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addedtothesilicateororganosilicatedielectricfilm.Usually thisisthroughadepththereofsuchthatatleast10%ofthe10 silanolmoietiesorbondscreatedbyremovalofcarboncon tainingmoietiesfromthesilicateororganosilicatedielectric filmaresilylated.Inanothercase,whenthesilicateororga nosilicatedielectricfilmhaspores,theSurfacemodification treatmentisconductedunderconditionssufficienttoseal 15 poresatasurfaceoftheorganosilicatedielectricfilmtoa depthofabout50Aorles.15.Theporesatthesurfaceofthe silicateororganosilicatedielectricfilmarepreferablysealed, tosuchanextentthataSubsequentexposureto(i)precursors forchemicalvapordepositionofnitride,carbide,metals,or (i)non-etchingwetcleaningmaterialsdoesnotallowapen etrationthereoftoadepthgreaterthan5timesthemaximum poresize. agentcompositionsincludealdehydes,esters,acidchlorides, andethers.Suitablealdehydesincludeacetaldehydeandben Zaldehyde;suitableestersincludeethylacetateandmethyl benzoate;suitableacidchloridesincludeacetylchlorideand benzylchloride;andsuitableethersincludediethyletherand anisole.Awidevarietyofsinglewaferormultiplewafer (batch)plasmasystemscanbeusedforthisproces;these systemsincludesocaleddownstreamashers,suchasthe GasonicsL3510photoresistasher,PECVDdielectricdepo sitionsystemssuchastheAppliedMaterialsP5000,orreac tiveionetch(“RIE)systems.Broadly,theconditionsforthe plasmaprocessarewithinthefollowingranges:chamber temperature,20°C.to450°C.;RFpower,50Wto1000W: chamberpresure,0.05to100tor;plasmatreatmenttime,5 secondsto5minutes;andSurfacemodificationflowrate, US 7,678,712B2 17 sccm(standardcubiccentimetersperminutemeasuredat0° C.andatmosphericpresure)orpreferablyfromabout500to about2,000sccmandmostpreferablyabout1,000sccm.The reactorgaspressurepreferablyrangesfromabout0.1toabout 760tor,morepreferablyfromabout0.2toabout400torrand5 mostpreferablyfromabout0.25toabout2.0tor. Inonecase,theSurfacemodificationagentcomposition treatmentisconducteduntilcarboncontainingmoietiesare Otherreagentsforplasmainducedsurfacemodification Optionallytheinventivemethodfurthercomprisesthesub 100-2000sccm;inertgasflowrate(typicalyargon),100 sequentstepofsubjectingthesilicateororganosilicatedielec25 2000ScCm. tricfilmtoatreatmentsuficienttoefect(i)anincreased Preferablytheoveralprocessofisconductedwithina aditionofcarboncontainingmoietiestothesilicateororga nosilicatedielectricfilmor(i)anincreasedsealingofsurface poresofthesilicateororganosilicatedielectricfilm;or(i) firstanincreasedaditionofcarboncontainingmoietiesto30 thesilicateororganosilicatedielectricfilmandthenan increasedsealingofsurfaceporesofthesilicateororgano silicatedielectricfilmor(iv)removingatleastSomeresidual activatingagent,Surfacemodificationagent,by-products; andcombinationsthereof.Thismaybedonebyheating,35 ultravioletradiation,plasmaenergy,electronbeam,ionbeam orcombinationsthereof,underconditionstoefectsuch results.Heatingmaybedoneatatemperatureoffromabout 20°C.toabout450°C.,preferablyfromabout100°C.to Wafersarecontinuouslymaintainedinanisolatedenviron about400°C.forfromabout10secondstoabout120min 40 utes,preferablyfromabout10secondstoabout120minutes. Inyetanotherembodiment,awetcleanusingchemicals suchasAP395ordiluteHFisperformedaftertheabove mentioned embodiments. The wet clean isuseful to remove anyresistresiduesremainingaftertheash.Untreatedlow-k45 dielectricmaterialsafteretchandasharepronetoatackby thewetcleanagents.TheSurfacemodificationagenttreat mentsignificantlyimprovesresistanceofthelow-kdielectric toatackbywetclean. Inyetanotherembodiment,thewetcleancanbeperformed50 beforethebakeprocessinthefirstcontemplatedembodi ment.Thehightemperaturebakestepisperformedafterthe wetclean.Anadvantageofthismethodcanbethatthewet cleancanremoveexcessSurfacemodificationagentandany reactionproduct.ThiscanresultinlowerVolatilecomponents55 inthedielectricmaterialandacleanercoppersurface.Both canresultinanimprovedlongtermreliability. mentataconstantvacuumpressurelevel,andtransferedinto andoutofanexternalatmosphericpressureenvironment throughoneormoreaccessportsorload-locks.Inatypical system,acaseteorcarierwithaseriesofwafersisplaced ataninterfaceportoftheclustertolandlatchesreleasethe portdor.Amanipulatorrobotpicksupthecaseteorindi vidualwaferanddirectsthemtodesiredprocessingstations withintheequipment.Afterprocessing,thereverseoperation takesplace.Suchawaferprocessingtechniqueesentialy eliminatescontaminatessincetreatmenttakesplaceafterthe wafersaresealedintheinternalvacuumenvironment,and theyarenotremovedpriortocompletionofprocesing.The configurationachievesasignificantimprovementoverthe conventionalhandlingofopencasetesinsideacleanroom. Inadition,sincethevacuumisnotbrokenfromSteptostep, theuseofclustertolsincreasesprocessproductivityand reducesdefectlevels.Theuseofaclustertolsignificantly aidssemiconductorprocessingthroughput.Asaresultchemi calvapordepositionandelectronbeamtreatmentcanbedone directlywithinaclustertolwithoutbreakingvacuumor removalofthesubstratefromtheclustertool. Inanotherembodiment,theSurfacemodificationagent compositionisprovidedbyexposingthedielectricfilmtoa plasmawhichisderivedfromanyoftheabovementioned60 Surfacemodificationagent.Inatypicalprocedure,theorga Theartisanwilapreciatethattheinventionisalsocon nosilicateglasdielectricfilmisplacedinaplasmagenerat ingchamber,suchasaplasmaenhancedchemicalvapor deposition(PECVD)system;thevaporofasurfacemodifi cationagentcompositionandargonvaporarepassedthrough 65 theplasmageneratingchamber,thenanRFenergysourceis activatedtocreateaplasma;theargongasisincludedtohelp templatedtoencompassmicroelectronicdevices,suchas semiconductordevicesorICsmanufacturedusingthese methodsarealsoapartofthepresentinvention. Themicroelectronicdevices,dielectriclayersandmateri alsmaybeutilizedorincorporatedintoanysuitableelec troniccomponent.Electroniccomponents,ascontemplated 18 promotetheformationofplasma.Theplasmaiscomposedof ionicfragmentsderivedfromtheSurfacemodificationagent composition;forexample,theionfragmentCHSi"isgener atedfrommethylsilane(CHSiH).Thisfragmentreactswith silanolgroupstoformhydrophobicSi-CHmoieties.Any oftheabovementionedsurfacemodificationagentcomposi tionscanbeusedforthisplasmainducedSurfacetreatment. clustertolhavingachamberadaptedforeachiftheinventive steps,suchasachamberfordepositingasilicateororgano silicatedielectricfilmonasubstrate.Avapor,gasorchemical vapordepositionchamber,andmeansfortransferingthefilm onSubstrateamongthevariouschambers.Thetreatmentin thechambersandthetransferingamongthechambersare preferablyconductedwhilecontinuouslymaintaining vacuumconditions.Clustertolsfortheprocessingofsemi conductorwafersarewellknownintheartandarewidely commerciallyavailable.SuchmaybeexemplifiedbyU.S. Pat.Nos.5,259.881:5,280,219;5,730,801:5,613,821and 5,380,682.PDF Image | VAPOR PHASE TREATMENT OF DELECTRIC MATERALS
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