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US 2020/0051709A1 Feb.13,2020 than50ohm/square).Inmanycases,thehybridfilmexhibits anopticaltransparencenolesthan90%whilemaintaining ashetresistancenohigherthan30ohm/square(oftenno higherthan20oreven10ohm/square).Insome examples,thehybridfilmexhibitsanopticaltransparenceno lesthan95%whilemaintainingashetresistancelower than20ohm/square. [05] ThehybridCNT/pristinegraphene-basedopticaly transparentandelectricalyconductivefilmmaybeafre standingfilm,ormaybesuportedonatransparentsub strate.Preferably,themeshormeshesofcarbonnanotubes aredisposedbetwenthepristinegrapheneandthetrans parentsubstrate.Alternatively,themeshormeshesofcarbon nanotubesmaybeembededinthepristinegrapheneor simplysuportedonthepristinegraphene. [056] Thepresentdisclosurealsoprovidesaprocesfor producingtheopticalytransparentandelectricalyconduc tivefilmdescribedabove.Theprocescomprises:(a)pre paringasolutionorsuspensionofpristinegrapheneina liquidmedium;(b)dispersingmetalnanowiresorcarbon nanotubesintothesolutionorsuspensiontoforma“mixture dispersion";(c)dispensinganddepositingthemixturedis persionatacontroledrateontoasuportingsubstrate;and (d)removingtheliquidmediumfromthemixturedispersion depositedonthesuportingsubstratetoform thedesired opticalytransparentandelectricalyconductivefilm. [057]Anotherembodimentofthepresentdisclosureisa procesforproducinganopticalytransparentandelectri calyconductivefilm.Theprocescomprises:(a)preparing afirstsolutionorsuspensionofpristinegrapheneinafirst liquidmedium;(b)preparingasecondsuspensionofmetal nanowiresorcarbonnanotubesinasecondliquidmedium; (c)dispensinganddepositingthefirstsolutionorsuspension andthesecondsuspension,concurentlyorsequentialy,at acontroledrateontoasuportingsubstrate;and(d)remov ingthefirstliquidmedium andthesecondliquidmedium to form theopticalytransparentandelectricalyconductive film.Inapreferedembodiment,step(c)includesdispensing anddepositingthesecondsuspensionpriortodispensing anddepositingthefirstsuspensiontoproducealayerof metalnanowiresorcarbonnanotubescoveredandprotected byalayerofpristinegrapheneintheopticalytransparent andelectricalyconductivefilm. BRIEF DESCRIPTION OF THE DRAWINGS [058] FIG.1(a)Aflowchartilustratingvariouspriorart procesesforproducingnanographeneplatelets(graphene oxide,reducedgrapheneoxide,andpristinegraphene)and exfoliatedgraphiteproducts(flexiblegraphitefoilsand flexiblegraphitecomposites). [059] FIG.1(b)Schematicdrawingilustratingthepro cesesforproducingfilmormembraneofsimplyagregated graphiteorNGPflakes/platelets;alprocesesbeginwith intercalationand/oroxidationtreatmentofgraphiticmate rials(e.g.naturalgraphiteparticles). [060] FIG.2(a)Shetresistanceandopticaltransmit tance,measuredat550nm wavelength,ofvariousAgNW, AgNW-RGO,andAgNW-pristinegraphenefilms. [061]FIG.2(6)Shetresistanceandopticaltransmit tanceofvariousAgNW/RGO andAgNW/pristinegraphene films. [0062]FIG.3Thecurentdensity-voltage(J-V)charac teristicsofbulkheterojunctionpolymersolarcelswith AgNW,AgNW-RGO,andAgNW-pristinegraphenetrans parentelectrodesunderilumination. [0063]FIG.4Shetresistanceandopticaltransmitance, at50nmwavelength,ofvariousCuNW,CuNW-RGO,and CuNW-pristinegraphenethinfilms. DESCRIPTION OF THE PREFERRED EMBODIMENTS [064] Apreferedembodimentofthepresentdisclosure isanopticalytransparentandelectricalyconductivefilm composedofamesh ormeshesofmetalnanowiresand pristinegraphenewithametalnanowire-to-grapheneweight ratiooffrom 1/9to9/1,whereinthepristinegraphene containsnooxygenandnohydrogen,andthefilm exhibits anopticaltransparencenolesthan80%andshetresis tancenohigherthan30ohm/square.Thefilm isthiner than 10nm,more often thinerthan 10 nm,evenmore oftenandpreferablythinerthan2nm,andcanbeasthin as 0.34 nm . [065] Thetwokeycomponentsinthistransparentand conductivefilmaremetalnanowires(e.g.silvernanowires, AgNW)andpristinegraphene. [06] Graphene normaly referstoashetofcarbon atomsthatarearangedinahexagonallaticeandtheshet isonecarbonatomthick.Thisisolated,individualplaneof carbonatomsiscommonlyreferedtoassingle-layergra phene.Astackofmultiplegrapheneplanesbondedthrough van derWaals forcesin thethicknesdirection with an inter-grapheneplanespacingof0.354nm iscomonly referedtoasamulti-layergraphene.Amulti-layergraphene platelethasupto30layersofgrapheneplanes(<10nmin thicknes).Whentheplatelethasupto5-10graphene planes,itiscommonlyreferedtoas"few-layergraphene" in the scientific community. Single-layer graphene and multi-layergrapheneshetsarecolectivelycaled"nano grapheneplatelets”(NGPs).Grapheneshets/plateletsor NGPsareanew clasofcarbonnanomaterial(a2-Dnano carbon)thatisdistinctfrom the0-Dfulerene,the1-DCNT, andthe3-Dgraphite. [0067] Intheinstantaplicationandinkepingwith commonly acepteddefinitionsinscientificcommunity, NGPsorgraphenematerialscanincludediscreteshets/ plateletsofsingle-layerandmulti-layerpristinegraphene, grapheneoxide,orreducedgrapheneoxidewithdiferent oxygencontents.Pristinegraphenehasesentialy0%oxy genand0%hydrogen.Grapheneoxide(GO)has0.01% 46 % by weight of oxygen and reduced graphene oxide (RGO)has0.01%-2.0% byweightofoxygen.Inother words,RGO isatypeofGO havinglowerbutnon-zero oxygencontent.Aditionaly,bothGO andRGOcontaina high population of edge- and surface-borne chemical groups, vacancies, oxidative traps, and other types of defects,andbothGO andRGO containoxygenandother non-carbonelements,e.g.hydrogen.Incontrast,thepristine grapheneshetsarepracticalydefect-freonthegraphene plane and contain no oxygen.Hence,GO and RGO are commonlyconsideredinthescientificcommunityasaclas of2-D nanomaterialthatisfundamentaly diferentand distinctfrompristinegraphene. [0068]NGPsarecommonlyobtainedbyintercalating naturalgraphiteparticleswithastrongacidand/oroxidizing agenttoobtainagraphiteintercalationcompound(GIC)or graphiteoxide(GO),asilustratedinFIG.1(a)(procesflow chart)andFIG.1(b)(schematicdrawing).Thepresenceof 5PDF Image | HIGHLY CONDUCTING AND TRANSPARENT FILM AND PROCESS
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