStaticSIMS 78
4.2.1 ABriefIntroductiontoStaticSIMS 78
4.2.2 AnalysisbeyondtheStaticLimit 79
4.2.3 IncreasedIonYields 80
4.2.4 Decreased Charging 81
4.2.5 SurfaceCleaning 82
CONTENTS vii
4.3 ExperimentalConsiderations 83
4.3.1 WhentoEmployClusterSourcesasOpposedtoAtomicSources 83
4.3.2 TypeofClusterSourceUsed 84
4.3.2.1 LiquidMetalIonGun(LMIG) 84
+
4.3.2.2 C forMassSpectralAnalysisandImagingApplications 85
60
4.3.2.3 TheGasClusterIonBeam(GCIB) 86
4.3.2.4 Au 4+ 86
400
4.3.2.5 OtherSources 88
4.3.3 ClusterSizeConsiderations 88
4.3.4 BeamEnergy 90
4.3.5 SampleTemperature 92
4.3.6 Matrix-EnhancedandMetal-AssistedClusterSIMS 92
4.3.7 MatrixEffects 95
4.3.8 OtherImportantFactors 96
4.4 DataAnalysisMethods 96
4.4.1 PrincipalComponentsAnalysis 96
4.4.1.1 BasicPrinciplesofPCA 97
4.4.1.2 ExamplesofPCAintheLiterature 98
4.4.2 GentleSIMS(G-SIMS) 101
4.5 OtherRelevantSurfaceMass-Spectrometry-BasedMethods 101
4.5.1 DesorptionElectrosprayIonization(DESI) 103
4.5.2 PlasmaDesorptionIonizationMethods 105
4.5.3 ElectrosprayDropletImpactSourceforSIMS 107
4.6 Advanced MassSpectrometersforSIMS 108
4.7 Conclusions 109
AppendixA:UsefulLateralResolution 110
References 110
5 MOLECULARDEPTHPROFILINGWITHCLUSTERIONBEAMS 117
ChristineM.MahoneyandAndreasWucher
5.1 Introduction 117
5.2 HistoricalPerspectives 120
5.3 DepthProfilinginHeterogeneous Systems 123
5.3.1 Introduction 123
5.3.2 Quantitative DepthProfiling 125
5.3.3 Reconstructionof3DImages 127
5.3.4 MatrixEffectsinHeterogeneous Systems 128
5.4 ErosionDynamics ModelofMolecularSputterDepthProfiling 130
5.4.1 ParentMoleculeDynamics 131
5.4.2 ConstantErosionRate 134
5.4.3 Fluence-Dependent ErosionRate 136
5.4.4 UsingMassSpectrometricSignalDecay toMeasureDamage
Parameters 138
5.4.5 SurfaceTransients 141
5.4.6 FragmentDynamics 141
5.4.7 Conclusions 145
5.5 TheChemistryofAtomicIonBeamIrradiationinOrganicMaterials 146
5.5.1 Introduction 146
viii CONTENTS
5.5.2 Understanding theBasicsofIonIrradiationEffects
inMolecularSolids 146
5.5.3 IonBeamIrradiationandtheGelPoint 147
5.5.4 TheChemistryofClusterIonBeams 150
5.5.5 ChemicalStructureChangesandCorrespondingChangesinDepth
ProfileShapes 152
5.6 OptimizationofExperimentalParametersforOrganicDepth
Profiling 156
5.6.1 Introduction 156
5.6.2 Organic DeltaLayersforOptimizationofExperimental
Parameters 157
5.6.3 SampleTemperature 159
5.6.4 Understanding theRoleofBeamEnergyDuringOrganicDepth
Profiling 167
5.6.5 Optimization ofIncidenceAngle 171
5.6.6 EffectofSampleRotation 174
5.6.7 IonSourceSelection 178
+
5.6.7.1 SF andOtherSmallClusterIons 178
5.6.7.2 C 5n+ andSimilarCarbonClusterSources 179
60
5.6.7.3 TheGasClusterIonBeam(GCIB) 180
5.6.7.4 LowEnergyReactiveIonBeams 188
5.6.7.5 ElectrosprayDropletImpact(EDI)SourceforSIMS 189
+ +
5.6.7.6 LiquidMetalIonGunClusters(Bi andAu ) 193
5.6.8 C +/Ar+ Co-sputtering 3 3 195
60
5.6.9 ChamberBackfillingwithaFreeRadicalInhibitorGas 197
5.6.10 OtherConsiderationsforOrganicDepthProfiling
Experiments 197
5.6.11 MolecularDepthProfiling:NovelApproaches andMethods 198
5.7 Conclusions 198
References 200
6 THREE-DIMENSIONALIMAGINGWITHCLUSTERIONBEAMS 207
AndreasWucher,GregoryL.Fisher,andChristineM.Mahoney
6.1 Introduction 207
6.2 GeneralStrategies 210
6.2.1 Three-DimensionalSputterDepthProfiling 210
6.2.2 Wedge Beveling 216
6.2.3 PhysicalCrossSectioning 217
6.2.4 FIB-ToFTomography 219
6.3 ImportantConsiderationsforAccurate 3DRepresentationofData 225
6.3.1 BeamRasteringTechniques 225
6.3.2 Geometry Effects 226
6.3.3 DepthScaleCalibration 228
6.4 Three-DimensionalImageReconstruction 233
6.5 DamageandAlteredLayerDepth 238
6.6 BiologicalSamples 242
6.7 Conclusions 243
References 244
CONTENTS ix
7 CLUSTERSECONDARYIONMASSSPECTROMETRY(SIMS)FOR
SEMICONDUCTORANDMETALSDEPTHPROFILING 247
GregGillenandJoeBennett
7.1 Introduction 247
7.2 PrimaryParticle–SubstrateInteractions 248
7.2.1 CollisionalMixingandDepthResolution 248
7.2.2 TransientEffects 249
7.2.3 Sputter-InducedRoughening 251
7.3 PossibleImprovements inSIMSDepthProfiling—TheUseofCluster
PrimaryIonBeams 253
7.4 Development ofClusterSIMSforDepthProfilingAnalysis 255
+
7.4.1 CF PrimaryIonBeams 255
3+ +
7.4.2 NO andO PrimaryIonBeams 256
2+ 3
7.4.3 SF PolyatomicPrimaryIonBeams 257
5 − −
7.4.4 CSC andC DepthProfiling 258
6 8
7.4.5 Os (CO) andIr (CO) PrimaryIonBeams 262
3 12 4 12
+
7.4.6 C PrimaryIonBeams 263
60
7.4.7 MassiveGaseousClusterIonBeams 265
7.5 ConclusionsandFutureProspects 266
References 266
8 CLUSTERTOF-SIMSIMAGINGANDTHECHARACTERIZATIONOF
BIOLOGICALMATERIALS 269
JohnVickermanandNickWinograd
8.1 Introduction 269
8.2 TheCapabilitiesofTOF-SIMSforBiologicalAnalysis 270
8.3 NewHybridTOF-SIMSInstruments 270
8.3.1 Introduction 270
8.3.2 BenefitsofNewDCBeamTechnologies 271
8.4 ChallengesintheUseofTOF-SIMSforBiologicalAnalysis 273
8.4.1 SampleHandlingofBiologicalSamplesforAnalysisinVacuum 273
8.4.2 AnalysisisLimitedtoSmalltoMediumSizeMolecules 274
8.4.3 IonYields LimitUsefulSpatialResolutionforMolecularAnalysis
tonotMuchBetterthan1μm 275
8.4.4 MatrixEffectsInhibitApplicationinDiscoveryModeandGreatly
Complicates Quantification 275
8.4.5 TheComplexityofBiologicalSystemscanResultinDataSetsthat
NeedMultivariateAnalysis(MVA)toUnravel 276
8.5 ExamplesofBiologicalStudiesUsingCluster-TOF-SIMS 276
8.5.1 AnalysisofTissue 277
8.5.2 DrugLocationinTissue 285
8.5.3 MicrobialMat—SurfaceandSubsurfaceAnalysisinStreptomyces 289
8.5.4 Cells 291
8.5.5 DepthScaleMeasurement 302
8.5.6 HighThroughputBiomaterialsCharacterization 306
8.6 FinalThoughtsandFutureDirections 310
Acknowledgments 310
References 310
x CONTENTS
9 FUTURECHALLENGESANDPROSPECTSOFCLUSTERSIMS 313
PeterWilliamsandChristineM.Mahoney
9.1 Introduction 313
9.2 TheClusterNiche 314
9.3 ClusterTypes 314
9.4 TheChallengeofMassiveMolecularIonEjection 315
9.4.1 ComparingwithMALDI:TheGoldStandard 316
9.4.2 ParticleImpactTechniques 317
9.5 Ionization 318
9.5.1 “Preformed”Ions 319
9.5.2 RadicalIonsandIonFragments 319
9.5.3 IonizationProcessesforMassiveClusters 320
9.6 MatrixEffectsandChallengesinQuantitative Analysis 321
9.7 SIMSInstrumentation 322
9.7.1 MassiveClusterIonSourceTechnology 323
9.8 ProspectsforBiologicalImaging 324
9.9 Conclusions 325
References 326
Index 329