Xrayfluorescence

FromWikipedia,thefreeencyclopedia

Xrayfluorescence(XRF)istheemissionofcharacteristic"secondary"(or
fluorescent)Xraysfromamaterialthathasbeenexcitedbybombardingwithhigh
energyXraysorgammarays.Thephenomenoniswidelyusedforelemental
analysisandchemicalanalysis,particularlyintheinvestigationofmetals,glass,
ceramicsandbuildingmaterials,andforresearchingeochemistry,forensicscience,
archaeologyandartobjects[1]suchaspaintings[2]andmurals.

Contents
1 Underlyingphysics
1.1 Characteristicradiation
1.2 Primaryradiation
1.3 Dispersion
1.4 Detection
1.5 Xrayintensity
2 Chemicalanalysis
2.1 Energydispersivespectrometry
2.1.1 Si(Li)detectors
2.1.2 Waferdetectors
2.1.3 Amplifiers
2.1.4 Processing
2.1.5 Usage
2.2 Wavelengthdispersivespectrometry
2.2.1 Samplepreparation
2.2.2 Monochromators
2.2.3 AnalysisLines
2.2.4 Crystals
2.2.5 Detectors
2.2.6 Extractinganalyticalresults
3 Otherspectroscopicmethodsusingthesameprinciple
4 Instrumentqualification
5 Seealso
6 Notes
7 References
8 Externallinks

APhilipsPW1606Xray
fluorescencespectrometerwith
automatedsamplefeedinacement
plantqualitycontrollaboratory

3DscanningoftheRembrandt
paintingSyndicsoftheDrapers'
Guild.

Underlyingphysics
WhenmaterialsareexposedtoshortwavelengthXraysortogammarays,
ionizationoftheircomponentatomsmaytakeplace.Ionizationconsistsofthe
ejectionofoneormoreelectronsfromtheatom,andmayoccuriftheatomis
exposedtoradiationwithanenergygreaterthanitsionizationpotential.Xraysand
gammarayscanbeenergeticenoughtoexpeltightlyheldelectronsfromtheinner
orbitalsoftheatom.Theremovalofanelectroninthiswaymakestheelectronic
Figure1:PhysicsofXray
structureoftheatomunstable,andelectronsinhigherorbitals"fall"intothelower
fluorescenceinaschematic
orbitaltofilltheholeleftbehind.Infalling,energyisreleasedintheformofa
representation.
photon,theenergyofwhichisequaltotheenergydifferenceofthetwoorbitals
involved.Thus,thematerialemitsradiation,whichhasenergycharacteristicofthe
atomspresent.Thetermfluorescenceisappliedtophenomenainwhichtheabsorptionofradiationofaspecificenergy
resultsinthereemissionofradiationofadifferentenergy(generallylower).

Characteristicradiation

Eachelementhaselectronicorbitalsofcharacteristicenergy.Following
removalofaninnerelectronbyanenergeticphotonprovidedbya
primaryradiationsource,anelectronfromanoutershelldropsintoits
place.Therearealimitednumberofwaysinwhichthiscanhappen,as
showninFigure1.Themaintransitionsaregivennames:anLK
transitionistraditionallycalledK,anMKtransitioniscalledK ,an
MLtransitioniscalledL,andsoon.Eachofthesetransitionsyields
afluorescentphotonwithacharacteristicenergyequaltothedifference
inenergyoftheinitialandfinalorbital.Thewavelengthofthis
fluorescentradiationcanbecalculatedfromPlanck'sLaw:
Figure2:TypicalwavelengthdispersiveXRF
spectrum

Thefluorescentradiationcanbeanalysedeitherbysortingtheenergies
ofthephotons(energydispersiveanalysis)orbyseparatingthe
wavelengthsoftheradiation(wavelengthdispersiveanalysis).Once
sorted,theintensityofeachcharacteristicradiationisdirectlyrelatedto
theamountofeachelementinthematerial.Thisisthebasisofa
powerfultechniqueinanalyticalchemistry.Figure2showsthetypical
formofthesharpfluorescentspectrallinesobtainedinthewavelength
dispersivemethod(seeMoseley'slaw).

Primaryradiation
Inordertoexcitetheatoms,asourceofradiationisrequired,with
sufficientenergytoexpeltightlyheldinnerelectrons.ConventionalX
Figure3:Spectrumofarhodiumtargettube
raygeneratorsaremostcommonlyused,becausetheiroutputcan
operatedat60kV,showingcontinuousspectrum
readilybe"tuned"fortheapplication,andbecausehigherpowercanbe
andKlines
deployedrelativetoothertechniques.However,gammaraysourcescan
beusedwithouttheneedforanelaboratepowersupply,allowingan
easieruseinsmallportableinstruments.WhentheenergysourceisasynchrotronortheXraysarefocusedbyanopticlike
apolycapillary,theXraybeamcanbeverysmallandveryintense.Asaresult,atomicinformationonthesubmicrometre
scalecanbeobtained.Xraygeneratorsintherange2060kVareused,whichallowexcitationofabroadrangeofatoms.
Thecontinuousspectrumconsistsof"bremsstrahlung"radiation:radiationproducedwhenhighenergyelectronspassing
throughthetubeareprogressivelydeceleratedbythematerialofthetubeanode(the"target").Atypicaltubeoutput
spectrumisshowninfigure3.

Dispersion
Inenergydispersiveanalysis,thefluorescentXraysemittedbythematerialsamplearedirectedintoasolidstatedetector
whichproducesa"continuous"distributionofpulses,thevoltagesofwhichareproportionaltotheincomingphoton
energies.Thissignalisprocessedbyamultichannelanalyser(MCA)whichproducesanaccumulatingdigitalspectrumthat
canbeprocessedtoobtainanalyticaldata.
Inwavelengthdispersiveanalysis,thefluorescentXraysemittedbythematerialsamplearedirectedintoadiffraction
gratingmonochromator.Thediffractiongratingusedisusuallyasinglecrystal.Byvaryingtheangleofincidenceandtake
offonthecrystal,asingleXraywavelengthcanbeselected.ThewavelengthobtainedisgivenbytheBraggEquation:

wheredisthespacingofatomiclayersparalleltothecrystalsurface.

Detection
Inenergydispersiveanalysis,dispersionanddetectionareasingleoperation,asalreadymentionedabove.Proportional
countersorvarioustypesofsolidstatedetectors(PINdiode,Si(Li),Ge(Li),SiliconDriftDetectorSDD)areused.Theyall
sharethesamedetectionprinciple:AnincomingXrayphotonionisesalargenumberofdetectoratomswiththeamountof

chargeproducedbeingproportionaltotheenergyoftheincomingphoton.Thechargeisthencollectedandtheprocess
repeatsitselfforthenextphoton.Detectorspeedisobviouslycritical,asallchargecarriersmeasuredhavetocomefrom
thesamephotontomeasurethephotonenergycorrectly(peaklengthdiscriminationisusedtoeliminateeventsthatseemto
havebeenproducedbytwoXrayphotonsarrivingalmostsimultaneously).Thespectrumisthenbuiltupbydividingthe
energyspectrumintodiscretebinsandcountingthenumberofpulsesregisteredwithineachenergybin.EDXRFdetector
typesvaryinresolution,speedandthemeansofcooling(alownumberoffreechargecarriersiscriticalinthesolidstate
detectors):proportionalcounterswithresolutionsofseveralhundredeVcoverthelowendoftheperformancespectrum,
followedbyPINdiodedetectors,whiletheSi(Li),Ge(Li)andSiliconDriftDetectors(SDD)occupythehighendofthe
performancescale.
Inwavelengthdispersiveanalysis,thesinglewavelengthradiationproducedbythemonochromatorispassedintoa
photomultiplier,adetectorsimilartoaGeigercounter,whichcountsindividualphotonsastheypassthrough.Thecounter
isachambercontainingagasthatisionisedbyXrayphotons.Acentralelectrodeischargedat(typically)+1700Vwith
respecttotheconductingchamberwalls,andeachphotontriggersapulselikecascadeofcurrentacrossthisfield.The
signalisamplifiedandtransformedintoanaccumulatingdigitalcount.Thesecountsarethenprocessedtoobtainanalytical
data.

Xrayintensity
Thefluorescenceprocessisinefficient,andthesecondaryradiationismuchweakerthantheprimarybeam.Furthermore,
thesecondaryradiationfromlighterelementsisofrelativelylowenergy(longwavelength)andhaslowpenetratingpower,
andisseverelyattenuatedifthebeampassesthroughairforanydistance.Becauseofthis,forhighperformanceanalysis,
thepathfromtubetosampletodetectorismaintainedundervacuum(around10Paresidualpressure).Thismeansin
practicethatmostoftheworkingpartsoftheinstrumenthavetobelocatedinalargevacuumchamber.Theproblemsof
maintainingmovingpartsinvacuum,andofrapidlyintroducingandwithdrawingthesamplewithoutlosingvacuum,pose
majorchallengesforthedesignoftheinstrument.Forlessdemandingapplications,orwhenthesampleisdamagedbya
vacuum(e.g.avolatilesample),aheliumsweptXraychambercanbesubstituted,withsomelossoflowZ(Z=atomic
number)intensities.

Chemicalanalysis
TheuseofaprimaryXraybeamtoexcitefluorescentradiationfromthesamplewasfirstproposedbyGlockerand
Schreiberin1928.[3]Today,themethodisusedasanondestructiveanalyticaltechnique,andasaprocesscontroltoolin
manyextractiveandprocessingindustries.Inprinciple,thelightestelementthatcanbeanalysedisberyllium(Z=4),but
duetoinstrumentallimitationsandlowXrayyieldsforthelightelements,itisoftendifficulttoquantifyelementslighter
thansodium(Z=11),unlessbackgroundcorrectionsandverycomprehensiveinterelementcorrectionsaremade.

Energydispersivespectrometry
Inenergydispersivespectrometers(EDXorEDS),thedetectorallowsthe
determinationoftheenergyofthephotonwhenitisdetected.Detectorshistorically
havebeenbasedonsiliconsemiconductors,intheformoflithiumdriftedsilicon
crystals,orhighpuritysiliconwafers.

Figure4:Schematicarrangementof
EDXspectrometer

Si(Li)detectors
Theseconsistessentiallyofa35mmthicksiliconjunctiontypepindiode(same
asPINdiode)withabiasof1000Vacrossit.Thelithiumdriftedcentrepartforms
thenonconductingilayer,whereLicompensatestheresidualacceptorswhich
wouldotherwisemakethelayerptype.WhenanXrayphotonpassesthrough,it
causesaswarmofelectronholepairstoform,andthiscausesavoltagepulse.To
obtainsufficientlylowconductivity,thedetectormustbemaintainedatlow
temperature,andliquidnitrogencoolingmustbeusedforthebestresolution.With
somelossofresolution,themuchmoreconvenientPeltiercoolingcanbe
employed.[4]
Waferdetectors

Figure5:SchematicformofaSi(Li)
detector

Morerecently,highpuritysiliconwaferswithlowconductivityhavebecomeroutinelyavailable.CooledbythePeltier
effect,thisprovidesacheapandconvenientdetector,althoughtheliquidnitrogencooledSi(Li)detectorstillhasthebest
resolution(i.e.abilitytodistinguishdifferentphotonenergies).
Amplifiers
Thepulsesgeneratedbythedetectorareprocessedbypulseshapingamplifiers.Ittakestimefortheamplifiertoshapethe
pulseforoptimumresolution,andthereisthereforeatradeoffbetweenresolutionandcountrate:longprocessingtimefor
goodresolutionresultsin"pulsepileup"inwhichthepulsesfromsuccessivephotonsoverlap.Multiphotoneventsare,
however,typicallymoredrawnoutintime(photonsdidnotarriveexactlyatthesametime)thansinglephotoneventsand
pulselengthdiscriminationcanthusbeusedtofiltermostoftheseout.Evenso,asmallnumberofpileuppeakswill
remainandpileupcorrectionshouldbebuiltintothesoftwareinapplicationsthatrequiretraceanalysis.Tomakethemost
efficientuseofthedetector,thetubecurrentshouldbereducedtokeepmultiphotonevents(beforediscrimination)ata
reasonablelevel,e.g.520%.
Processing
Considerablecomputerpowerisdedicatedtocorrectingforpulsepileupandforextractionofdatafrompoorlyresolved
spectra.Theseelaboratecorrectionprocessestendtobebasedonempiricalrelationshipsthatmaychangewithtime,sothat
continuousvigilanceisrequiredinordertoobtainchemicaldataofadequateprecision.
Usage
EDXspectrometersaredifferentfromWDXspectrometersinthattheyaresmaller,simplerindesignandhavefewer
engineeredparts,howevertheyarenotasaccurate.WDXhasgreaterresolutionpowerthanEDX.Theycanalsouse
miniatureXraytubesorgammasources.Thismakesthemcheaperandallowsminiaturizationandportability.Thistypeof
instrumentiscommonlyusedforportablequalitycontrolscreeningapplications,suchastestingtoysforlead(Pb)content,
sortingscrapmetals,andmeasuringtheleadcontentofresidentialpaint.Ontheotherhand,thelowresolutionand
problemswithlowcountrateandlongdeadtimemakestheminferiorforhighprecisionanalysis.Theyare,however,very
effectiveforhighspeed,multielementalanalysis.FieldPortableXRFanalyserscurrentlyonthemarketweighlessthan
2kg,andhavelimitsofdetectionontheorderof2partspermillionoflead(Pb)inpuresand.

Wavelengthdispersivespectrometry
Inwavelengthdispersivespectrometers(WDXorWDS),thephotonsareseparated
bydiffractiononasinglecrystalbeforebeingdetected.Althoughwavelength
dispersivespectrometersareoccasionallyusedtoscanawiderangeofwavelengths,
producingaspectrumplotasinEDS,theyareusuallysetuptomakemeasurements
onlyatthewavelengthoftheemissionlinesoftheelementsofinterest.Thisis
achievedintwodifferentways:

Figure6:Schematicarrangementof
wavelengthdispersivespectrometer

"Simultaneous"spectrometershaveanumberof"channels"dedicatedto
analysisofasingleelement,eachconsistingofafixedgeometrycrystal
monochromator,adetector,andprocessingelectronics.Thisallowsanumber
ofelementstobemeasuredsimultaneously,andinthecaseofhighpowered
instruments,completehighprecisionanalysescanbeobtainedinunder30s.
Anotheradvantageofthisarrangementisthatthefixedgeometry
monochromatorshavenocontinuouslymovingparts,andsoareveryreliable.
Reliabilityisimportantinproductionenvironmentswhereinstrumentsare
expectedtoworkwithoutinterruptionformonthsatatime.Disadvantagesof
Chemistoperatesagoniometerused
simultaneousspectrometersincluderelativelyhighcostforcomplexanalyses,
sinceeachchannelusedisexpensive.Thenumberofelementsthatcanbe
forXrayfluorescenceanalysisof
measuredislimitedto1520,becauseofspacelimitationsonthenumberof
individualgrainsofmineral
monochromatorsthatcanbecrowdedaroundthefluorescingsample.The
specimens,U.S.GeologicalSurvey,
needtoaccommodatemultiplemonochromatorsmeansthataratheropen
1958.
arrangementaroundthesampleisrequired,leadingtorelativelylongtube
samplecrystaldistances,whichleadstolowerdetectedintensitiesandmore
scattering.Theinstrumentisinflexible,becauseifanewelementistobemeasured,anewmeasurementchannelhas
tobeboughtandinstalled.

"Sequential"spectrometershaveasinglevariablegeometrymonochromator(butusuallywithanarrangementfor
selectingfromachoiceofcrystals),asingledetectorassembly(butusuallywithmorethanonedetectorarrangedin
tandem),andasingleelectronicpack.Theinstrumentisprogrammedtomovethroughasequenceofwavelengths,in
eachcaseselectingtheappropriateXraytubepower,theappropriatecrystal,andtheappropriatedetector
arrangement.Thelengthofthemeasurementprogramisessentiallyunlimited,sothisarrangementisveryflexible.
Becausethereisonlyonemonochromator,thetubesamplecrystaldistancescanbekeptveryshort,resultingin
minimallossofdetectedintensity.Theobviousdisadvantageisrelativelylonganalysistime,particularlywhenmany
elementsarebeinganalysed,notonlybecausetheelementsaremeasuredinsequence,butalsobecauseacertain
amountoftimeistakeninreadjustingthemonochromatorgeometrybetweenmeasurements.Furthermore,the
frenziedactivityofthemonochromatorduringananalysisprogramisachallengeformechanicalreliability.
However,modernsequentialinstrumentscanachievereliabilityalmostasgoodasthatofsimultaneousinstruments,
evenincontinuoususageapplications.
Samplepreparation
Inordertokeepthegeometryofthetubesampledetectorassemblyconstant,thesampleisnormallypreparedasaflatdisc,
typicallyofdiameter2050mm.Thisislocatedatastandardized,smalldistancefromthetubewindow.BecausetheXray
intensityfollowsaninversesquarelaw,thetolerancesforthisplacementandfortheflatnessofthesurfacemustbevery
tightinordertomaintainarepeatableXrayflux.Waysofobtainingsamplediscsvary:metalsmaybemachinedtoshape,
mineralsmaybefinelygroundandpressedintoatablet,andglassesmaybecasttotherequiredshape.Afurtherreasonfor
obtainingaflatandrepresentativesamplesurfaceisthatthesecondaryXraysfromlighterelementsoftenonlyemitfrom
thetopfewmicrometresofthesample.Inordertofurtherreducetheeffectofsurfaceirregularities,thesampleisusually
spunat520rpm.Itisnecessarytoensurethatthesampleissufficientlythicktoabsorbtheentireprimarybeam.For
higherZmaterials,afewmillimetresthicknessisadequate,butforalightelementmatrixsuchascoal,athicknessof30
40mmisneeded.
Monochromators
Thecommonfeatureofmonochromatorsisthemaintenanceofasymmetrical
geometrybetweenthesample,thecrystalandthedetector.Inthisgeometrythe
Braggdiffractionconditionisobtained.
TheXrayemissionlinesareverynarrow(seefigure2),sotheanglesmustbe
definedwithconsiderableprecision.Thisisachievedintwoways:

Figure7:Braggdiffractioncondition

FlatcrystalwithSollercollimators
TheSollercollimatorisastackofparallelmetalplates,spacedafewtenthsofamillimetreapart.Toimproveangle
resolution,onemustlengthenthecollimator,and/orreducetheplatespacing.Thisarrangementhastheadvantageof
simplicityandrelativelylowcost,butthecollimatorsreduceintensityandincreasescattering,andreducetheareaof
sampleandcrystalthatcanbe"seen".Thesimplicityofthegeometryisespeciallyusefulforvariablegeometry
monochromators.
Curvedcrystalwithslits
TheRowlandcirclegeometryensuresthattheslitsarebothinfocus,butinorderfor
theBraggconditiontobemetatallpoints,thecrystalmustfirstbebenttoaradius
of2R(whereRistheradiusoftheRowlandcircle),thengroundtoaradiusofR.
Thisarrangementallowshigherintensities(typically8fold)withhigherresolution
Figure8:FlatcrystalwithSoller
(typically4fold)andlowerbackground.However,themechanicsofkeeping
collimators
Rowlandcirclegeometryinavariableanglemonochromatorisextremelydifficult.
Inthecaseoffixedanglemonochromators(foruseinsimultaneousspectrometers),
crystalsbenttoalogarithmicspiralshapegivethebestfocusingperformance.The
manufactureofcurvedcrystalstoacceptabletolerancesincreasestheirpriceconsiderably.
AnalysisLines
Thespectrallinesusedforchemicalanalysisareselectedonthebasisofintensity,accessibilitybytheinstrument,andlack
oflineoverlaps.Typicallinesused,andtheirwavelengths,areasfollows:

Figure9:Curvedcrystalwithslits

element line

wavelength
(nm)

element line

wavelength
(nm)

element line

wavelength
(nm)

element line

wavelength
(nm)

Li

22.8

Ni

K1 0.1658

L1 0.3149

Pt

L1 0.1313

Be

11.4

Cu

K1 0.1541

Xe

L1 0.3016

Au

L1 0.1276

6.76

Zn

K1 0.1435

Cs

L1 0.2892

Hg

L1 0.1241

4.47

Ga

K1 0.1340

Ba

L1 0.2776

Tl

L1 0.1207

3.16

Ge

K1 0.1254

La

L1 0.2666

Pb

L1 0.1175

2.362

As

K1 0.1176

Ce

L1 0.2562

Bi

L1 0.1144

K1,2 1.832

Se

K1 0.1105

Pr

L1 0.2463

Po

L1 0.1114

Ne

K1,2 1.461

Br

K1 0.1040

Nd

L1 0.2370

At

L1 0.1085

Na

K1,2 1.191

Kr

K1 0.09801

Pm

L1 0.2282

Rn

L1 0.1057

Mg

K1,2 0.989

Rb

K1 0.09256

Sm

L1 0.2200

Fr

L1 0.1031

Al

K1,2 0.834

Sr

K1 0.08753

Eu

L1 0.2121

Ra

L1 0.1005

Si

K1,2 0.7126

K1 0.08288

Gd

L1 0.2047

Ac

L1 0.0980

K1,2 0.6158

Zr

K1 0.07859

Tb

L1 0.1977

Th

L1 0.0956

K1,2 0.5373

Nb

K1 0.07462

Dy

L1 0.1909

Pa

L1 0.0933

Cl

K1,2 0.4729

Mo

K1 0.07094

Ho

L1 0.1845

L1 0.0911

Ar

K1,2 0.4193

Tc

K1 0.06751

Er

L1 0.1784

Np

L1 0.0888

K1,2 0.3742

Ru

K1 0.06433

Tm

L1 0.1727

Pu

L1 0.0868

Ca

K1,2 0.3359

Rh

K1 0.06136

Yb

L1 0.1672

Am

L1 0.0847

Sc

K1,2 0.3032

Pd

K1 0.05859

Lu

L1 0.1620

Cm

L1 0.0828

Ti

K1,2 0.2749

Ag

K1 0.05599

Hf

L1 0.1570

Bk

L1 0.0809

K1 0.2504

Cd

K1 0.05357

Ta

L1 0.1522

Cf

L1 0.0791

Cr

K1 0.2290

In

L1 0.3772

L1 0.1476

Es

L1 0.0773

Mn

K1 0.2102

Sn

L1 0.3600

Re

L1 0.1433

Fm

L1 0.0756

Fe

K1 0.1936

Sb

L1 0.3439

Os

L1 0.1391

Md

L1 0.0740

Co

K1 0.1789

Te

L1 0.3289

Ir

L1 0.1351

No

L1 0.0724

Otherlinesareoftenused,dependingonthetypeofsampleandequipmentavailable.
Crystals
Thedesirablecharacteristicsofadiffractioncrystalare:
Highdiffractionintensity

Highdispersion
Narrowdiffractedpeakwidth
Highpeaktobackground
Absenceofinterferingelements
Lowthermalcoefficientofexpansion
StabilityinairandonexposuretoXrays
Readyavailability
Lowcost
Crystalswithsimplestructuretendtogivethebestdiffractionperformance.Crystalscontainingheavyatomscandiffract
well,butalsofluorescethemselves,causinginterference.Crystalsthatarewatersoluble,volatileororganictendtogive
poorstability.
CommonlyusedcrystalmaterialsincludeLiF(lithiumfluoride),ADP(ammoniumdihydrogenphosphate),Ge
(germanium),graphite,InSb(indiumantimonide),PE(tetrakis(hydroxymethyl)methane:pentaerythritol),KAP
(potassiumhydrogenphthalate),RbAP(rubidiumhydrogenphthalate)andTlAP(thallium(I)hydrogenphthalate).In
addition,thereisanincreasinguseof"layeredsyntheticmicrostructures",whichare"sandwich"structuredmaterials
comprisingsuccessivethicklayersoflowatomicnumbermatrix,andmonatomiclayersofaheavyelement.Thesecanin
principlebecustommanufacturedtodiffractanydesiredlongwavelength,andareusedextensivelyforelementsinthe
rangeLitoMg.
Propertiesofcommonlyusedcrystals
material

plane

d(nm)

min(nm) max(nm)

thermal
expansion

intensity

durability

LiF

200

0.2014

0.053

0.379

+++++

+++

+++

LiF

220

0.1424

0.037

0.268

+++

++

+++

LiF

420

0.0901

0.024

0.169

++

++

+++

ADP

101

0.5320

0.139

1.000

++

++

Ge

111

0.3266

0.085

0.614

+++

+++

graphite

001

0.3354

0.088

0.630

++++

+++

InSb

111

0.3740

0.098

0.703

++++

+++

PE

002

0.4371

0.114

0.821

+++

+++++

KAP

1010

1.325

0.346

2.490

++

++

++

RbAP

1010

1.305

0.341

2.453

++

++

++

Si

111

0.3135

0.082

0.589

++

+++

TlAP

1010

1.295

0.338

2.434

+++

++

++

YB66

400

0.586

6nmLSM

6.00

1.566

11.276

+++

++

Detectors
Detectorsusedforwavelengthdispersivespectrometryneedtohavehighpulseprocessingspeedsinordertocopewiththe
veryhighphotoncountratesthatcanbeobtained.Inaddition,theyneedsufficientenergyresolutiontoallowfilteringout
ofbackgroundnoiseandspuriousphotonsfromtheprimarybeamorfromcrystalfluorescence.Therearefourcommon
typesofdetector:
gasflowproportionalcounters
sealedgasdetectors
scintillationcounters
semiconductordetectors
Gasflowproportionalcountersareusedmainlyfordetectionoflongerwavelengths.Gasflowsthroughitcontinuously.
Wheretherearemultipledetectors,thegasispassedthroughtheminseries,thenledtowaste.Thegasisusually90%
argon,10%methane("P10"),althoughtheargonmaybereplacedwithneonorheliumwhereverylongwavelengths(over
5nm)aretobedetected.TheargonisionisedbyincomingXrayphotons,andtheelectricfieldmultipliesthischargeintoa

measurablepulse.Themethanesuppressestheformationoffluorescentphotons
causedbyrecombinationoftheargonionswithstrayelectrons.Theanodewireis
typicallytungstenornichromeof2060mdiameter.Sincethepulsestrength
obtainedisessentiallyproportionaltotheratioofthedetectorchamberdiameterto
thewirediameter,afinewireisneeded,butitmustalsobestrongenoughtobe
maintainedundertensionsothatitremainspreciselystraightandconcentricwith
thedetector.Thewindowneedstobeconductive,thinenoughtotransmittheX
rayseffectively,butthickandstrongenoughtominimizediffusionofthedetector
gasintothehighvacuumofthemonochromatorchamber.Materialsoftenusedare
berylliummetal,aluminisedPETfilmandaluminisedpolypropylene.Ultrathin
windows(downto1m)forusewithlowpenetrationlongwavelengthsarevery
expensive.Thepulsesaresortedelectronicallyby"pulseheightselection"inorder
toisolatethosepulsesderivingfromthesecondaryXrayphotonsbeingcounted.

Figure10:Arrangementofgasflow
proportionalcounter

Sealedgasdetectorsaresimilartothegasflowproportionalcounter,exceptthat
thegasdoesnotflowthroughit.Thegasisusuallykryptonorxenonatafew
atmospherespressure.Theyareappliedusuallytowavelengthsinthe0.150.6nmrange.Theyareapplicableinprinciple
tolongerwavelengths,butarelimitedbytheproblemofmanufacturingathinwindowcapableofwithstandingthehigh
pressuredifference.
Scintillationcountersconsistofascintillatingcrystal(typicallyofsodiumiodidedopedwiththallium)attachedtoa
photomultiplier.Thecrystalproducesagroupofscintillationsforeachphotonabsorbed,thenumberbeingproportionalto
thephotonenergy.Thistranslatesintoapulsefromthephotomultiplierofvoltageproportionaltothephotonenergy.The
crystalmustbeprotectedwitharelativelythickaluminium/berylliumfoilwindow,whichlimitstheuseofthedetectorto
wavelengthsbelow0.25nm.Scintillationcountersareoftenconnectedinserieswithagasflowproportionalcounter:the
latterisprovidedwithanoutletwindowoppositetheinlet,towhichthescintillationcounterisattached.Thisarrangement
isparticularlyusedinsequentialspectrometers.
Semiconductordetectorscanbeusedintheory,andtheirapplicationsareincreasingastheirtechnologyimproves,but
historicallytheiruseforWDXhasbeenrestrictedbytheirslowresponse(seeEDX).
Extractinganalyticalresults
Atfirstsight,thetranslationofXrayphotoncountratesintoelementalconcentrationswouldappeartobestraightforward:
WDXseparatestheXraylinesefficiently,andtherateofgenerationofsecondaryphotonsisproportionaltotheelement
concentration.However,thenumberofphotonsleavingthesampleisalsoaffectedbythephysicalpropertiesofthesample:
socalled"matrixeffects".Thesefallbroadlyintothreecategories:
Xrayabsorption
Xrayenhancement
samplemacroscopiceffects
AllelementsabsorbXraystosomeextent.Eachelementhasacharacteristicabsorptionspectrumwhichconsistsofa
"sawtooth"successionoffringes,eachstepchangeofwhichhaswavelengthclosetoanemissionlineoftheelement.
AbsorptionattenuatesthesecondaryXraysleavingthesample.Forexample,themassabsorptioncoefficientofsiliconat
thewavelengthofthealuminiumKlineis50m/kg,whereasthatofironis377m/kg.Thismeansthatagiven
concentrationofaluminiuminamatrixofirongivesonlyoneseventhofthecountratecomparedwiththesame
concentrationofaluminiuminasiliconmatrix.Fortunately,massabsorptioncoefficientsarewellknownandcanbe
calculated.However,tocalculatetheabsorptionforamultielementsample,thecompositionmustbeknown.Foranalysis
ofanunknownsample,aniterativeprocedureisthereforeused.Itwillbenotedthat,toderivethemassabsorption
accurately,datafortheconcentrationofelementsnotmeasuredbyXRFmaybeneeded,andvariousstrategiesare
employedtoestimatethese.Asanexample,incementanalysis,theconcentrationofoxygen(whichisnotmeasured)is
calculatedbyassumingthatallotherelementsarepresentasstandardoxides.
EnhancementoccurswherethesecondaryXraysemittedbyaheavierelementaresufficientlyenergetictostimulate
additionalsecondaryemissionfromalighterelement.Thisphenomenoncanalsobemodelled,andcorrectionscanbemade
providedthatthefullmatrixcompositioncanbededuced.

Samplemacroscopiceffectsconsistofeffectsofinhomogeneitiesofthesample,
andunrepresentativeconditionsatitssurface.Samplesareideallyhomogeneous
andisotropic,buttheyoftendeviatefromthisideal.Mixturesofmultiplecrystalline
componentsinmineralpowderscanresultinabsorptioneffectsthatdeviatefrom
thosecalculablefromtheory.Whenapowderispressedintoatablet,thefiner
mineralsconcentrateatthesurface.Sphericalgrainstendtomigratetothesurface
morethandoangulargrains.Inmachinedmetals,thesoftercomponentsofanalloy
tendtosmearacrossthesurface.Considerablecareandingenuityarerequiredto
minimizetheseeffects.Becausetheyareartifactsofthemethodofsample
preparation,theseeffectscannotbecompensatedbytheoreticalcorrections,and
mustbe"calibratedin".Thismeansthatthecalibrationmaterialsandtheunknowns
mustbecompositionallyandmechanicallysimilar,andagivencalibrationis
applicableonlytoalimitedrangeofmaterials.Glassesmostcloselyapproachthe
idealofhomogeneityandisotropy,andforaccuratework,mineralsareusually
preparedbydissolvingtheminaborateglass,andcastingthemintoaflatdiscor
"bead".Preparedinthisform,avirtuallyuniversalcalibrationisapplicable.
Furthercorrectionsthatareoftenemployedincludebackgroundcorrectionandline
overlapcorrection.ThebackgroundsignalinanXRFspectrumderivesprimarily
fromscatteringofprimarybeamphotonsbythesamplesurface.Scatteringvaries
withthesamplemassabsorption,beinggreatestwhenmeanatomicnumberislow.
Whenmeasuringtraceamountsofanelement,orwhenmeasuringonavariable
lightmatrix,backgroundcorrectionbecomesnecessary.Thisisreallyonlyfeasible
onasequentialspectrometer.Lineoverlapisacommonproblem,bearinginmind
thatthespectrumofacomplexmineralcancontainseveralhundredmeasurable
lines.Sometimesitcanbeovercomebymeasuringalessintense,butoverlapfree
line,butincertaininstancesacorrectionisinevitable.Forinstance,theKisthe
onlyusablelineformeasuringsodium,anditoverlapsthezincL(L2M4)line.
Thuszinc,ifpresent,mustbeanalysedinordertoproperlycorrectthesodium
value.

Otherspectroscopicmethodsusingthesame
principle
ItisalsopossibletocreateacharacteristicsecondaryXrayemissionusingother
incidentradiationtoexcitethesample:
electronbeam:electronmicroprobe
ionbeam:particleinducedXrayemission(PIXE).
WhenradiatedbyanXraybeam,thesamplealsoemitsotherradiationsthatcanbe
usedforanalysis:

Aglass"bead"specimenforXRF
analysisbeingcastataround1100C
inaHerzogautomatedfusion
machineinacementplantquality
controllaboratory.1(top):fusing,2:
preheatingthemould,3:pouringthe
melt,4:coolingthe"bead"

electronsejectedbythephotoelectriceffect:Xrayphotoelectronspectroscopy(XPS),alsocalledelectron
spectroscopyforchemicalanalysis(ESCA)
ThedeexcitationalsoejectsAugerelectrons,butAugerelectronspectroscopy(AES)normallyusesanelectronbeamas
theprobe.
ConfocalmicroscopyXrayfluorescenceimagingisanewertechniquethatallowscontroloverdepth,inadditionto
horizontalandverticalaiming,forexample,whenanalysingburiedlayersinapainting.[5]

Instrumentqualification
A2001review,[6]addressestheapplicationofportableinstrumentationfromQA/QCperspectives.Itprovidesaguideto
thedevelopmentofasetofSOPsifregulatorycomplianceguidelinesarenotavailable.

Seealso
Emissionspectroscopy
Listofmaterialsanalysismethods
MicroXrayfluorescence
Mssbauereffect,resonantfluorescenceofgammarays
Xrayfluorescenceholography

Notes
1.DeViguerieL,SoleVA,WalterP,MultilayersquantitativeXrayfluorescenceanalysisappliedtoeaselpaintings(http://www.ncbi.
nlm.nih.gov/pubmed/19688344),AnalBioanalChem.2009Dec395(7):201520.doi:10.1007/s0021600929970
2.XRayFluorescenceatColourLex(http://colourlex.com/project/xrayfluorescence/)
3.Glocker,R.,andSchreiber,H.,AnnalenderPhysik.,85,(1928),p.1089
4.DavidBernardWilliamsC.BarryCarter(1996).Transmissionelectronmicroscopy:atextbookformaterialsscience.2.Springer.
p.559.ISBN030645324X.
5.L.Vincze(2005)."ConfocalXrayFluorescenceImagingandXRFTomographyforThreeDimensionalTraceElement
Microanalysis".MicroscopyandMicroanalysis.11:682.doi:10.1017/S1431927605503167.
6.Kalnickya,DennisJ.RajSinghvi(2001)."FieldportableXRFanalysisofenvironmentalsamples".JournalofHazardous
Materials.83(12):93122.doi:10.1016/S03043894(00)003307.PMID11267748.

References
Beckhoff,B.,Kanngieer,B.,Langhoff,N.,Wedell,R.,Wolff,H.,HandbookofPracticalXRayFluorescence
Analysis(https://books.google.com/books?id=c6d8EPYHn1EC&printsec=frontcover),Springer,2006,ISBN3540
286039
Bertin,E.P.,PrinciplesandPracticeofXraySpectrometricAnalysis,KluwerAcademic/PlenumPublishers,ISBN
0306308096
Buhrke,V.E.,Jenkins,R.,Smith,D.K.,APracticalGuideforthePreparationofSpecimensforXRFandXRD
Analysis,Wiley,1998,ISBN0471194581
Jenkins,R.,XrayFluorescenceSpectrometry,Wiley,ISBN0471299421
Jenkins,R.,DeVries,J.L.,PracticalXraySpectrometry,SpringerVerlag,1973,ISBN0387910298
Jenkins,R.,R.W.Gould,R.W.,Gedcke,D.,QuantitativeXraySpectrometry(https://books.google.com/books?id=Z
WQYy4aQLQC&printsec=frontcover),MarcelDekker,ISBN0824795547
PennerHahn,JamesE.(2013)."Chapter2.TechnologiesforDetectingMetalsinSingleCells.Section4,IntrinsicX
RayFluorescence".InBanci,Lucia.MetallomicsandtheCell.MetalIonsinLifeSciences.12.Springer.
doi:10.1007/9789400755611_2.ISBN9789400755604.electronicbookISBN9789400755611ISSN1559
0836(https://www.worldcat.org/search?fq=x0:jrnl&q=n2:15590836)electronicISSN18680402(https://www.world
cat.org/search?fq=x0:jrnl&q=n2:18680402)
VanGrieken,R.E.,Markowicz,A.A.,HandbookofXRaySpectrometry(https://books.google.com/books?id=i_iDR
Tp75AsC&printsec=frontcover)2nded.MarcelDekkerInc.:NewYork,2002Vol.29ISBN0824706005

Externallinks
Spectroscopy(https://www.dmoz.org/Science/Instruments_and_Supplies/Laboratory_Equipment/Spectroscopy/)at
DMOZ
XRayFluorescenceinAnalysisofPaintings(http://colourlex.com/project/xrayfluorescence/),ColourLex
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Xray_fluorescence&oldid=741530431"
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