Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, Second Edition

1100 Pages·2012·21.502 MB·English

Edited by
Gero Decher and
Joseph B. Schlenoff
Multilayer Thin Films
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Edited by
Gero Decher and Joseph B. Schlenoff
Multilayer Thin Films
Sequential Assembly of Nanocomposite Materials
Second, Completely Revised and Enlarged Edition
TheEditors AllbookspublishedbyWiley-VCHarecarefully
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V
Contents
List of Contributors XXV
Volume 1
1 Layer-by-LayerAssembly(PuttingMoleculestoWork) 1
GeroDecher
1.1 TheWholeisMorethantheSumofitsParts 1
1.2 FromSelf-AssemblytoDirectedAssembly 1
1.3 HistoryandDevelopmentoftheLayer-by-LayerAssemblyMethod 4
1.4 LbL-AssemblyistheSynthesisofFuzzySupramolecularObjects 6
1.5 ReproducibilityandChoiceofDepositionConditions 7
1.6 MonitoringMultilayerBuild-up 10
1.7 Spray-andSpin-AssistedMultilayerAssembly 13
1.8 RecentDevelopments 14
1.8.1 Self-patterningLbL-Films 14
1.8.2 DepositionofLbL-FilmsonVerySmallParticles 15
1.8.3 PurelyInorganicLbL-‘‘Films’’ 17
1.9 FinalRemarks 18
References 19
PartI PreparationandCharacterization 23
2 Layer-by-LayerProcessedMultilayers:ChallengesandOpportunities 25
MichaelF.RubnerandRobertE.Cohen
2.1 Introduction 25
2.2 FundamentalChallengesandOpportunities 25
2.2.1 LbLAssemblyonNanoscaleElementsandinConfinedGeometries 25
2.2.2 LivingCellsasFunctionalElementsofPolyelectrolyteMultilayers 28
2.2.3 MultilayerCellularBackpacks 28
2.2.4 DirectLbLProcessingofLivingCells 29
2.3 TechnologicalChallengesandOpportunities 31
2.3.1 ImprovingProcessingTimeandVersatility 31
2.3.2 TowardsMechanicallyRobustMultilayerCoatings 32
2.4 ThePathForward 36
References 36
VI Contents
3 Layer-by-LayerAssembly:fromConventionalto
UnconventionalMethods 43
GuangluWuandXiZhang
3.1 Introduction 43
3.2 ConventionalLbLMethods 44
3.2.1 ElectrostaticLbLAssembly 44
3.2.2 Hydrogen-BondedLbLAssembly 47
3.2.3 LbLAssemblyDrivenbyCoordinationInteraction 50
3.2.4 ToCombineLbLAssemblyandPost-ChemicalReactionforthe
FabricationofRobustThinFilms 50
3.3 UnconventionalLbLMethods 52
3.3.1 ElectrostaticComplexforUnconventionalLbLAssembly 52
3.3.1.1 NanoreactorswithEnhancedQuantumYield 53
3.3.1.2 ‘‘IonTraps’’forEnhancingthePermselectivity
andPermeability 53
3.3.1.3 SurfaceImprintedLbLFilms 54
3.3.1.4 Cation-SelectivemCPBasedonSMILbLFilm 58
3.3.2 Hydrogen-BondedComplexforUnconventionalLbLAssembly 58
3.3.3 BlockCopolymerMicellesforUnconventionalLbLAssembly 61
3.3.4 p–pInteractionComplexforElectrostaticLbLAssembly 62
3.4 SummaryandOutlook 64
References 64
4 NovelMultilayerThinFilms:HierarchicLayer-by-Layer(Hi-LbL)
Assemblies 69
KatsuhikoAriga,QingminJi,andJonathanP.Hill
4.1 Introduction 69
4.2 Hi-LbLforMulti-CellularModels 70
4.3 Hi-LbLforUnusualDrugDeliveryModes 72
4.4 Hi-LbLforSensors 75
4.4.1 MesoporousCarbonHi-LbL 75
4.4.2 MesoporousCarbonCapsuleHi-LbL 76
4.4.3 Graphene/Ionic-LiquidHi-LbL 78
4.5 FuturePerspectives 79
References 80
5 Layer-by-LayerAssemblyUsingHost-GuestInteractions 83
JannekeVeerbeek,DavidN.Reinhoudt,andJurriaanHuskens
5.1 Introduction 83
5.2 SupramolecularLayer-by-LayerAssembly 84
5.3 3DPatternedMultilayerAssembliesonSurfaces 85
5.4 3DSupramolecularNanoparticleCrystalStructures 88
5.5 Porous3DSupramolecularAssembliesinSolution 90
5.6 Conclusions 95
References 95
Contents VII
6 LbL Assemblies Using van der Waals or Affinity Interactions and Their
Applications 99
TakeshiSerizawa,MitsuruAkashi,MichiyaMatsusaki,HioharuAjiro,and
ToshiyukiKida
6.1 Introduction 99
6.2 StereospecificTemplatePolymerizationofMethacrylatesby
StereocomplexFormationinNanoporousLbLFilms 100
6.2.1 Introduction 100
6.2.2 LbLit-PMMA/st-PMMAStereocomplexUultrathinFilm 102
6.2.3 FabricationofTemplateNanospacesinFilms 104
6.2.4 Polymerization within Template Nanospaces Using a Double-Stranded
Assembly 106
6.2.5 StudiesonthePorousStructureObtainedbyLbLAssembly 111
6.3 PreparationandPropertiesofHollowCapsulesComposedofLayer-by-
LayerPolymerFilmsConstructedthroughvanderWaals
Interactions 113
6.3.1 Introduction 113
6.3.2 Preparation of Hollow Nanocapsules Composed of Poly(methyl
methacrylate)StereocomplexFilms 114
6.3.3 Preparation and Fusion Properties of Novel Hollow Nanocapsules
ComposedofPoly(lacticacid)sStereocomplexFilms 116
6.4 Fabrication of Three-Dimensional Cellular Multilayers Using Layer-by-
LayerProteinNanofilmsConstructedthroughAffinityInteraction 120
6.4.1 Introduction 120
6.4.2 HierarchicalCellManipulation 121
6.4.3 HighCellularActivitiesInducedby3D-LayeredConstructs 124
6.4.4 Quantitative 3D-Analyses of Nitric Oxide Diffusion in a 3D-Artery
Model 124
6.5 Conclusion 129
References 129
7 Layer-by-LayerAssemblyofPolymericComplexes 135
JunqiSun,XiaokongLiu,andJiacongShen
7.1 Introduction 135
7.2 ConceptofLbLAssemblyofPolymericComplexes 136
7.2.1 LbL Assembly of Polyelectrolyte Complexes for the Rapid and Direct
FabricationofFoamCoatings 136
7.2.2 LbLAssemblyofHydrogen-BondedPolymericComplexes 138
7.2.3 LbLAssemblyofPolyelectrolyte-SurfactantComplexes 139
7.3 StructuralTailoringofLbL-AssembledFilmsofPolymeric
Complexes 140
7.3.1 MixingRatioofPECs 140
7.3.2 LbLCodepositionofPECsandFreePolyelectrolytes 142
7.3.3 SaltEffect 143
7.4 LbL-AssembledFunctionalFilmsofPolymericComplexes 144
VIII Contents
7.4.1 Self-HealingSuperhydrophobicCoatings 144
7.4.2 MechanicallyStableAntireflection-andAntifogging-Integrated
Coatings 146
7.4.3 TransparentandScratch-ResistantCoatingswithWell-Dispersed
Nanofillers 147
7.5 Summary 149
References 149
8 MakingAqueousNanocolloidsfromLowSolubilityMaterials:LbLShells
onNanocores 151
YuriLvov,PravinPattekari,andTatsianaShutava
8.1 Introduction 151
8.2 FormationofNanocores 153
8.2.1 StabilizersversusLayer-by-LayerPolyelectrolyteShell 153
8.3 Ultrasonication-AssistedLbLAssembly 154
8.3.1 Top-DownApproach 154
8.3.2 Bottom-UpApproach 158
8.4 Solvent-AssistedPrecipitationIntoPreformedLbL-CoatedSoftOrganic
Nanoparticles 159
8.5 Washless(Titration)LbLTechnique 161
8.6 FormationofLbLShellsonNanocores 163
8.7 DrugReleaseStudy 165
8.8 Conclusions 168
References 168
9 Cellulose Fibers and Fibrils as Templates for the Layer-by-Layer (LbL)
Technology 171
LarsWågberg
9.1 Background 171
9.2 FormationofLbLsonCelluloseFibers 172
9.3 TheuseofLbLtoImproveAdhesionbetweenWoodFibers 176
9.4 TheUseofLbLtoPrepareAntibacterialFibers 179
9.5 TheuseofNFC/CNCtoPrepareInteractiveLayersUsingtheLbL
Approach 182
9.6 Conclusions 185
References 186
10 FreelyStandingLbLFilms 189
ChaoyangJiangandVladimirV.Tsukruk
10.1 Introduction 189
10.2 FabricationofFreelyStandingUltrathinLbLFilms 189
10.2.1 LbLFilmswithGoldNanoparticlesandSilverNanowires 191
10.2.2 LbLFilmswithQuantumDots 193
10.2.3 LbLFilmswithNanocrystals 194
10.2.4 LbLFilmswithGrapheneOxidesandCarbonNanotubes 195
Contents IX
10.2.5 LbLwithBiomaterials 198
10.2.6 MechanicalandOpticalProperties 199
10.2.7 SurfaceMorphologyandInternalMicrostructure 201
10.3 PorousandPatternedFreelyStandingLbLFilms 204
10.3.1 NanoporousLbLFilms 204
10.3.2 PatternedLbLFilms 205
10.3.3 SculpturedLbLFilms 207
10.4 FreelyStandingLbLFilmswithWeakInteractions 208
10.4.1 ResponsiveLbLFilms 208
10.4.2 AnisotropicLbLMicrocapsules 209
10.4.3 LbL-ShellsforCellEncapsulation 210
References 214
11 NeutronReflectometryatPolyelectrolyteMultilayers 219
ReginevonKlitzing,RalfKöhler,andChloeChenigny
11.1 Introduction 219
11.2 NeutronReflectometry 219
11.2.1 SpecularReflectometry 220
11.2.2 ContrastVariation:InterestingFeaturesforPEMs 222
11.2.2.1 SuperlatticeStructure 222
11.2.2.2 BlockStructure 223
11.2.3 Fitting 223
11.3 PreparationTechniquesforPolyelectrolyte
Multilayers 224
11.3.1 Dipping 224
11.3.2 Spraying 228
11.3.3 Spin-Coating 231
11.3.4 ComparisonoftheTechniquesandModel 231
11.4 TypesofPolyelectrolytes 233
11.4.1 AStrongPolyanionandaWeakPolycation 233
11.4.2 TwoStrongPolyelectrolytes 235
11.4.3 TwoWeakPolyelectrolytes 237
11.4.4 MultilayerswithNon-ElectrostaticInteractions 238
11.5 PreparationParameters 238
11.5.1 IonEffects 238
11.5.1.1 IonicStrength 238
11.5.1.2 Counterions 239
11.5.2 pH 241
11.5.3 Temperature 241
11.6 InfluenceofExternalFieldsAfterPEMAssembly 242
11.6.1 ScalarFields:IonicStrength 242
11.6.2 ScalarFields:Temperature 244
11.6.3 ScalarFields:Water 246
11.6.3.1 SwellinginWater 247
11.6.3.2 ModelsforDeterminationoftheWaterContent 252
X Contents
11.6.3.3 Effect of Polymer Charge Density and Ions During Preparation on
SwellinginWater 254
11.6.3.4 Odd-EvenEffect 256
11.6.4 DirectedExternalFields:MechanicalandElectricalFields 257
11.6.4.1 MechanicalStress 257
11.6.4.2 ElectricField 258
11.7 PEMasaStructuralUnit 259
11.7.1 Cushion 259
11.7.1.1 Cell-MembraneMimicSystems 260
11.7.1.2 MultilayersBeyondPolyelectrolytes 261
11.7.2 Matrix 261
11.8 ConclusionandOutlook 261
References 262
12 PolyelectrolyteConformationinandStructureofPolyelectrolyte
Multilayers 269
StephanBlock,OlafSoltwedel,PeterNestler,andChristianeA.Helm
12.1 Introduction 269
12.2 Results 270
12.2.1 TheFirstPolyelectrolyteLayer:Brushand/orFlatlyAdsorbed
Chains 270
12.2.2 AdsorptionofAdditionalLayersandInterdiffusion 275
12.2.3 TheOutermostLayer:FromOdd–Evento
Even–OddEffect 277
12.3 ConclusionandOutlook 279
References 280
13 ChargeBalanceandTransportinIon-PairedPolyelectrolyte
Multilayers 281
JosephB.Schlenoff
13.1 Introduction 281
13.2 AssociationMechanism:CompetitiveIonPairing 283
13.2.1 Intrinsicvs.ExtrinsicChargeCompensation 285
13.2.1.1 KeyEquilibria 285
13.2.1.2 InteractionEnergies 287
13.2.1.3 MultilayerDecomposition 290
13.2.1.4 Doping-moderatedMechanicalProperties 292
13.3 SurfaceversusBulkPolymerCharge 292
13.3.1 DistributionofSurfaceChargeinLayer-by-LayerBuild-up:
Mechanism 297
13.4 PolyelectrolyteInterdiffusion 301
13.4.1 Equilibrium versus Non-Equilibrium Conditions for Salt and Polymer
Sorption 304
13.5 IonTransportThroughMultilayers:the‘‘Reluctant’’Exchange
Mechanism 305