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Organic and Inorganic Nanostructures ForalistingofrecenttitlesintheArtechHouseMEMSSeries, turntothebackofthisbook Organic and Inorganic Nanostructures Alexei Nabok artechhouse.com LibraryofCongressCataloging-in-PublicationData AcatalogrecordofthisbookisavailablefromtheLibraryofCongress. BritishLibraryCataloguinginPublicationData Nabok,Alexei Organicandinorganicnanostructures.—(ArtechHouseMEMSseries) 1.Nanotechnology 2.Nanostructures 3.Thinfilms I.Title 602.5 ISBN1-58053-818-5 CoverdesignbyIgorValdman ©2005ARTECHHOUSE,INC. 685CantonStreet Norwood,MA02062 Allrightsreserved.PrintedandboundintheUnitedStatesofAmerica.Nopartofthisbook maybereproducedorutilizedinanyformorbyanymeans,electronicormechanical,includ- ing photocopying, recording, or by any information storage and retrieval system, without permissioninwritingfromthepublisher. Alltermsmentionedinthisbookthatareknowntobetrademarksorservicemarkshave beenappropriatelycapitalized.ArtechHousecannotattesttotheaccuracyofthisinforma- tion.Useofaterminthisbookshouldnotberegardedasaffectingthevalidityofanytrade- markorservicemark. InternationalStandardBookNumber:1-58053-818-5 10987654321 Contents Preface ix Acknowledgments xi CHAPTER 1 Introduction 1 1.1 ABriefHistoryofNanorevolution 1 1.2 PhysicalLimitationsofTraditionalSemiconductorElectronics 2 1.3 QuantumNanoelectronicDevicesandQuantumComputing 4 1.4 RevolutionaryNanotechnologies 6 1.5 SolidStateAgainstSoftMatterinNanotechnologies 9 1.6 TheBookStructure 11 References 11 CHAPTER 2 Wet Technologies for the Formation of Organic Nanostructures 13 2.1 TraditionalChemicalRoutesforNanostructureProcessing 13 2.1.1 FormationofColloidNanoparticles 13 2.1.2 Self-AssemblyofColloidNanoparticles 15 2.1.3 ElectrodepositionofNanostructuredMaterials 16 2.1.4 Sol-GelDeposition 18 2.2 ElectrostaticSelf-Assembly 23 2.2.1 TheIdeaofElectrostaticSelf-Assembly 23 2.2.2 ESADepositioninDetail 24 2.2.3 ESADepositionEquipment 27 2.2.4 CompositeESAFilms 29 2.3 Langmuir-BlodgettTechnique 33 2.3.1 LBClassics 33 2.3.2 SpecialTypesofLBFilms—CompositeLBFilms 43 2.3.3 FormationofII-VISemiconductorParticlesinLBFilms 48 2.4 SpinCoating 54 2.5 Résumé 58 References 59 v vi Contents CHAPTER 3 Structural Study of Organic/Inorganic Nanocomposites 71 3.1 MorphologyandCrystallographyofNanostructuredMaterials PreparedbyChemicalRoutes 71 3.1.1 MethodsofMorphologyStudy 72 3.1.2 MethodsofCrystallographyStudy 75 3.1.3 TheLayer-by-LayerStructureofThinFilms 76 3.1.4 MorphologyofLBFilmsContainingNanoparticles 79 3.1.5 MorphologyandCrystallographyofChemically Self-AssembledNanoparticles 81 3.1.6 TheMorphologyandStructureofSol-Geland ElectrodepositedMaterials 84 3.2 ElementalandChemicalCompositionofOrganic/Inorganic Nanostructures 87 3.2.1 ExperimentalMethodsofCompositionStudy 87 3.2.2 ExamplesofCompositionStudyofMaterialsPrepared byChemicalRoutes 88 3.2.3 ControlofImpuritiesinChemicallyDepositedNanostructures 90 References 92 CHAPTER 4 Optical Properties of Organic/Inorganic Nanostructures 95 4.1 OpticalConstantsofOrganic/InorganicNanostructures 95 4.1.1 MethodofEllipsometry 95 4.1.2 MethodofSPR 100 4.1.3 OpticalConstantsofThinOrganicFilms 104 4.1.4 OpticalParametersofOrganicFilmsContainingNanoparticles 110 4.2 TheEffectofQuantumConfinementonOpticalPropertiesof Low-DimensionalSystems 114 4.2.1 ElectroninaQuantumBox 114 4.2.2 QuantumConfinementandtheMainOpticalPropertiesof Low-DimensionalSemiconductorStructures 116 4.3 OpticalSpectraSemiconductorNanoparticlesinOrganicFilms 122 4.3.1 SemiconductorNanoparticlesinLBandSpunFilms 122 4.3.2 SemiconductorNanoparticlesinElectrostatically Self-AssembledFilms 127 References 129 CHAPTER 5 Electron Transport in Organic/Inorganic Nanostructures 133 5.1 ConductivityofThinFilms 133 5.1.1 DefinitionsandExperimentalMethods 133 5.1.2 ConductivityofNanocrystallineMaterials 138 5.1.3 OrganicSemiconductors 141 5.2 ElectronTunneling 144 5.2.1 TheConceptandMainFeaturesofElectronTunneling 144 5.2.2 ElectronTransferThroughThinOrganicFilms 146 Contents vii 5.2.3 ElectronTunnelingThroughMultilayeredLBFilms 149 5.2.4 ResonanceTunneling 151 5.2.5 InelasticTunnelingandInelasticTunnelingSpectroscopy 154 5.3 SingleElectronPhenomena 155 5.3.1 CoulombBlockadeandStaircaseI-VCharacteristics 155 5.3.2 Single-ElectronDevicesandTheirPracticalRealization 158 5.3.3 Single-ElectronPhenomenainOrganicFilmsContaining Nanoparticles 160 References 162 CHAPTER 6 Applications of Organic/Inorganic Nanostructures in Microelectronics and Optoelectronics 171 6.1 OrganicFilmsinConventionalMicroelectronics 171 6.1.1 OrganicFilmsasInsulatingandPassivatingLayers 171 6.1.2 ActiveOrganic/InorganicDevices 172 6.2 Organic/InorganicOptoelectronicDevices 174 6.2.1 NanostructuredPhotovoltaicDevicesandSolarCells 175 6.2.2 Light-EmittingDevices 181 6.2.3 OpticalMemoryDevices 183 6.3 QuantumNanoelectronicDevices 185 6.3.1 QuantumComputing 186 6.3.2 PracticalRealizationofArraysofQuantumDots 188 References 190 CHAPTER 7 Chemical and Biosensors 205 7.1 ClassificationandMainParametersofChemicalandBiosensors 205 7.1.1 MainDefinitionsandClassificationofSensors 205 7.1.2 ParametersofSensors 208 7.2 PhysicalTransducingPrinciplesforSensors 212 7.2.1 GravimetricSensors 212 7.2.2 ElectricalandElectrochemicalSensors 215 7.2.3 OpticalSensors 220 7.3 NanostructuredMaterialsforSensing 231 7.3.1 SensorsBasedonInorganicMaterials 231 7.3.2 SensorsBasedonOrganicMaterials 232 7.3.3 OrganicVaporSensorsBasedonCalixarenes 233 7.4 Biosensors 238 7.4.1 CompositeMembranesforBiosensing 238 7.4.2 ImmuneSensors 240 7.4.3 EnzymeSensors 245 References 251 About the Author 261 Index 263 . Preface Thisbookisanattempttosummarizetheknowledgeandpersonalexperienceaccu- mulatedthroughout18yearsofworkinthefieldofphysicsandtechnologyofthin organicfilms,organic-inorganicnanostructures,andchemicalandbiosensing. Initiallythebookwasplannedasaresearchmonograph,butlaterintheprocess ofwritingIintroducedaquitesubstantialscientificbackgroundineverychapterin ordertomakethesubjectmoreunderstandableforawidescientificaudience.Then Irealizedthatthebookmightbeveryusefulforpostgraduateandevenundergradu- ate students. The book contains the original scientific results obtained by the author,aswellassubstantialliteraturereviewsineverychapter,whichmakesituse- fulforacademicsandresearchersworkinginthefieldofnanotechnology. I began writing with the enthusiasm and the feeling that I knew something aboutscienceinmyfield.Now,Iamnotthatsureaboutit.Ilearnedalotduringthe writingofthisbook,butIalsorealizedhowvastandfast-growingtheareaofnano- technologyis,andhowsmallmycontributiontoitis.SeveraltimesIwantedtoquit andoccupymyselfwithsomethinglessstressful.Ifinishedthebookanyway,andI hopesomepeoplewillmakeuseofit. ix