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US 2020/0051709A1 Feb.13,2020 tionedrequirements.Thepristinegrapheneisoxygen-fre, hydrogen-fre,and grainboundary-fre(single-grain or single-crystaline). shetresistanceof54ohm/squareat95%transparenceand 43ohm/squareat97%transparency.Thelowestshetresis tanceachievedthusfarhasben8ohm/square.These fromtheCVD graphene,whichispolycrystalineandinher entlyhasasignificantamountofnon-carbonatomschemi calybondedthereto.Moreover,theCVD graphenecontains manydefects,e.g.,grainboundaries,linedefects,vacancies, andotherlaticeimperfections,suchasthosemanycarbon are selected from nanowires of silver (Ag), gold (Au), coper(Cu),platinum(Pt),zinc(Zn),cadmium(Cd),cobalt (Co),molybdenum (Mo),aluminum (Al),analoythereof, or acombinationthereof.Particularlydesiredmetal nanowiresaresilvernanowires,butmetalnanowiresmaybe 4 benproposedtoserveasatransparentandconductive 90%andshetresistancenohigherthan10ohm/square (preferablynohigherthan40ohm/squareandfurtherpref mentsoftransparency,conductivity,oxidationresistanceor erablynohigherthan30ohm/square).Inmanycases,the long-termstability,mechanicalintegrityandflexibility,sur filmexhibitsanopticaltransparencenolesthan95%ata facequality,chemicalpurity,procesease,andlowcost. shetresistancenohigherthan10ohm/square(oftenno [043]Thus,itisanobjectofthepresentdisclosureto higherthan40ohm/squareandsomeevenlesthan30 provideapristinegraphene-basedorpristinegraphene ohm/square). enabledhybridfilmthatmeetsmostoraloftheaforemen [0049]Mostsurprisingly,someofourbestfilmsachievea electrode,butnonehasmetthestringentcombinedrequire [0044]Itisanotherobjectofthepresentdisclosureto performancelevelsareunprecedentedandhaveexceded provideaprocesforproducingapristinegraphene-basedor pristine graphene-enabled hybrid film that is a variable alternativetoITO. SUMMARY [0045] Thepresentdisclosureprovidesanopticalytrans parentandelectricalyconductivefilmcomposedofmetal nanowires(and/orcarbonnanotubes)andpristinegraphene withametalnanowire-to-grapheneweightratioornano tube-to-grapheneratiooffrom 1/9to9/1,whereinthe pristinegraphenecontainsnooxygenandnohydrogen,and thefilmexhibitsanopticaltransparencenolesthan80% andshetresistancenohigherthan30ohm/square. [046] Normaly,apristinegrapheneisasingle-grainor single-crystalinestructureofhexagonalcarbon atoms whereinthegrapheneplaneisesentialydefect-freexcept atthegrapheneplaneedges.Thepristinegraphenenormaly doesnotcontainanynon-carbonatoms(e.g.oxygenand hydrogen).Thepristinegrapheneisfundamentalydistinct [0051]Inapreferedembodiment,themetalnanowires atomsthatarearangedinpentagons,heptagons,orocta selectedfromnanowiresofatransitionmetaloranaloyof gons,asoposedtothenormalhexagoninpristinegra phene.Theterm “pristinegraphene”asclaimedinthe instantaplicationlogicalyexcludestheCVDgraphene. tivefilmmaybeafre-standingfilmorsuportedona [0047]Thepristinegrapheneusedhereinistypicaly transparentsubstrate.Inapreferedconfiguration,thefilmis single-layerorfew-layergraphene(upto10planesof suportedonatransparentsubstrateandthemeshormeshes ofmetalnanowiresaredisposedbetwenthepristinegra importanttopointoutthatthenumberofgrapheneplanesof pheneandthetransparentsubstrate.Themeshormeshesof carbonatoms,butmoretypicalyupto5planes).Itis atoms(i.e.thenumberofhexagonalplanesofcarbonatoms) inagrapheneplateletisanesentialfactorthatdiferentiates one type of graphene from another type. A single-layer grapheneisasemi-metalwithazeroenergygap.Adouble layer grapheneshet/plateletisasemiconductorwith a non-zeroenergygap.Asthenumberofgrapheneplanes [0053]Anotherpreferedembodimentofthepresentdis increasesfrom3to10layers,thegraphenematerialis closureisanopticalytransparentandelectricalyconduc transitionedfromasemiconductortoametal(orconductor). tivefilmcomposedofameshormeshesofcarbonnanotubes Hence,single-layergraphene,double-layergraphene,few andpristinegraphenewithacarbonnanotube-to-graphene layergraphene(3-10layers),andthickergrapheneplatelets weightratiooffrom1/9to9/1,whereinthepristine (>10layers)arealconsideredasdistinctanddiferenttypes graphenecontainsnooxygenandnohydrogen,andthefilm ofmaterialsinscientificcomunity. exhibitsanopticaltransparencenolesthan80%andshet [0048]Preferablyandtypicaly,thethinfilmofhybrid resistancenohigherthan30ohm/square(typicalyno pristinegraphene-metalnanowiresexhibitsanopticaltrans parencenolesthan85%andshetresistancenohigherthan higherthan 20ohm/square).Thepristinegraphenecan containsingle-layer,double-layer,orfew-layergraphene 10ohm/square.Morepreferablyandmoretypicaly,the shets(upto10layers),eachhavingonesinglegrain. filmexhibitsanopticaltransparencenolesthan85%and [0054]Typicalyandpreferably,thehybridCNT/pristine shetresistancenohigherthan40ohm/square(preferablyno graphene-basedfilmexhibitsanopticaltransparencenoles higherthan30ohm/square).Stilmorepreferablyandtypi than85%andshetresistancenohigherthan20ohm/ caly,thefilmexhibitsanopticaltransparencenolesthan square(oftennohigherthan10ohm/squareandevenles theverybestvaluesofalgrapheneorgraphene-based hybridmaterialfilmseverreported.Thesevaluesarecom parable or superior to those of ITO -based films and gra phene-basedfilmsareflexible,durable,mechanicalstrong, environmentaly stable,andpotentialymuch lesexpen sive. [050] Forthepurposeofdefiningtheclaim languages, the“metalnanowire”intheinstantaplicationreferstoan elongatedmetalnanostructurehavingalargestdimension (e.g.length)andasmalestdimension(e.g.thicknesor diameter)whereinthelargestdimension-to-smalestdimen sionratio isno lesthan 3and thesmallestdimension isno greaterthan20nm (preferablynogreaterthan100nm). Themetalnanowirereferstoametalnanostructurehaving arod,wire,shet,belt,ortubeshapethatmeetstheafore mentioneddimensionrequirements.Inotherwords,the metal nanowire can include nano-rod,nano-wire,nano shet,nano-belt,ornano-tube. atransitionmetal. [052] Theopticalytransparentandelectricalyconduc metalnanowiresmaybeembededinthepristinegraphene orsuportedonthepristinegraphene.Thehybridmetal nanowire/pristinegraphene-basedopticalytransparentand electricalyconductivefilmmay furthercontaincarbon nanotubes or carbon nano -fibers.PDF Image | HIGHLY CONDUCTING AND TRANSPARENT FILM AND PROCESS
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