1、ISOInternationalStandardISO11505Secondedition2025-06Surfacechemicalanalysis一GeneralproceduresforquantitativecompositionaldepthprofilingbyglowdischargeopticalemissionspectrometryAnalysechimiquedessurfacesModesOperatoiresgenerauxpourIeprofilageenprofondeurCompositionnelquantitatifparSpectrometriedemis
2、sionoptiqueadechargeIuminescenteReferencenumberISO11505:2025(en)COPYRIGHTPROTECTEDDOCUMENTISO2025Allrightsreserved.Unlessotherwisespecified,orrequiredinthecontextofitsimplementation,nopartofthispublicationmaybereproducedorutilizedotherwiseinanyformorbyanymeans,electronicormechanical,includingphotoco
3、pying,orpostingontheinternetoranintranet,withoutpriorwrittenpermission.PermissioncanberequestedfromeitherISOattheaddressbeloworISO,smemberbodyinthecountryoftherequester.ISOcopyrightofficeCP401Ch.deBlandonnet8CH-1214Vernier,GenevaPhone:+41227490111Email:copyrightiso.orgWebsite:www.iso.orgPublishedinS
4、witzerlandContentsPageForewordv1 Scope12 Normativereferences13 Termsanddefinitions14 Principle15 Apparatus25.1 Glowdischargeopticalemissionspectrometer25.1.1 General25.1.2 Selectionofspectrallines25.1.3 Selectionofglowdischargesourcetype26 Adjustingtheglowdischargespectrometersystemsettings36.1 Gene
5、ral.36.2 SettingthedischargeparametersofaDCsource46.2.1 Constantappliedcurrentandvoltage46.2.2 Constantappliedcurrentandpressure56.2.3 Constantappliedvoltageandpressure56.3 SettingthedischargeparametersofanRFsource66.3.1 Constantappliedpowerandpressure66.3.2 ConstantappliedpowerandDCbiasvoltage66.3.
6、3 ConstanteffectivepowerandRFvoltage76.4 Minimumperformancerequirements76.4.1 General76.4.2 Controloflampcleanlinessandstart-upperformance76.4.3 Minimumrepeatabilitry96.4.4 Detectionlimit97 Sampling118 Calibration118.1 General118.2 Calibrationspecimens118.2.1 General118.2.2 Low-alloyironorsteelspeci
7、mens128.2.3 Stainless-steelspecimens128.2.4 High-oxygenspecimens128.2.5 High-carbonspecimens128.2.6 High-nitrogenspecimens128.2.7 High-puritycopperspecimens128.2.8 High-purityzincspecimens138.3 Validationspecimens138.4 Determinationofthesputteringrateofcalibrationandvalidationspecimens138.5 Emission
8、intensitymeasurementsofcalibrationspecimens148.6 Calculationofcalibrationformulae148.7 Validationofthecalibration148.7.1 General148.7.2 Checkinganalyticalaccuracyusingbulkreferencematerials158.7.3 Checkinganalyticalaccuracyusingsurfacelayerreferencematerials158.8 Verificationanddriftcorrection159 An
9、alysisoftestspecimens169.1 Adjustingdischargeparameters169.2 Settingofmeasuringtimeanddataacquisitionrate169.3 Quantifyingdepthprofilesoftestspecimens1610 Expressionofresults1610.1 Expressionofquantitativedepthprofile1610.2 Determinationoftotalcoatingmassperunitarea1710.3 Determinationofaveragemassf
10、ractions1811 Precision1812 Testreport18AnnexA(normative)Calculationofcalibrationconstantsandquantitativeevaluationofdepthprofiles19AnnexB(informative)Suggestedspectrallinesfordeterminationofgivenelements32Bibliography34ForewordISO(theInternationalOrganizationforStandardization)isaworldwidefederation
11、ofnationalstandardsbodies(ISOmemberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnicalcommittees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhastherighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-
12、governmental,inliaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnicalCommission(IEC)onallmattersofelectrotechnicalstandardization.TheproceduresusedtodevelopthisdocumentandthoseintendedforitsfurthermaintenancearedescribedintheISO/IECDirectives,Part1.Inparticul
13、ar,thedifferentapprovalcriterianeededforthedifferenttypesofISOdocumentshouldbenoted.ThisdocumentwasdraftedinaccordancewiththeeditorialrulesoftheISO/IECDirectives,Part2(seeWWW.iso.org/directives).ISOdrawsattentiontothepossibilitythattheimplementationofthisdocumentmayinvolvetheuseof（八）patent(三).ISOtak
14、esnopositionconcerningtheevidence,validityorapplicabilityofanyclaimedpatentrightsinrespectthereof.Asofthedateofpublicationofthisdocument,ISOhadnotreceivednoticeof（八）patent(三)whichmayberequiredtoimplementthisdocument.However,implementersarecautionedthatthismaynotrepresentthelatestinformation,whichmay
15、beobtainedfromthepatentdatabaseavailableatWWW.iso.org/patents.ISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.Anytradenameusedinthisdocumentisinformationgivenfortheconvenienceofusersanddoesnotconstituteanendorsement.Foranexplanationofthevoluntarynatureofstandards,themeaningofISOsp
16、ecifictermsandexpressionsrelatedtoconformityassessment,aswellasinformationaboutISOsadherencetotheWorldTradeOrganization(WTo)principlesintheTechnicalBarrierstoTrade(TBT工seeWWW.iso.org/iso/foreword.htmLThisdocumentwaspreparedbyTechnicalCommitteeISO/TC201,Surfacechemicalanalysis,SubcommitteeSC8,Glowdis
17、chargespectroscopy.Thissecondeditioncancelsandreplacesthefirstedition(ISe)Il505:2012),whichhasbeentechnicallyrevised.Themainchangesareasfollows: thelistedtypesofarraydetectorshavebeenupdated; advancesinmeasurementtechniquesandapparatushaveexpandedtheapplicablesamplesizes,andmodificationshavebeenmade
18、tooptimizetheoptics,vacuumanddetectionsystems; thetext“settingofthehighvoltageforthedetectors“isreplacedwith“settingoftheparametersfordetectorsensitivitythroughoutthedocuments; theinstructionstooptimizethecratershapehasbeenchangedfrommandatorytooptional.Anyfeedbackorquestionsonthisdocumentshouldbedi
19、rectedtotheusersnationalstandardsbody.AcompletelistingofthesebodiescanbefoundatWWW.iso.org/membnrs.html.SurfacechemicalanalysisGeneralproceduresforquantitativecompositionaldepthprofilingbyglowdischargeopticalemissionspectrometry1 ScopeThisdocumentspecifiesaglowdischargeopticalemissionSpectrometric(G
20、D-OES)methodforthedeterminationofthethickness,massperunitareaandchemicalcompositionofsurfacelayerfilms.TheapplicabilityofthisdocumentislimitedtodescriptionofgeneralproceduresforquantificationofthechemicalcompositionandthicknessinGD-OEScompositionaldepthprofiling.Thisdocumentisnotdirectlyapplicablefo
21、rquantificationofindividualmaterialshavingvariousthicknessesandelementstobedetermined.2 NormativereferencesThefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheircontentconstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelates
22、teditionofthereferenceddocument(includinganyamendments)applies.ISO14707,SurfacechemicalanalysisGlowdischargeopticalemissionspectrometry(GD-OES)Introductiontouse3 TermsanddefinitionsNotermsanddefinitionsarelistedinthisdocument.ISOandIECmaintainterminologydatabasesforuseinstandardizationatthefollowing
23、addresses: ISOOnlinebrowsingplatform:availableathttps:WWW.iso.org/obp IECElectropedia:availableathttps:WWW.electropedia.org/4PrincipleTheanalyticalmethoddescribedinthisdocumentinvolvesthefollowingprocesses:a) cathodicsputteringofthesurfacelayerinadirectcurrentorradiofrequencyglowdischargedevice;b) e
24、xcitationoftheanalyteatomsandionsintheplasmaformedintheglowdischargedevice;c) Spectrometricmeasurementoftheintensitiesofcharacteristicspectralemissionlinesoftheanalyteatomsandionsasafunctionofsputteringtime(qualitativedepthprofile);d) conversionofthequalitativedepthprofileinunitsofintensityversustim
25、etomassfractionversusdepthbymeansofcalibrationfunctions(quantification).Calibrationofthesystemisachievedbymeasurementsoncalibrationspecimensofknownchemicalcompositionandmeasuredsputteringrate.5Apparatus5.1 Glowdischargeopticalemissionspectrometer5.1.1 GeneralTherequiredinstrumentationincludesanoptic
26、alemissionspectrometersystemconsistingofaGrimmtype6orsimilarglowdischargesource(directcurrentorradiofrequencypowered)andasimultaneousopticalspectrometerwhichshallbeinaccordancewithISO14707,capableofprovidingsuitablespectrallinesfortheanalyteelements.Sequentialopticalspectrometers(monochromators)aren
27、otsuitable,sinceseveralanalyticalwavelengthsmustbemeasuredsimultaneouslyathighdataacquisitionspeed.Anarraytypedetector,suchasachargecoupleddevice(CCD)1acomplementarymetal-oxide-semiconductordevice(CMOS)orachargeinjectiondevice(ClD)canalsobeusedforsimultaneousdetectiontocoverawidespectralrangeofthean
28、alyticallines.Theinnerdiameterofthehollowanodeoftheglowdischargesourceshouldbeintherange1mmto8mm.Acoolingdeviceforthinspecimens,suchasametalblockwithcirculatingcoolingliquid,isalsorecommended,butnotstrictlynecessaryforimplementationofthemethod.Sincetheprincipleofdeterminationisbasedoncontinuoussputt
29、eringofthesurfacelayer,thespectrometershallbeequippedwithadigitalreadoutsystemfortime-resolvedmeasurementoftheemissionintensities.Asystemcapableofadataacquisitionspeedofatleast100measurements/secondperspectralchannelisrecommended,but,foralargenumberofapplications,speedsof50measurements/secondperspec
30、tralchannelareacceptable.NOTEPulsedmodeofglowdischargesourceisavailableinsomecommercialinstrumentsandcanbebeneficialintheanalysisofheat-sensitivesamples,forreductionOfsputteringrate.5.1.2 SelectionofspectrallinesForeachanalytetobedetermined,thereexistanumberofspectrallineswhichcanbeused.Suitableline
31、sshallbeselectedonthebasisofseveralfactors,includingthespectralrangeofthespectrometerused,theanalytemassfractionrange,thesensitivityofthespectrallinesandanyspectralinterferencefromotherelementspresentinthetestspecimens.Forapplicationswhereseveraloftheanalytesofinterestaremajorelementsinthespecimens,
32、specialattentionshallbepaidtotheoccurrenceofself-absorptionofcertainhighlysensitivespectrallines(so-calledresonancelines).Self-absorptioncausesnonlinearcalibrationcurvesathighanalytemassfractionlevels,andstronglyself-absorbedlinesshouldthereforebeavoidedforthedeterminationofmajorelements.Suggestions
33、concerningsuitablespectrallinesaregiveninTabIeB.l.Spectrallinesotherthanthoselistedmaybeused,aslongastheyhavefavourablecharacteristics.5.1.3 Selectionofglowdischargesourcetype5.1.3.1 AnodesizeMostGD-OESinstrumentsonthemarketaredeliveredwithoptionstousevariousanodediameters,with2mm,4mmand8mmbeingthem
34、ostcommon.Someolderinstrumentshaveoneanodeonly,usually8mm,whilethemostcommonlyusedanodeinmoderninstrumentsis4mm.Alargeranoderequireslargerspecimensandhigherpowerduringanalysis;therefore,thespecimenisheatedtoagreaterextent.Howeverlalargeranodegivesrisetoaplasmaoflargervolumethatemitsmorelight,resulti
35、nginlowerdetectionlimits(i.e.higheranalyticalsensitivity).Furthermore,alargeranodehelpstomaskinhomogeneitywithinasurfacelayer.Thiscanbeanadvantagedependingontheapplication.Inalargenumberofapplications,the4mmanodeisagoodcompromise.However,insurfaceanalysisapplicationsitisrathercommontoencounterproble
36、msofoverheatingofthespecimensdueto,e.g.surfacelayersofpoorheatconductivityand/orverythinspecimens.Insuchcases,asmalleranodeispreferable(typically2mmor2,5mm),evenifthereissomelossofanalyticalsensitivity.5.1.3.2 TypeofpowersupplyTheglowdischargesourcecanbeeitheratypepoweredbyadirectcurrent(DC)powersup
37、plyoraradiofrequency(RF)type.ThemostimportantdifferenceisthattheRFtypecansputterbothconductiveandnon-conductivespecimens;hencethisistheonlytypethatcanbeusedfor,e.g.polymercoatingsandinsulatingoxidelayers.However,itistechnicallysimplertomeasureandcontroltheelectricalsourceparameters(voltage,current,p
38、ower)ofaDCtype.SeveralcommerciallyavailableGD-OESsystemscanbedeliveredwiththeoptiontoswitchbetweenDCandRFoperation,butRF-onlysystemsalsoexist.Inshort,thereareaverylargenumberofapplicationswhereDCorRFsourcescanbeusedandseveralwhereonlyanRFsourcecanbeused.5.1.3.3 ModeofoperationBothDCandRFsourcescanbe
39、operatedinseveraldifferentmodeswithrespecttothecontroloftheelectricalparameters(current,voltage,power)andthepressure.Thereareseveralreasonsforthis:一“historicalreasons(olderinstrumentshavesimplerbutfunctionalpowersupplies,whilethetechnologyhasevolvedsothatnewermodelshavemorepreciseandeasier-to-operat
40、esourcecontrol); differentmanufacturershavechosendifferentsolutionsforsourcecontrol; therearesomeapplication-relatedissueswhereaparticularmodeofoperationistobepreferred.Thisdocumentgivesinstructionsforoptimizingthesourceparametersbasedonseveralavailablemodesofoperation.Themostimportantreasonforthisi
41、stomaketheseinstructionscomprehensivesoastoincludeseveraltypesofinstruments.Inmostapplications,thereisnomajordifferencebetweenthesemodesintermsofanalyticalperformance,butthereareotherdifferencesintermsofpracticalityandeaseofoperation.Forinstance,asystemequippedwithactivepressureregulationwillautomat
42、icallybeadjustedtothesameelectricalsourceparameterseverytimeaparticularanalyticalmethodisused.Withoutthistechnology,somemanualadjustmentofthepressuretoachievethedesiredelectricalsourceparametersisnormallyrequired.Alternatively,amethodtocorrectforimpedancevariationsbymeansofempiricallyderivedfunction
43、sEcanbeused,provideditisimplementedinthesoftwareoftheGD-OESsystems.NOTEInthiscontext,whatisknownastheemissionyieldformsthebasisforcalibrationandquantificationasdescribedinthisdocument(2.Theemissionyieldhasbeenfoundtovarywiththecurrent,thevoltageand,toalesserextent,thePreSSUreZiii.itisimpossibleinpra
44、cticetomaintainallthreeparametersconstantforalltestspecimens,duetovariationsintheelectricalcharacteristicsofdifferentmaterials.Inseveralinstrumenttypes,theelectricalsourceparameterstheplasmaimpedance)canthereforebemaintainedconstantbymeansofautomaticsystemsthatvarythepressureduringanalysis.6Adjustin
45、gtheglowdischargespectrometersystemsettings6.1 GeneralFollowthemanufacturerlSinstructionsorlocallydocumentedproceduresforpreparingtheinstrumentforuse.RFsourcesdifferfromDCsourcesintherespectthatforseveralinstrumentmodels,onlytheapplied(forward)RFpowercanbemeasured,nottheactualpowerdevelopedintheglow
46、dischargeplasma.TheappliedRFpowerisnormallyintherange10Wto100W,butitneedstobenotedthattheRFpowerlossesinconnectors,cables,etc.varyconsiderablybetweendifferentinstrumentmodels.Typicalpowerlossesareintherange10%to50%oftheappliedpower.Furthermore,thepossibilitiestomeasuretheadditionalelectricalparamete
47、rsvoltageandcurrentintheplasmaaremoreorlessrestrictedduetotechnicaldifficultieswithRFsystems,andseveralexistinginstrumentmodelscanonlymeasuretheappliedRFpower.ThereisnodifferencebetweenDCandRFconcerningthepossibilitiestomeasurethepressure.However,therearelargepressuresdifferentialsinaGrimmtypesource
48、andpressurereadingsobtaineddependonthelocationofthepressuregauge.Someinstrumentmodelshaveapressuregaugeattachedtomeasuretheactualpressureintheplasma,whileothershaveapressuregaugelocatedona“lowpressure1/sideofthesourceclosertothepump.Therefore,thepressurereadingscan,forseveralinstruments,justbeusedtoadjustthesourceparametersofthatparticularinstrument,notasameasureoftheactualoperatingpressureintheplasma.Fortestspecimens,calibrationsamplesandvalidationsamples,itisimportanttoensu
