X射线光电子能谱课件（英文版）.pdf

X-Ray Photoelectron Spectroscopy(XPS)/Electron Spectroscopy for Chemical Analysis(ESCA)香港城市大擘City UniversityOf Hong KongX-ray Photoelectron SpectroscopyIn t roduc t ionIn st rumen t a t ionQua lit a t ive a n a lysisQua n t it a t ive a n a lysisDept h prof ilin gSma ll a rea a n a lysis a n d XPS ima gin gApplic a t ion exa mplesCha rgin g c ompen sa t ionPhotoelectric EffectEin st ein,Nobel Prize 1921Phot oemission a s a n a n a lyt ic a l t oolKa i Siegba hn,Nobel Prize 1981香港城市大擘City UniversityOf Hong KongXPS,a lso k n own a s ESCA,is a widely used surf a c e a n a lysis t ec hn ique bec a use of it s rela t ive simplic it y in use a n d da t a in t erpret a t ion.XPS X-ra y Phot oelec t ron Spec t rosc opyESCA Elec t ron Spec t rosc opy f br Chemic a l An a lysisUPS Ult ra violet Phot oelec t ron Spec t rosc opy PES Phot oemission Spec t rosc opyElec t ron en ergy a n a lyser香港城市大擘City UniversityOf Hong KongICEj=hv BE spect BE=hv KE spectVacuum levelXPS spectrum of a UHV cleaved InP(110)surfece.Work f unction(|)3d_ c 3p 3sCon duc t ionVa len c eEf 3/2/1 L 11/24(3 3 S/S J U=O D)a w s u b u ihv:Al Ka(1486.6eV)2s41s4-t00 o008o 20 004 o60oBinding Energy(eV)P2sP 2P123/2Kin et ic En ergyPeak NotationsL-S Couplin g(-I s)For p9 d a n d f pea k s,t wo pea k s a re observed.U 4d5/2The sepa ra t ion bet ween t he t wo pea k s a re n a medspin orbital splitting.The va lues of spin orbit a l split t in g of a c ore level of a n elemen t in dif f eren t 4d3/2 1c ompoun ds a re n ea rly t he sa me.IThe peak area ratios of a c ore level of a n Ielemen t in dif f eren t c ompoun ds a re a lso n ea rly 11t he sa me.J ISpin orbit a l split t in g a n d pea k a rea ra t ios a ssist in elemen t a l iden t if ic a t ionXPS spectrum of a UHV cleaved InP(Utt)sor&ca(3as/SJU=0u)叁 SU5UI1000 800 600 400 200Binding Energy7(eV)0)Ap u 山 6pug0,-FERMI LEVEL-5d200 一-5P3/2 5P1/2 5s400 4f 5/2600 4d5/2800 5d 3/21000 4P3/21200 1400-4p1/2Rela t ive bin din g en ergies a n d ion iza t ion c rosssec t ion f or UIonization Cross-Section香港城市大擘City UniversityOf Hong KongAnalysis DepthIn ela st ic mea n f ree pa t h(X)is t he mea n dist a n c e t ha t a n elec t ron t ra vels wit hout en ergy lossdIs=Ioe-d/x32e 0oo2eX 1dxX工dx10For XPS,X in t he ra n ge of 5-35Aol-e-3二-=0.951Only the photoelectrons in the near surface region can escape the sample surface with identifiable energyMeasures top 3九 or 50-100AX-ray Induced Auger Electrons香港城市大擘City UniversityOf Hong KongVG ESCALAB 220i-XLKratos XPS systemTop ViewIn side:Hea t in g st a ge(ma x.1200 C)a n d f ila men t f br ra dic a l gen era t ionWien Filt erTa rget c ha mberGa t e va lveIon bea m sourc eUHV STM5 k eV a rgon ion gunMg x-ra y gunDosin g un itUHV e-bea m eva pora t orQMS f br TDSMa gn etJCMA-QMSLow en ergy ion bea m syst emHea t in g/c oolin g st a ge f or TDS 八Det a c ha ble n it rogen glove boxUV sourc e f br UPSSa mple st a ge wit h hea t in g/c oolin gX-ra y mon oc hroma t orXPS唱詈 LWobblest ic kLEEDEn t ry loa dloc kXPS system suitable for industrial samplesVacuum Chamber Control ElectronicsIon pumpTurbopumpSample Introduction ChamberVacuum System5.8E-09 Torr香港城市大擘City UniversityOf Hong KongUHV ChamberSample Introduction SystemMax.Sample Height:28mmSample Transport SystemOptics Mounting BlockBParking StationlFiveAAis StageParking StationyC Introduction Chamber.。J Platen Transfer ArmPrep Chamber Mount香港城市大擘 City UniversityOf Hong KongSample Positioning Station(SPS)MicroscopeSamplePlatenBase withPositionEncodersCameraA high ma gn if ic a t ion video ima gin g syst em c a pt ures opt ic a l ima ges wit h t he posit ion in f orma t ion a t t a c hed t o t he f ileThe posit ion in f orma t ion drives sa mple st a ge t o t he a n a lysis a rea when t he SPS ima ge f ile is rea d by t he Qua n t um 2000 syst emc omput er香港城市大擘City UniversityOf Hong KongX-ray induced secondary electron imaging for precise location of the analysis areasec on da ry elec t ron sSPS ima ge of a mic roc irc uit t ra n sf erred t o t he Qua n t um 2000 where t he a n a lysis poin t s c a n be def in ed.Observe t he det a ils t ha t is presen t f rom buried la yers,in a n opt ic a l ima ge500 x 500pmSXI ima ge f rom a selec t ed a rea of t he SPS phot o.Observe t he SPS ima ge regist ra t ion a c c ura c y香港城市大擘 City UniversityOf Hong KongX-ray Source in Quantum 2000Scanning FocusedElectron BeamAluminum AnodeScanning Focused X-ray BeamEllipsoidalMonochromatorAnalyzer Input LensSamplePHI Quantum 2000香港城市大擘City UniversityOf Hong KongInstrumentation Elec t ron en ergy a n a lyzer X-ra y sourc e Ar ion gun Neut ra lizer Va c uum syst em Elec t ron ic c on t rols Comput er syst emUlt ra high va c uum IO-9 Torr(6U-P20JI862oq6_uA3PJOO0JHEMISPHERICAL SECTOR ANALYSERamplifierratemeterchannel i1 electron-1multiplier!X-Y recorderelectron energy _*06EO al alwds-EW+Cylin dric a l Mirror An a lyzerCM A:Rela t ively high sign a l a n d good resolut ion 1 eV香港城市大擘City UniversityOf Hong KongConcentric Hemispherical Analyzer(CHA)S slit plate width.1F slit plate width,w2FactorsPa ss en ergyAn a lyzer ra diusSlit widt hElemen t s in t he t ra n sf er len sEn ergy of t he phot oelec t ron s香港城市大擘City UniversityOf Hong KongDual Anode X-ray SourceAn ode f a c e ICooling water shields4 Fila men t 2日cd上Anode face 2香港城市大擘City UniversityOf Hong KongCommon ly usedX-ray linesLineEnergy,eVWidth,eV13230.47ZrM;15140.77NbM17L41.21MoM?19231.53TiLa395.33.0Cr La572.83.0NiLa851.52.5CuLa929.73.8Mg Ka1253.60.7Al Ka1486.60.85Si Kt1739.51.0YLa1922.61.5ZrLa2042.41.7T1K24510.02.0CrKa5417。2 ACuKa8048.02.6X-ra y sourc e:Mg KaSiO2 sample0 IsB l s u a u J600 400 2001000 8000Bin din g En ergy(eV)O KLL f or Mg Ka a t 743 eV O KLL f or Al Ka a t 976eV香港城市大擘City UniversityOf Hong KongX-ray monochromatorX-Ray Source(anode)nX=2dsin0For Al Ka九二 8.3Ause(lOTO)pla n es of qua rt z c ryst a l d=4.25A 6=78.5Adva n t a ges of usin g x-ra y mon oc hroma t or Na rrow pea k widt h Reduc ed ba c k groun d No sa t ellit e&ghost pea k s香港城市大擘City UniversityOf Hong KongGeneral methods in assisting peak identification(1)Chec k pea k posit ion s a n d rela t ive pea k in t en sit ies of 2 or more pea k s(phot oemission lin es a n d Auger lin es)of a n elemen t(1)Chec k spin orbit a l split t in g a n d a rea ra t ios f br p,d9 f pea k sThe f ollowin g elemen t s a re f oun d:O,C,Cl,Si,F,N,S,Al,Na,Fe?K,Cu,Mn,Ca,Cr?Ni,Sn,Zn,Ti,Pb,V香港城市大擘City UniversityOf Hong KongChemical ShiftB.E.=En ergy of Fin a l st a t e-En ergy of in it ia l st a t eFinal state(on e a ddit ion a l+ve c ha rge)Initial state+qRedist ribut ion of elec t ron den sit y BE provides information on chemical environment香港城市大擘City UniversityOf Hong KongExample of Chemical ShiftHICIHoo cF IC IFCARBON Is500o1190 1195Kin et ic en ergy(eV)_295 290 280Bin din g en ergy(eV)香港域市大擘City UniversityOf Hong KongExample of Chemical ShiftShif t(eV)Oxida t ion st a t e香港城市大擘City UniversityOf Hong KongChemical Shifts4f7/2 Bin din g En ergy(eV)Compoun d Type 83AuAuSnAuSiuYbAu2ClAuPh3PClAu(Ph3P)2CbAuPh3P(Ph3P)AuNO3 ClAu(Ph3As)(AuSPEt 2s-)2(-AuCH2PEt2CH2-)284 85 86 87 88Chemical ShiftsCompoundTVPe 982p Binding Energy(eV)101 104SilicidesSiliconCarbidesNitridesSiliconesSilicatesSilica1 香港城市大擘City UniversityOf Hong KongUse of Different Photon Energy(a)Zr Loc(b)Mg Koc(c)Ti KocoxideSi2040 eV1253.6 eV4510 eV香港城市大擘City UniversityOf Hong KongX-ray Induced Auger PeaksAuger pea k s a re a lso sen sit ive t o c hemic a l en viron men tBinding Energy(eV)Cu Chemical State in Cu ClustersAuger Pa ra met er=B.E.(Cu 2p3/2)+K.E.(Cu LMM)Copper Auger LMM Pea kCopper 2p3/2 Pea k938 936 934 932 930 928904 906 908 910 912 914 916 918 920 922 924 926K.E.(eV)En erget ic Cu ion sFused silic aSurf a c e CuCopper 2p3/2 Pea kCopper Auger LMM Pea kAuger Pa ra met er=1847.2 eV940 938 936 934 932 930 928B.E.(eV)904 906 908 910 912 914 916 918 920 922 924 926K.E.(eV)Lit era t ure da t a of Auger pa ra met er:Met a llic Copper(0)=1850.5-1851.9 eVCopper(I)Oxide=1848.4-1849.7 eVQuantitative Analysisx 100%Pea k Area of elemen t AAt omic%=Sen sit ivit y f a c t or of elemen t APea k Area s/Sen sit ivit yf a c t ors of a ll ot her elemen t sPea k Area mea suremen tNeed ba c k groun d subt ra c t ion29 msuslll908082848688Binding Energy(eV)Factors Affecting Photoelectron IntensitiesFor a homogen ous sa mple,t he mea sured phot oelec t ron in t en sit y is given by/.=f-M-c r.-2-c osT/J I LI,c:Phot oelec t ron in t en sit y f or c ore level c of elemen t i f:X-ra y f lux in phot on s per un it a rea per un it t ime NNumber of a t oms of elemen t i per un it volume O：Phot oelec t ric c ross-sec t ion f br c ore level c of elemen t i,Det ec t ordXf九：In ela st ic mea n f ree pa t h of t he phot oelec t ron in t he sa mple ma t rix 0:An gle bet ween t he direc t ion of phot oelec t ron elec t ron a n d t he sa mple n orma lF:An a lyzer solid a n gle of a c c ept a n c eT:An a lyzer t ra n smission f un c t ionD:Det ec t or ef f ic ien c yA:Area of sa mple f rom whic h phot oelec t ron s a re det ec t edEmpirical Approachk=c on st a n tSA=sen sit ivit y f a c t or of aIA=kSAMA c ore level of elemen t AMa=No.of A in t he empiric a l f ormulaIA _ S A s _ 2a M f丁 一 1 A Usua lly a ssume SF=1iF 3p if AFor exa mple,Tef lon(-CF2-)o 4 23c=-If 1 熹港市大看I City University Of Hong KongExamples of Sensitivity FactorsLin eElemen tCompoun dIsLiLi2c O3 L12SO4Bkbf4NH4BF40Na2SO3 CuSO4 K2SO4 Ag(COCF3)3 Na 5P3O io C6H2NS2K3O9Ref eren c eX-ra yslin eMgAlC Is0.0670.069S2p0.0690.067K2p0.500.50N Is0.550.57S2p2.95S2p3.25S2p2.902.85F Is2.622.81Na 2s3.40K2p2.893.051 N必，下nn umber of c ompoun ds t est ed香港城市大擘I City UniversityOf Hong KongTransmission FunctionTra n smission f un c t ion is t he det ec t ion ef f ic ien c y of t he elec t ron en ergy a n a lyzer,whic h is a f un c t ion of elec t ron en ergies.Tra n smission f un c t ion a lso depen ds on t he pa ra met ers of t he elec t ron en ergy a n a lyzer,suc h a s pa ss en ergy.Pure Au after Ar+sputteringPass encigy.网 W1050 900 750 600 450 300 150 010mA 5 mA10mA*5 mABin din g En ergy(eV)1050 900 750 600 450 300 150 0Bin din g En ergy(eV)Correction of sensitivity factor Det ermin e t he t ra n smission f un c t ion of t he XPS syst em t ha t wa s used t o gen era t e t he sen sit ivit y f a c t ors Det ermin e t he t ra n smission f un c t ion of our XPS syst emrpOAwhere SA is t he sen sit ivit y f a c t or of a c ore level of elemen t A,TA is t he t ra n smission f un c t ion of t he in st rumen t a t t he k in et ic en ergy of t he c ore level,a n d supersc ript o is f br t he in st rumen t t ha t is used t o gen era t e t he sen sit ivit y f a c t or香港城市大擘City UniversityOf Hong KongQuantification UncertaintiesAn error of 15%is generally quotede.g.20%of Cu wa s obt a in ed.The%Cu c on c en t ra t ion should be in t he ra n ge of 17-23%.An error of 1-2%can be achieved if samples with known concentrations are used as standardse.g.Det ermin a t ion of t he c on c en t ra t ion s of Si a n d N in SiNx f ilms wit h a Si3N4 st a n da rd.香港城市大擘City UniversityOf Hong KongDepth ProfilingSput t ered ma t eria lsAr+Sput t erin g TimeDepth Scale Calibration1.Sput t erin g ra t e det ermin ed f rom t he t ime required t o sput t er t hrough a la yer of t he sa me ma t eria l of k n own t hic k n ess2.Af t er t he sput t erin g a n a lysis,t he c ra t er dept h is mea sured usin g dept h prof ilomet ry a n d a c on st a n t sput t erin g ra t e is a ssumedASput t erin g Time香港城市大擘City UniversityOf Hong KongTypical ApplicationsI Semic on duc t or ma t eria ls a n d n ia gn et ic media-Survey a n a lysis of ha zes on semic on duc t or surf a c es-An a lysis of proc ess c ompon en t s on wa f ers or devic e st ruc t ures一Dept h prof ile c omposit ion a l a n a lysis of t hin f ilms一Lubric a n t t hic k n ess on ha rd disk s一Con t a min a n t s on prin t ed c irc uit boa rds(PCB s)I Opt ic a l ma t eria ls Iden t if ic a iion of c omposit ion ol ha zes a n d c on t a min a n t s on opt ic a l c ompon en t s(mirrors,et c.)-Composit ion a l a n a lysis of opt ic a l t hin f ilms一Fa ilure a n a lysis of la ser c ompon en t s1 Met a llurgic a l a n d in sula t or sa mples一Composiiion a l surf a c e a n a lysis of met a ls,semic on duc t ors,a n d in sula t ors-Va ria t ion of surf a c e c omposit ion vs.proc essin g-Survey a n a lysis of produc t surf a c esI Orga n ic/polyn ier surf a c e a n a lysis-Iden t if ic a t ion of surf a c e c on t a min a n t on polymers一Iden t if ic a t ion of c hemic a l bon din gSilicon Wafer DiscolorationBinding Energy(eV)Depth Profiling Architectural Glass CoatingSample platen 75 X 75mm Architectural glass coatinglOOnm thick coatingcrater香港城市大擘City UniversityOf Hong KongDepth profile of Architectural Glass Coating00801604020200Sputter Depth(nm)()u o m u o j u o。J I E O l v SurfaceDepth profiling of a multilayer structureNickel(30.3 nm)Chromium(31.7 nm)Chromium Oxide(31.6 nm)Nickel(29.9 nm)Chromium(30.1 nm)Silicon(substrate)()O-EO5Depth Profiling with Sample RotationHigh energy ionsIon s:4 k eV Sa mple st illSampleCr/Si interface width(80/20%)=23.5nmUO_1B-1U0)OUOO O-EOIon s:4 k eV Hi饪n ergy ion sWit h Za la r rot a t ion F,Sample rotatesCr/Si interface width(80/20%)=11.5nmSputtering depth(nm)185Ion s:500 eV,Low energy ionsWit h Za la r rot a t ion/Sample rotatesCr/Si interface width(80/20%)=8.5nmDepth Profile of MOS Capacitor with Sample Rotation于二-o二 utUUCHI。).i=low8 6XL4 2Polvsilicon Si Substrate3Instrumental FactorsAffecting Depth Profiles Adsorpt ion f rom residua l ga s a t mosphere Re-deposit ion of sput t ered spec ies Impurit ies in ion bea m Non-un if orm ion bea m in t en sit y Time-depen den t ion bea m in t en sit y香港城市大擘City UniversityOf Hong KongSample Characteristics Affecting Depth Profiles Origin a l surf a c e roughn ess Cryst a llin e st ruc t ure a n d def ec t s(Cha n n elin g)Alloys,c ompoun ds,sec on d pha ses(pref eren t ia l sput t erin g a n d in duc ed roughn ess)香港城市大擘City UniversityOf Hong KongRadiation-Induced Effects Prima ry ion impla n t a t ion At omic mixin g Sput t erin g-in duc ed roughn ess Pref eren t ia l sput t erin g a n d dec omposit ion of c ompoun ds En ha n c ed dif f usion a n d segrega t ion Elec t ron-in duc ed desorpt ion Cha rgin g of in sula t ors香港城市大擘City UniversityOf Hong KongSmall area analysis and XPS ImagingPhotoelectrons Aperture of/Analyzer lens、/SampleSpot size determined by the analyserBoth monochromated and dual anode x-ray sources can be usedPhotoelectrons Aperture of/Analyzer lensSample1 T Spot size determined by the x-ray beam香港城市大擘.City University Of Hong Kong(1)Moving sample stageImage:x,y position versus photoelectron intensityResolution:50|im(2)Use of scanning platesScanning plates ApertureImage:Voltages V&V scanned:D D x yPhotointensity collected from different points in time sequenceResolution:(3)Use of multichannel plateMCPAn array of e-detectorsSlit plateHemispherical mirror analyzerMagnetic lensMPC detector Slit plate set Spot size apertureyACharge neutralizerScanning plates 7 x-ra