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H-SisR-SiOshd m Hos Si.5-1.s.l.Ros-10 SiO15-1.s.l., Ho-10 Sils,R-SiO15, H-Sits).[R-SiOslSiO2), wherein: Formula(1) Formula(2) Formula(3) Formula(4) 10 US 7,678,712B2 78 ApplicationPCT/US01/50812filedDec.31,2001,whichare alincorporatedhereinbyreference. Suitableorganohydridosiloxaneresinsutilizedhereinhave thefollowinggeneralformulas: ofthisdefinition,becauseanaphthalenecompoundoran aromaticspirocompounddonothaveone,ormorethanone bridge. Contemplatedcagecompoundsneednotnecesarilybe limitedtobeingcomprisedsolelyofcarbonatoms,butmay alsoincludeheteroatomssuchasN,S,O,P,etc.Heteroatoms may advantageously introduce non-tetragonal bond angle configurations.Withrespecttosubstituentsandderivatiza tionsofcontemplatedcagecompounds,itshouldberecog nizedthatmanySubstituentsandderivatizationsareappro priate.Forexample,wherethecagecompoundsarerelatively hydrophobic,hydrophilicsubstituentsmaybeintroducedto increasesolubilityinhydrophilicsolvents,orviceversa. Alternatively,incaseswherepolarityisdesired,polarside groupsmaybeaddedtothecagecompound.Itisfurther contemplatedthatappropriateSubstituentsmayalsoinclude thermolabilegroups,nucleophilicandelectrophilicgroups.It shouldalsobeappreciatedthatfunctionalgroupsmaybe utilizedinthecagecompound(e.g.,tofacilitatecroslinking reactions,derivatizationreactions,etc.).Cagemoleculesor compounds,asdescribedindetailherein,canalsobegroups thatareattachedtoapolymerbackbone,andtherefore,can formnanoporousmaterialswherethecagecompoundforms onetypeofvoid(intramolecular)andwherethecroslinking ofatleastonepartofthebackbonewithitselforanother backbonecanformanothertypeofvoid(intermolecular). Additionalcagemolecules,cagecompoundsandvariations ofthesemoleculesandcompoundsaredescribedindetailin PCT/US01/32569 filed on Oct. 18, 2001, which is herein incorporatedbyreferenceinitsentirety.Contemplatedpoly mersmayalsocompriseawiderangeoffunctionalorstruc turalmoieties,includingaromaticsystems,andhalogenated groups.Furthermore,appropriatepolymersmayhavemany configurations,includingahomopolymer,andaheteropoly mer.Moreover,alternativepolymersmayhavevariousforms, Suchaslinear,branched,Super-branched,orthree-dimen sional. The molecular weight of contemplated polymers spansawiderange,typicalybetween400Daltonand400000 Daltonormore.Additivescanalsobeusedtoenhanceor impartparticularproperties,asisconventionallyknowninthe polymerart,includingstabilizers,flameretardants,pigments, plasticizers,Surfactants,andthelike.Compatibleornon compatiblepolymerscanbeblendedintogiveadesired property.Adhesionpromoterscanalsobeused.Suchpromot ersaretypifiedbyhexamethyldisilazane,whichcanbeused tointeractwithavailablehydroxylfunctionalitythatmaybe presentonaSurface.Suchassilicondioxide,thatwasexposed tomoistureorhumidity.Polymersformicroelectronicappli cationsdesirablycontainlowlevels(generalylesthan1 ppm,preferablylesthan10ppb)ofionicimpurities,particu larlyfordielectricinterlayers. thesumofnandm,ortheSumorx,yandZisfromabout8to15 about5000,andmoryisselectedsuchthatcarboncontaining constituentsarepresentineitheranamountoflesthanabout 40percent(LowOrganicContent=LOSP)orinanamount greater than about 40 percent (High Organic Content=HOSP);Risselectedfromsubstitutedandunsub stituted,normalandbranchedalkyls(methyl,ethyl,butyl, propyl,pentyl),alkenylgroups(vinyl,alyl,isopropenyl), cycloalkyls,cycloalkenylgroups,aryls(phenylgroups,ben Zylgroups,naphthalenylgroups,anthracenylgroupsand phenanthrenylgroups),andmixturesthereof,andwhereinthe25 specificmolepercentofcarboncontainingSubstituentsisa functionoftheratiooftheamountsofstartingmaterials.In someLOSPembodiments,particularlyfavorableresultsare obtainedwiththemolepercentofcarboncontainingSubstitu entsbeingintherangeofbetweenabout15molepercentto30 about25molepercent.InsomeHOSPembodiments,favor ableresultsareobtainedwiththemolepercentofcarbon containingSubstituentsareintherangeofbetweenabout55 molepercenttoabout75molepercent. Nanoporoussilicadielectricfilmswithdielectricconstants35 rangingfromabout1.5toabout4canalsobeusedasoneof thelayers.Nanoporoussilicafilmsarelaiddownasasilicon basedprecursor,agedorcondensedinthepresenceofwater andheatedsuficientlytoremovesubstantialyaloftheporo genandtoformvoidsinthefilm.Thesilicon-basedprecursor40 compositioncomprisesmonomersorprepolymersthathave theformula:R SiL,whereinRisindependently selectedfromalkylgroups,arylgroups,hydrogenandcom binations thereof L is an electronegative moiety. Such as alkoxy,carboxy,amino,amido,halide,isocyanatoandcom 45 binationsthereof,Xisanintegerrangingfrom0toabout2, andyisanintegerrangingfromabout2toabout4.Other nanoporouscompoundsandmethodscanbefoundinU.S. Pat.Nos.6,171,687;6,172,128;6.214,746;6,313,185;6,380, 347;and6.380.270,whichareincorporatedhereinintheir50 entirety. Thephrases“cagestructure”,“cagemolecule',and“cage Thematerials,precursorsandlayersdescribedhereincan compoundareintendedtobeusedinterchangeablyandrefer toamoleculehavingatleast10atomsarrangedsuchthatat leastonebridgecovalentlyconnectstwoormoreatomsofa55 ringsystem.Inotherwords,acagestructure,cagemolecule orcagecompoundcomprisesapluralityofringsformedby covalentlyboundatoms,whereinthestructure,moleculeor compounddefinesaVolume,Suchthatapointlocatedwiththe VolumecannotleavetheVolumewithoutpassingthroughthe60 ring.Thebridgeand/ortheringsystemmaycompriseoneor moreheteroatoms,andmaybearomatic,partialysaturated, orunsaturated.Furthercontemplatedcagestructuresinclude fulerenes,andcrownethershavingatleastonebridge.For example,anadamantaneordiamantaneisconsideredacage65 structure,whileanaphthalenecompoundoranaromaticspiro compoundarenotconsideredacagestructureunderthescope beandinmanywaysaredesignedtobesolvatedordissolved inanysuitablesolvent,solongastheresultingsolutionscan beappliedtoaSubstrate,aSurface,awaferorlayeredmate rial.Typicalsolventsarealsothosesolventsthatareableto Solvatethemonomers,isomericmonomermixturesandpoly mers.ContemplatedsolventsincludeanySuitablepureor mixtureoforganicorinorganicmoleculesthatarevolatilized atadesiredtemperature.Suchasthecriticaltemperature,or thatcanfacilitateanyoftheabove-mentioneddesigngoalsor needs.ThesolventmayalsocompriseanySuitablesingle polarandnon-polarcompoundsormixturethereof.Asused herein,theterm“polarmeansthatcharacteristicofamol eculeorcompoundthatcreatesanunequalcharge,partial chargeorspontaneouschargedistributionatonepointofor alongthemoleculeorcompound.Asusedherein,thetermPDF Image | VAPOR PHASE TREATMENT OF DELECTRIC MATERALS
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