141
Figure15.(a)SEMimageofalargesinglesheetdepositedonSiO2.(b)Schematicviewofatop-contact,back-gateddevice.(c)Photograph(left),opticalimage(middle),andSEMimage(right)ofaworkingdevicewithachannellengthof7µm.(Reprintedwithpermissionfromref101.Copyright2009NaturePublishingGroup.)
Figure16.Chemicallyderivedgrapheneprovidesapracticalroutetographene-basedresistivesensors.Theresistanceofthep-typematerialdecreasesuponexposuretoelectronwithdrawers(e.g.,NO2)andincreasesuponexposuretoelectrondonors(e.g.,NH3).(Reprintedwithpermissionfromref103.Copyright2009AmericanChemicalSociety.)
Itisinterestingtonotethedifferencesinresponseofchemicallyderivedgraphenesensorsandmechanicallyexfoliatedones.Asdiscussedearlier,electrondonatingorwithdrawinggroupsincreaseelectronorholepopulationsinpristinegrapheneandthusbothleadtoincreasedconductiv-ity.Chemicallyderivedgrapheneisnominallyp-type.Therefore,electronwithdrawinggroupscontributeadditionalcarriers,butelectrondonatorsactuallyservetodepleteholesfromthevalenceband.Hence,NO2andNH3ledtooppositedirectionsofresponseinoursensors.
solarcell,whichhadapowerconversionef ciency(PCE)of0.26%.Chhowalla’sgrouplaterfabricatedapolymersolarcellwithaPCEof0.1%usingasimilar lm.112,113TheperformanceofthesecellswaslessthanthatofthecorrespondingcontroldevicesonITO,buttheyprovideaproof-of-conceptforlow-costtransparentcoatingsbasedongraphene.
5.2.TotalOrganicSynthesis
Althoughgraphiteoxidehasproducedthe rstchemicallyderivedmicrometer-scalegraphene,synthetictechniquesforsmallerplanar,benzene-basedmacromoleculeshavebeenknownforsometime.33,34,114-117Thesegraphene-likepolya-cyclichydrocarbons(PAHs)occupyaninterestingplaceinbetween“molecular”and“macromolecular”structuresandarenowattractingnewinterestasapossiblealternativeroutetographene.
PAHsareattractivebecausetheyarehighlyversatileandcanbesubstitutedwitharangeofaliphaticchainstomodifysolubility.36Thusfar,themajordrawbackofPAHshasbeentheirlimitedsizerange.Thisisduetothefactthatincreasingmolecularweightgenerallydecreasessolubilityandincreasestheoccurrenceofsidereactions.Undertheseconditions,preservationofdispersibilityandaplanarmorphologyforlargePAHshasbeenverychallenging.
Amajoradvancecamein2008,whenMullenandco-workersreportedthesynthesisofnanoribbon-likePAHsupto12nminlength(seeFigure17).35Althoughtheelectronicpropertiesofthesenanoribbonshaveyettobecharacterized,
5.1.5.TransparentElectrodes
Solutionprocessingofchemicallyderivedgrapheneandthedepositionsachievedsoonledresearcherstoconsiderusingthematerialintransparentconductors.Thedemandforsuchcoatingshasgrownrapidlyduetooptoelectronicdevicesincludingdisplays,LEDs,andsolarcells.Whilethecurrentindustrystandardisindiumtinoxide(ITO),carbonnanotubeshavelongbeentoutedasapossiblealternativeduetotheirlowdimensionalityandabilitytoformapercolatingconductivenetworkatextremelylowdensities.Thesamemeritsmakegrapheneanobviouschoice.
Mullenandco-workersdemonstratedthe rstgraphene-basedtransparentconductor.111Filmsweredepositedbydip-coatingwithGOandreducingbythermalannealing.Sheetresistancesaslowas0.9k /)wereobtainedat70%transmittance.WhiletheperformancewasconsiderablylessthanthatofITO(70 /)at90%transmittance),the lmswerelow-costanddidnotrequirevacuumsputtering.Thegroupalsousedthe lmastheanodeinadye-sensitized
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