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1XPS…………2PhotoelectronSpectroscopyElectronSpectroscopyforChemicalAnalysisESCAXX-rayPhotoelectronSpectroscopyXPSX-ray200-2000eVUltravioletPhotoelectronSpectroscopyUPSUV10-45eV(hν)X-ray(hν)UVXPSUPSXPSUPSXPS3UppsalaUniversityKaiM.Siegbahn196220KarlManneGeorgSiegbahn1886~1978TheNobelPrizeinPhysics1924forhisdiscoveriesandresearchinthefieldofX-rayspectroscopyKarlSiegbahn‘ssonKaiM.Siegbahn1918~TheNobelPrizeinPhysics1981forhiscontributiontothedevelopmentofhigh-resolutionelectronspectroscopy4¾hνhνhνEb(bindingenergy,BE)EK(kineticenergy,KE)5−++→+eAhA*νXhAAν+⎯⎯→⎯++*AESeAA−+++⎯⎯→⎯2*6¾hνhνEbφSEKErEbhνEFEfEKφSErrSKbEEEh+++=φν7ErhνErMmhνEr2*)(21υmMEr−=Mmυ*)(MmhErν=XEreV0.010.2Rb0.020.4K0.040.7Na0.12Li0.916HAlKαMgKα8EbMmhνEr≈10-1∼10-2eVAlKαXAlKαMgKαXEKφSEKEbφSrSbKEEhE−−−=φν9φSφSPφSφSφSPEKEKspErbSKEEh++=φνbSPKspEEh++=φν10φSPEKspEbhνφSPeVEKspEbφSSPKspSKEEφφ+=+bSPKspbSKEEEEh++=++=φφνSPKspbEhEφν−−=SKEφ+SPKspEφ+11¾AlKαMgKαX50∼1487eVÅ5∼20ÅAESAuger20λÅ102000eV55012¾σrWagnerF1SF1SIX/IF1sZ=1∼12ZZ=12Z=1∼122S2S1S201S2/1r∝σ13Z=1∼121SZZZ122PZZ=31102030405060708090100(IX/IF1s)1S2P3d4f12316290ZZ=1∼121SZ=13∼311PZ=32∼623dZ=63∼904f14¾XPSHeisenbergτ10-14∼10-15sΓ10-1∼100eVXPSAESEPMA)(101.415eVhττ−×==Γ15XPSXPSZXPSKL10203040Z∆E16¾EbEKXPSEbXEKXPSEbEKEbXEKSPbKEhEφν−−=EbEK17¾XPSφSPEbEKFe2O3Fe3+Fe261S22S22P63S23P63d64S2Fe3+1S22S22P63S23P63d53dSPbKEhEφν−−=18Fe3+3S3S3d3P3S2e-hν3d3P3S123d3P3S119XPS1MnF2MnOMnO2FeF3K4Fe(CN)43S(2)3S(1)3P(3)3P(2)3P(1)3P(1)3P(2)3P(3)3S(1)3S(2)3S5∼6eV20¾“”ωbħωb15.515.5Al2S117.515.515.5EK21XXσiXI0IXI0X/cm2·seciσiYλexp(-x/λ)λA22iniθXTσiYλSF1SSF1s=1S=Si/SF1s=SiWagner62135TAnYIIiiθλσ0=SITAYIInii==θλσ023SiIixAESXPS∑∑==iiixxiixxSISInnC//24EbESCAESCAEb25(Tio)TiO2(Ti4+)Ti2pXPS9~4.6eV9∆E∆E26ESCAXPS¾¾¾27XPS“”XPSθXPSXPS28XhνCθCdACdBAθAC=d/sinθhνPhotoelectronC]exp[0λACII−=AC=3λλ5%5%3λd=ACsinθ=3λsinθ≤3λθdθ3λ29PSCO32-COO-C=OC-Oθ=10oθ=90oC1SMgKαXλ=2.3nmθ=90o3λ=6.9nmθ=10od=3λsinθ=1.2nm1∼1.5nmθ=90od=3λ=6.9nmCHXCHXθ=10od=1.2nm293287281C1SeVCO32-COO-C=OC-O30X31XPSX32KratosAxisULTRAX-rayPhotoelectronSpectrometerHighenergyresolutionspectroscopy(0.3eV)Parallelphotoelectronimaging(5µm)Sampleprocessingchambers(pretreatmentandthin-filmgrowth)MonochromaticsourceChangeneutralizationIongunforsputteringandionscatteringspectroscopyAngleresolvedXPS33XPSKα1L3→K34¾ZσiXXNZZ0.51.0AlKαKαWN/WN/WN/35¾XKα1L3→KKα2L2→KXPSKα1∆E2222EEEE∆+∆+∆=∆Kα1L3→KKα1L3KZL3K∆E=h/τσiZXPSXXAlKα1MgKα1L1K010203040Z1.02.03.0∆EL3L2L3KKα2Kα136Kα1Kα1Kα2Kα1Kα2Kα1Kα2∆EKα1∆EKα1ZKα1Kα2L3L2∆εZZ22Kα1Kα2∆ε∆EKα1Kα1Kα2XPSZ22Kα1Kα2Kα2Kα1∆ε∆EKα1∆EKα137hνKα1Kα2AlKα1MgKα1X0.45(hν)132.3YKξY0.77(hν)151.4ZrKξZr25417CrKαCr28055CuKαCu0.831486.6AlKα1Al0.681253.6MgKα1Mg∆EKα1(eV)X-rayWN/38¾XPSRowlandRRowlandφλX∆a∆SRowland∆αX∆fφR)2/(22φαλλtgRfRSa×∆+∆+∆+∆=∆39r1r2-VPErd)11(212rrdVEPr−−=υ0dr2r1r-VPυ0Erf1reEmaf==140rf2f1=f2rd=rErr=(r1+r2)/2r1r2E01/(2mυ0)edmmaf2002υ==)11(21220rrreVrmeEfPr−===υ)()(2)]11([2112021122021220rrrreErrrremrrrermVP−=−=−•=υυ41-VPE0∆E=E0W/2r≈0.26eVW)()(2)]11([2112021122021220rrrreErrrremrrrermVP−=−=−•=υυ42Z≥2H43XPSZ≥2SN48hPbNH2N1SS2PS4+S6+SO2SO42-44NMRIIIRIXPSIS2PIIS2PISRR’OOSSRR’OOSII4546¾Na2S2O3iSS2PiiSS2POiiS2PXPSS2P1/22P3/2S1:1SO42-SXPSS2P1/2S2P1/2S2P3/2S2P3/2iSiiSS2P1/2S2P3/2EbSO42-SOSSOO2-iii47¾Fe1-XOPFeO2-Fe3+Fe2+3Fe2+→2Fe3++VFe2+Fe23+VFe2+O3Fe2+Fe3+KCr3O8Fe2+Fe3+Fe3SFe3SFe2PFe2PEbCr3PCr3SCr3+Cr6+Cr3+Cr6+2Cr6+1Cr3+48¾N1SRCONH2398400402404406408N1S(eV)R4N-RCNRRC≡NRNO2RNO3NO3-NO2-CN-[N=N=N]-R-N=N-RON1SNO3-NO2-CN-N=ON=NN≡CN=ON=NN≡CXPS49M2+O·Fe23+O3M2+Fe3+Zn2+(Fe3+)2O4Fe3+(Fe3+M2+)O4XPSFe2PFe2P50XPSUPSN1SC1S51¾35Li2O-65SiO2O1SXPS(Si-O-SiOb)(Si-O-R+Onb)(O2-)Li2ONa2OK2OSiO2R+Z/rLi+→Na+→K+ObOnb52¾Sol-gel-Sol-gelSiO2800oC∼600oCXPSsol-gel-glassXPSObOnbObgelXPSOb53gelSi-OTTLSi-O-SiOb%THTLTHTMTLTMTHT(oC)Ob%gelTTMgelPLIRBETXPSObS54¾MoO2Mo3dXPSO27O2Mo3dXPS225231237Mo3dEb(eV)O27O255¾Be10-5torrAlAlKαBe1SXPS10-5torrBeOBe1SBeBe1S2.9eV10-5torrBeBeZrBeBeOBe1SBeXPSBePO2115110105Be1SEb(eV)2.9BeOBe1S10-5torr10-5torrZrBeBe1S56¾PbO-SiO2PbO-SiO2PbO-SiO2H2Pb4fEK(eV)4f2/34f1/3Pb2+Pb2+Pb+Pb+Pb0Pb0XPSH2PbPbO-SiO2H2“”100nmPb“”57¾SiPBnpSi2PEbpnSi2PEbnpSi2PEb(eV)58¾TiO2TiO2TiO2TiO2TiO2SiO2Al2O3“”SiO2Al2O3TiO259XPSTiO2SiO2ITi2PISi2P=0TiO2SiO2Ti2PSi2PITi2PISi2PSiO2ITi2PSiO2SiO2d=3λITi2P≈05%λSiO2ISi2PSiO2d≈3λISi2P/ITi2Pd/λd/λISi2P/ITi2Pd≈3λISi2P/ITi2P≈∞]/exp[0λdII−=60SiO2TiO2SiO2TiO2SiO2SiO2d≈3λ“”SiO2TiO2SiO201234d/λITi2PISi2P1.00.50ISi2P/ITi2PISi2P/ITi2PISi2PITi2P1.00.50TiO2“”SiO2ITi2PISi2P/ITi2Pd/λ61