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IR spectroscopy studies of silver and copper nano-films [Elektronische Ressource] / presented by Fanzhen Meng

145 pages
ofDissertationOralsubmittedFtodegreethetedComornbined10FDoacultiesSciencesforyNaturalMengScienceWandJanfor2007MathematicsofofctortheNaturalRuppresenerto-CarclabUnivM.ScersitanzhenybofinHeidelbeifang,Chinaerg,examination:GermanuaryythforthePucciIRReferees:SpBilleectroscopDr.yDr.StudiesNano-lmsofProf.SilvAnnemarieerProf.andJosefCopper< 100scofbSilvransmissions-bzw.erdierencesandohlCopphstumseronnano-lmsKupfer-NanolmenTheobpresenempt(AFM)wMoorkhiedliciseitenfoInfrarotuncusedtriertonauftheoninfrared?hrendoptical(UHV)propwurdeertiesInfrarot-Refektivit?tsminimofhaftenthinhriebAgvandonCuonlmsCugrothewnanonArbMgO(001)dieander-theheSurface-Enhancederst?rkteInfraredadsorbiertemAbsorptionals(SEIRA)bofUltrahoCOinonObthesesitumetalklms.desDuringDieb?nnenothMedien-MotheDiedephiedenenositionkofAuctheCOmetalhenmorphologielmser?conGr??etoshoMgO(001)endingandislandgashexper-osurevtokthehmetalhenlmsd?nneratKupferlme,loMgO(001)-Obwwurden,tempheneratures(SEIRA)(diesenstudiesSoIR?hrendAbscderK)hinGasangebUltratiefenHigh(<100K)Vh-VacuumInfrarotsp(UHV),ininfraredaufgenommen.sphen-ectrahlie?endwRasterkraft-Mikroskereermessen.capturedteinwsituwinwtransmissionhenorFilmereectionhgeometrybzw..bAfterwwardserlmethevsurfaceeraturenmorphologyhiedenenofuntheMor-lmsSEIRAwAg-FilmenasstarkexaminedObexSEIRAsituaufbzeigtyonatomicCu-Inseln.forcelmsmicroscopwsydep(AFM).onFCuorsize.
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ofDissertationOralsubmittedFtodegreethetedComornbined10FDoacultiesSciencesforyNaturalMengScienceWandJanfor2007MathematicsofofctortheNaturalRuppresenerto-CarclabUnivM.ScersitanzhenybofinHeidelbeifang,Chinaerg,examination:GermanuaryythforthePucciIRReferees:SpBilleectroscopDr.yDr.StudiesNano-lmsofProf.SilvAnnemarieerProf.andJosefCopper< 100
scofbSilvransmissions-bzw.erdierencesandohlCopphstumseronnano-lmsKupfer-NanolmenTheobpresenempt(AFM)wMoorkhiedliciseitenfoInfrarotuncusedtriertonauftheoninfrared?hrendoptical(UHV)propwurdeertiesInfrarot-Refektivit?tsminimofhaftenthinhriebAgvandonCuonlmsCugrothewnanonArbMgO(001)dieander-theheSurface-Enhancederst?rkteInfraredadsorbiertemAbsorptionals(SEIRA)bofUltrahoCOinonObthesesitumetalklms.desDuringDieb?nnenothMedien-MotheDiedephiedenenositionkofAuctheCOmetalhenmorphologielmser?conGr??etoshoMgO(001)endingandislandgashexper-osurevtokthehmetalhenlmsd?nneratKupferlme,loMgO(001)-Obwwurden,tempheneratures(SEIRA)(diesenstudiesSoIR?hrendAbscderK)hinGasangebUltratiefenHigh(<100K)Vh-VacuumInfrarotsp(UHV),ininfraredaufgenommen.sphen-ectrahlie?endwRasterkraft-Mikroskereermessen.capturedteinwsituwinwtransmissionhenorFilmereectionhgeometrybzw..bAfterwwardserlmethevsurfaceeraturenmorphologyhiedenenofuntheMor-lmsSEIRAwAg-FilmenasstarkexaminedObexSEIRAsituaufbzeigtyonatomicCu-Inseln.forcelmsmicroscopwsydep(AFM).onFCuorsize.thetersucrstungentime,SilbanundinfraredDiereectanceorliegendeminimeitumonzenwsicasauffoundinfrarotoptiscduringEigen-thehaftenmetalSilblmundgrodiewth.dieTheer?cinfraredaufgedampftopticalundproper?certiesvofInfrarot-AbsorptionsomevlmsaufcanFilmenbCO.ewdescribweddesbheidensyMetalllmetheaucDrude-twypdereotemoeidelToreraturentheimEectivceakuumMediumwurdenMoektrendel.situTheTAgReexionsgeometrielmsDieshoer?cwMorphologiedierenansctexsurfacemittelsmorphologiesopieatvdierenErstmaligtonnsubstrateeintempumeratures?hrendandMetalllmatacdierengefundenterden.nalinfrararotoptiscthicEigenscknesses.einigerAlsokthedurcSEIRADrude-artigeofdelleCOEektiv-adsorbdelleedesconenAgerden.lmsSilbiszeigenstronglyeirelatedersctoSubstrattemptheundsurfaceerscmorphologies.FilmdicTheenCutersclmshepreparedphologien.athrovomauftempadsorbiertemeratureh?ngtshovwderislander?clikab.evsurfaceCOmorphologyCu-Ob.henSEIRAAbh?ngigkofvCOderadsorbderedon25Con.ten.ts.1.In.tro.duction251.2.Basic.Theory.3.2.1.IR.Sp.ectroscop.y........tomic...Preparation.....Films.41.........Metals.CO...3.1...UHV...Sp...e..............3.2.2.T.ransmissionExpandFilmsReection.atAgIn.terfaces..............dsorb.....on.....Exp.Setup......5.2.2.1.T.w.o-phase.System....3.1.3.Measured.....y.....3.3.......39.....Metal.......Exp.........and5MgO(001)2.2.2omThree.Phase.System-ThinransmissionFilmonOptics2.8.2...............CO............7.2.3COSEIRAoneect......25.dsorb...........30.tal.erimen.Metho...........3.1.1.b.............3.1.2..........10.2.4.DrudewTectrayp.e.Mo.del..3.2.orce.............Preparation...............MgO(001).........39.osition............113.42.5.Eectiv.e.Medium.Mo.del.(Bruggeman.Mo.del)40.tal.I:.wn.4.1.at.emp.........IR.ectra.Gro..12i2.6ChemisorptionMetal.Film.Gro.wth......................2.8.2.1...............................2.8.2.2.A.ed13Noble2.7.MgO,.Ag.and.Cu......2.8.3.A.ed.MgO(001).....................3.erimen.33.Exp.tal.and.d..............16.2.7.1.MgO..33.The.Cham.er.........................33.FTIR.ectrometer.........................35.Ho16Relativ2.7.2SpAgareand.Cu..............36.A.F.Microscop.(AFM).....................38.Sample..............17.2.7.3.Optical.Prop.erties.of.Thin.Films..3.3.1.Substrate...................3.3.2.Dep........23.2.8.A.dsorption.Theory.and.A.dsorbate.CO..40.Gas.osure..............................24.2.8.14PherimenysisorptionResults.Analysis.Ag.Gro.on.41.Ag.Prepared.Ro.T.erature.................4.1.1.T.Sp.of.Films.wn.MgO(001)...43.242
.ten.tsat4.1.2AgIR.T.ransmission.Sp94ectraResultsofofAg.Films.Groothwn.onRoMgO(001)empwithAGasransmissionExp.osure....Islands.of.Small.SEIRA.emp...4.5.4.4.5.4.1.the.on.......wn.on.....Drude.ectra.AFM...ed.....Cu.and..47.4.1.3dsorbCalculationatof.IR.T.ransmission.SpAectraBigofAAgparedFilms.GroCOwnwnon.MgO(001)....on...5.I:.5.1.Cu.om.........Sp.Mo.115.Gro.emp.Gro.....of.Films.........ed.....y50Islands4.1.4.IR.Reection86SpCOectraonofFilmsAg/MgO(001)om.................of.ed.Sho.Islands.of.ed58erature4.2FilmsAgercolationFilms.PreparedSEIRAatdsorbLoFilmswHighT.emp.eratures.Co.oled.with.Liquid4.5.5NofConedAgor.Liquid.Heerimen.Analysis.Films.MgO(001).IR.ectra.Gro.at.emp...............5.2.T.with.yp.....Reection.Cu.on.om.118.of.on.........5.4.1.A69Ultrathin4.2.1ofIR.Sp.ectra.of.Ag.Films.Gro.wn5.4.2onAMgO(001)Thicat.ab.out.506K127.ii.Ag..69.4.2.2.IR.Sp.ectra.of4.5.3AgofFilmsAGroedwnSmoonAgMgO(001)PreparedatRoabTouterature100.K.....74.4.2.3.Fitted.T.ransmission.Sp.ectra.of.Ag.Films.Gro93wnSEIRAonCOMgO(001)dsorbaton50lmsKwingandSeparated10094KSEIRA.CO.dsorb.on.om-temp.Pre-.Ag.Near.P.Threshold.....4.5.4.2.of.A.ed.Ag.Gro.at.T.eratures............76.4.3.Ag.Films.Prepared.at105HighDiscussionTSEIRAempCOeraturesdsorb(400onK,Films450.K,.500.K)109.Exp.tal.and.I79Cu4.3.1GroIRonT111ransmissionMeasuredSpTectraSpofofAgFilmsFilmswnGroMgO(001)wnRoonTMgO(001)erature......80.4.3.2.IR.Reection.Sp.ectra.of.Ag.Films.Gro.wn.on111MgO(001)Fit.the.ransmission.ectra.the.T81e4.4delAFM.Images.of.Ultrathin5.3AgSpFilmsofConsistingFilmsofwnSmallMgO(001)IslandsRo.T.eraure.5.4.Images84Cu4.5wnSEIRAMgO(001)of.CO.A.dsorb.ed.on.Sev.eral.Kinds119ofSEIRAAgCOFilmsdsorb.on.Cu.Consisting.Small..........85.4.5.1.SEIRA.of.CO.A.dsorb.ed.on.Cold-dep122ositedSEIRAAgCOFilmsdsorb.on.k.Films......85.4.5.2.SEIRA123ofConclusionCODiscussionABibliographdsorb131edon4σ
4σ = σ + σ ¡ σ σ σf i s f i
σs
ine-titativlotowtheir1000stagesnm.ucleationNanosizedsubstratemetal[5].lmsatareatin[3,terestingdevmaterialsthisbThereecauseRamanof(AFM,theirynonvcelgrocvhemical,denedph?ysical,al.mecwthhanicalpropand,opticalmeansprop(LEED),ertiesandcomparedytooftheybulkoutmaterials.yManwthyedepotherositiondiusion,teceenhnologiesatomisticaretheasizevtransitionailablegroforcitetheypreparationgivofnmetalillustratenano-lmssurface(seetempRefinuence[1]enforofaofreview).LoOnetroscopofIRtheMicroscopoldestIRtecFhniquesthermalSPM)evunderapAlthoughorationsolvoritvyacuumthresholdevendenapandorationisSucstillvwidelysurfaceused.bindingThinprolmTheorygroucleationwthhasiselopusuallyeclassiedcessesinedtogrothreeAmoasdesdescribingbasedtheontothermostage.dynamicwar-kineticgumenedts:enablesthewhicFarank-vdescriptionanandderhelpsMerwresultseork.moindeand(2Dofgrodrasti-wth),surfacethecrystallographicVetc.olmer-Waeberimenerthemolmsdefor(3DElectrongrospwth),and(SERS),thetionStranski-KrastanoProbv(SPM)moedeec-(rstA2DMicroscopthenkind3Dthegrogrowth).ariousBauerwhasspdevnotel-theopgroedinformationalmthermoAdynamicpcriterionindicatedforfrequencythetransmittancegroucleationwthgromostages.deh[2]inunderolvequilibriumadsorption,conditions.diusion,Thehemicalcriterionandstatesatomicthatcessesthesurfaces.groofwthnmoanddewthisbdetermineddevbedydescribantheenergyprodierenceinbolvellin:lmwwthis4].themcriticalofwdimensionoftenoneforleasttheatfromifnnano-materialsstagenamedthe,wthwhereInare2.6MaterialseisthetheequationssurfaceelopfreebenergyVofetthe[3],lm,hductionestroquanisetheoffreeucleationenergygroofandintoterfacesomeandinInw1Thethinorcterfacedueertiessurfacethetamination,eratureucleationthefects,canmobilitcally,edlmisharacteristicsthetosurfaceconfreenenergyef-ofsurfacetheysubstrate.adsorb2Dgases,gromorphologywthandisori-preferredtationif[1].thearesignlotofexpthetalenergeticfordierenceanalysisisthinpandositivsurfaces,e.example,Thew-energyStranski-KrastanoDiractionvIRmoec-deyisSurface-enhancedtheScatteringinSurface-enhancedtermediateAbsorp-case,(SEIRA),whereScanningthiseenergeticydierenceetc.cWhangesapplysignspattroscopaandcriticaltomiclaorceyyeronethicofknessforprostudyvlmokingwthavtransitionconditionsfromthis2Dork.toIR3Dectroscopgrocanwth.re-Hoewsub-monolaeverer,wth,theoersgroabwththeisconductivita.non-equilibriumlmphenomenon.theMetalercolationlmisgrobwthausuallyindepprotceeds1throughcon1andInnanolms.trotheductionlmsineIRthespandectroscopareyto[6].adsorptionAlittlepcercolatedthelmadsorptioncantainsbresultse[13].describ[15,edinbAgysurfacesaanDrudefatofypoureorkmo,del.thinThehaptereectofofanalysisthecsubstrateettempforerature,adsorbadsorbwedofgasesyandIRtheprosubstrateonsurfaceonpreparedtempbvybdierenwhictywresearcaasysbasiconthetheusedlmduced.groeectivwthmetalareofalsogroundrecognizabletrofromerimenIRthespwn.ectroscoptalyand.Cu/MgO(001)WitheAFMthistheeensurfaceerymorphologiesenhancemenofoflmsonprepared100underalreadyvTheariousthesisconditionstheareFTIRexam-estigatingined.ertiesTheregroareofalreadyCurepandortsCO[7]habloouthatheeentempAg/MgO(001)eratureterestingdepofendenmisttismorphologyoredofothCuerimenlms.TheInthesisthisws:w2,orkrelatedwanalysiseertiespresenwtthistheintemporeraturetheorydepmediumendentheorytgromorphologypropofmetalAgandlmsofgroshortlywnInontheMgO(001)tecsurfaces.ts,Themethoeectareof4surfaceexpenhancedandIRAg/MgO(001)absorptionhapter(SEIRA)thatwFinallyas6,rstsummarizediscotedv2eredwonislandsislandvmetalcruciallmsthebtySEIRAHartsteinCOetedal.Cuinat1980sK[8].asSEIRAstudiedof16].COaimduethistoisatomicdemonstratescaleabilitroughnessofwforasvoftentheobservpropedofonThecold-depwthositedcesslmsultra-thinatandalmstempMgO(001)eraturethebofelogaswsuc50lmKat[9,w10,eratures11,v12].bHoinwestigated.eviserinthesystemSEIRAecauseoftheCOlatticeadsorb(<3%),edhonthereforeAgvlmsbatb100theoreticalKexpistalrarelyhers.reporganizationorted.thisAistfollo100InK,hapterwsomeetheoriesndtothatdatatheandSEIRApropeectofismaterialveeryinstrongwwhenareCOtroadsorbsFonexample,AgDrudelms,preparedeattheoryortheabofolmvwth,eoptical300ertiesK.bulkThisandstronglms,enhancementhettheoryisgasattributedaretointheduced.excitationcof3,transvexpersetalcollectivhniqueseinstrumenelectronandresonancespreparationbdysamplestheshoincidenChaptertconradiationtheperimenolarizedresultsparallelthetoofthesystemarracy5oftainsislandsof[13,system.14].inThehaptersmallwcbrieyhannelsthe(abpresenoutin5thesis.nm)b