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5.3PhotoelectronSpectroscopy
Photoelectronspectroscopyulizesphotoionizaonandanalysisofthekinecenergydistribuonoftheemied
photoelectronstostudythecomposionandelectronicstateofthesurfaceregionofasample.
Tradionally,whenthetechniquehasbeenusedforsurfacestudiesithasbeensubdividedaccordingtothesource
ofexcingradiaoninto:
XrayPhotoelectronSpectroscopy(XPS)
UltravioletPhotoelectronSpectroscopy(UPS)

usingsoxrays(withaphotonenergyof2002000eV)
toexaminecorelevels.
usingvacuumUVradiaon(withaphotonenergyof10
45eV)toexaminevalencelevels.

Thedevelopmentofsynchrotronradiaonsourceshasenabledhighresoluonstudiestobecarriedoutwith
radiaonspanningamuchwiderandmorecompleteenergyrange(55000+eV)butsuchworkremainsasmall
minorityofallphotoelectronstudiesduetotheexpense,complexityandlimitedavailabilityofsuchsources.

PhysicalPrinciples
Photoelectronspectroscopyisbaseduponasinglephotonin/electronoutprocessandfrommanyviewpointsthis
underlyingprocessisamuchsimplerphenomenonthantheAugerprocess.
TheenergyofaphotonofalltypesofelectromagnecradiaonisgivenbytheEinsteinrelaon:
E=h
where

hPlanckconstant(6.62x1034Js)
frequency(Hz)oftheradiaon

Photoelectronspectroscopyusesmonochromacsourcesofradiaon(i.e.photonsofxedenergy).
InXPSthephotonisabsorbedbyanatominamoleculeorsolid,leadingtoionizaonandtheemissionofacore
(innershell)electron.Bycontrast,inUPSthephotoninteractswithvalencelevelsofthemoleculeorsolid,leading
toionisaonbyremovalofoneofthesevalenceelectrons.
Thekinecenergydistribuonoftheemiedphotoelectrons(i.e.thenumberofemiedphotoelectronsasa
funconoftheirkinecenergy)canbemeasuredusinganyappropriateelectronenergyanalyseranda
photoelectronspectrumcanthusberecorded.
Theprocessofphotoionizaoncanbeconsideredinseveralways:onewayistolookattheoverallprocessas
follows:
A+hA++e
Conservaonofenergythenrequiresthat:
E(A)+h=E(A+)+E(e)
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Sincetheelectron'senergyispresentsolelyaskinecenergy(KE)thiscanberearrangedtogivethefollowing
expressionfortheKEofthephotoelectron:
KE=h(E(A+)E(A))
Thenalterminbrackets,represenngthedierenceinenergybetweentheionizedandneutralatoms,is
generallycalledthebindingenergy(BE)oftheelectronthisthenleadstothefollowingcommonlyquoted
equaon:
KE=hBE
Analternaveapproachistoconsideraoneelectronmodelalongthelinesofthefollowingpictorial
representaon;thismodeloftheprocesshasthebenetofsimplicitybutitcanberathermisleading.

TheBEisnowtakentobeadirectmeasureoftheenergyrequiredtojustremovetheelectronconcernedfromits
inialleveltothevacuumlevelandtheKEofthephotoelectronisagaingivenby:
KE=hBE
NOTEthebindingenergies(BE)ofenergylevelsinsolidsareconvenonallymeasuredwithrespecttotheFermi
levelofthesolid,ratherthanthevacuumlevel.Thisinvolvesasmallcorrecontotheequaongivenabovein
ordertoaccountfortheworkfuncon()ofthesolid,butforthepurposesofthediscussionbelowthiscorrecon
willbeneglected.
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ExperimentalDetails
Thebasicrequirementsforaphotoemissionexperiment(XPSorUPS)are:
1.asourceofxedenergyradiaon(anxraysourceforXPSor,typically,aHedischargelampforUPS)

2.anelectronenergyanalyser(whichcandispersetheemiedelectronsaccordingtotheirkinecenergy,and
therebymeasuretheuxofemiedelectronsofaparcularenergy)

3.ahighvacuumenvironment(toenabletheemiedphotoelectronstobeanalysedwithoutinterferencefrom
gasphasecollisions)
Suchasystemisillustratedschemacallybelow:

Therearemanydierentdesignsofelectronenergyanalyserbutthepreferredoponforphotoemission
experimentsisaconcentrichemisphericalanalyser(CHA)whichusesanelectriceldbetweentwohemispherical
surfacestodispersetheelectronsaccordingtotheirkinecenergy.

5.3.1XrayPhotoelectronSpectroscopy(XPS)
Foreachandeveryelement,therewillbeacharacteriscbindingenergyassociatedwitheachcoreatomicorbital
i.e.eachelementwillgiverisetoacharacteriscsetofpeaksinthephotoelectronspectrumatkinecenergies
determinedbythephotonenergyandtherespecvebindingenergies.
Thepresenceofpeaksatparcularenergiesthereforeindicatesthepresenceofaspecicelementinthesample
understudyfurthermore,theintensityofthepeaksisrelatedtotheconcentraonoftheelementwithinthe
sampledregion.Thus,thetechniqueprovidesaquantaveanalysisofthesurfacecomposionandissomemes
knownbythealternaveacronym,ESCA(ElectronSpectroscopyforChemicalAnalysis).
Themostcommonlyemployedxraysourcesarethosegivingriseto:
MgKradiaon:h=1253.6eV
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AlKradiaon:h=1486.6eV
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Theemiedphotoelectronswillthereforehavekinecenergiesintherangeofca.01250eVor01480eV.
SincesuchelectronshaveveryshortIMFPsinsolids(seeSecon5.1),thetechniqueisnecessarilysurface
sensive.
Example1theXPSspectrumofPdmetal
ThediagrambelowshowsarealXPSspectrumobtainedfromaPdmetalsampleusingMgKradiaon

themainpeaksoccuratkinecenergiesofca.330,690,720,910and920eV.
Sincethephotonenergyoftheradiaonisalwaysknownitisatrivialmaertotransformthespectrumsothatit
isploedagainstBEasopposedtoKE.

Themostintensepeakisnowseentooccuratabindingenergyofca.335eV
Workingdownwardsfromthehighestenergylevels......
1.thevalenceband(4d,5s)emissionoccursatabindingenergyofca.08eV(measuredwithrespecttothe
Fermilevel,oralternavelyatca.412eVifmeasuredwithrespecttothevacuumlevel).
2.theemissionfromthe4pand4slevelsgivesrisetoveryweakpeaksat54eVand88eVrespecvely
3.themostintensepeakatca.335eVisduetoemissionfromthe3dlevelsofthePdatoms,whilstthe3pand
3slevelsgiverisetothepeaksatca.534/561eVand673eVrespecvely.
4.theremainingpeakisnotanXPSpeakatall!itisanAugerpeakarisingfromxrayinducedAugeremission.
Itoccursatakinecenergyofca.330eV(inthiscaseitisreallymeaninglesstorefertoanassociated
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bindingenergy).
Theseassignmentsaresummarisedbelow...

Itmaybefurthernotedthat
therearesignicantdierencesinthenaturalwidthsofthevariousphotoemissionpeaks
thepeakintensiesarenotsimplyrelatedtotheelectronoccupancyoftheorbitals
Exercise1theXPSspectrumofNaCl
Thediagramoppositeshowsanenergyleveldiagram
forsodiumwithapproximatebindingenergiesforthe
corelevels.

IfweareusingMgK(h=1253.6eV)radiaon...
...atwhatkinecenergywilltheNa1s
photoelectronpeakbeobserved?
(the1speakisthatresulngfromphotoionisaonof
the1slevel)
...atwhatkinecenergywilltheNa2sand2p
photoelectronpeaksbeobserved?
SpinOrbitSpling
Closerinspeconofthespectrumshowsthatemissionfromsomelevels(mostobviously3pand3d)doesnotgive
risetoasinglephotoemissionpeak,butacloselyspaceddoublet.
Wecanseethismoreclearlyif,forexample,weexpandthespectrumintheregionofthe3demission...

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The3dphotoemissionisinfactsplitbetweentwopeaks,oneat334.9eVBEandtheotherat340.2eVBE,withan
intensityraoof3:2.Thisarisesfromspinorbitcouplingeectsinthenalstate.Theinnercoreelectronic
conguraonoftheinialstateofthePdis:
(1s)2(2s)2(2p)6(3s)2(3p)6(3d)10....
withallsubshellscompletelyfull.
Theremovalofanelectronfromthe3dsubshellbyphotoionizaonleadstoa(3d)9conguraonforthenal
statesincethedorbitals(l=2)havenonzeroorbitalangularmomentum,therewillbecouplingbetweenthe
unpairedspinandorbitalangularmomenta.
Spinorbitcouplingisgenerallytreatedusingoneoftwomodelswhichcorrespondtothetwolimingwaysin
whichthecouplingcanoccurthesebeingtheLS(orRussellSaunders)couplingapproximaonandthejjcoupling
approximaon.
IfweconsiderthenalionisedstateofPdwithintheRussellSaunderscouplingapproximaon,the
(3d)9conguraongivesrisetotwostates(ignoringanycouplingwithvalencelevels)whichdierslightlyinenergy
andintheirdegeneracy...
2D5/2

gJ=2x{5/2}+1=6

2D3/2

gJ=2x{3/2}+1=4

ThesetwostatesarisefromthecouplingoftheL=2andS=1/2vectorstogivepermiedJvaluesof3/2and5/2.
ThelowestenergynalstateistheonewithmaximumJ(sincetheshellismorethanhalffull),i.e.J=5/2,hence
thisgivesrisetothe"lowerbindingenergy"peak.Therelaveintensiesofthetwopeaksreectsthe
degeneraciesofthenalstates(gJ=2J+1),whichinturndeterminestheprobabilityoftransiontosuchastate
duringphotoionizaon.
TheRussellSaunderscouplingapproximaonisbestappliedonlytolightatomsandthissplingcanalternavely
bedescribedusingindividualelectronlscoupling.Inthiscasetheresultantangularmomentaarisefromthesingle
holeinthedshell;adshellelectron(orhole)hasl=2ands=1/2,whichagaingivespermiedjvaluesof3/2and
5/2withthelaerbeinglowerinenergy.
Thepeaksthemselvesareconvenonallyannotatedasindicatednotetheuseoflowercaseleering
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Thisspinorbitsplingisofcoursenotevidentwithslevels(l=0),butisseenwithp,d&fcorelevelswhichall
showcharacteriscspinorbitdoublets.
ChemicalShis
Theexactbindingenergyofanelectrondependsnotonlyuponthelevelfromwhichphotoemissionisoccurring,
butalsoupon:
1.theformaloxidaonstateoftheatom
2.thelocalchemicalandphysicalenvironment
Changesineither(1)or(2)giverisetosmallshisinthepeakposionsinthespectrumsocalledchemicalshis.
SuchshisarereadilyobservableandinterpretableinXPspectra(unlikeinAugerspectra)becausethetechnique:
isofhighintrinsicresoluon(ascorelevelsarediscreteandgenerallyofawelldenedenergy)
isaoneelectronprocess(thussimplifyingtheinterpretaon)
Atomsofahigherposiveoxidaonstateexhibitahigherbindingenergyduetotheextracoulombicinteracon
betweenthephotoemiedelectronandtheioncore.Thisabilitytodiscriminatebetweendierentoxidaon
statesandchemicalenvironmentsisoneofthemajorstrengthsoftheXPStechnique.
Inpracce,theabilitytoresolvebetweenatomsexhibingslightlydierentchemicalshisislimitedbythepeak
widthswhicharegovernedbyacombinaonoffactors;especially
theintrinsicwidthoftheiniallevelandthelifemeofthenalstate
thelinewidthoftheincidentradiaonwhichfortradionalxraysourcescanonlybeimprovedbyusingx
raymonochromators
theresolvingpoweroftheelectronenergyanalyser
Inmostcases,thesecondfactoristhemajorcontribuontotheoveralllinewidth.
Examplesofchemicalshis
Eg.1Oxidaonstatesof
tanium[Ti2pspectra].

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AngleDependentStudies
AsdescribedinSecon5.1,thedegreeofsurfacesensivityofanelectronbasedtechniquesuchasXPSmaybe
variedbycollecngphotoelectronsemiedatdierentemissionanglestothesurfaceplane.Thisapproachmay
beusedtoperformnondestrucveanalysisofthevariaonofsurfacecomposionwithdepth(withchemical
statespecicity).
Examples
Angledependentnnalysisofasiliconwaferwithanaveoxidelayer
(courtesyofPhysicalElectronics,Inc.(PHI))

5.3.2UltravioletPhotoelectronSpectroscopy(UPS)
InUPSthesourceofradiaonisnormallyanoblegasdischargelamp;frequentlyaHedischargelampemingHe
Iradiaonofenergy21.2eV.
Suchradiaonisonlycapableofionisingelectronsfromtheoutermostlevelsofatomsthevalencelevels.The
advantageofusingsuchUVradiaonoverxraysistheverynarrowlinewidthoftheradiaonandthehighuxof
photonsavailablefromsimpledischargesources.ThemainemphasisofworkusingUPShasbeeninstudying:
1.theelectronicstructureofsolidsdetailedangleresolvedstudiespermitthecompletebandstructuretobe
mappedoutinkspace.
2.theadsorponofrelavelysimplemoleculesonmetalsbycomparisonofthemolecularorbitalsofthe
adsorbedspecieswiththoseofboththeisolatedmoleculeandwithcalculaons.

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