基于二噻吩并引達省的a-d-a共軛分子及其制備方法和應(yīng)用【
技術(shù)領(lǐng)域：
】[0001]本發(fā)明涉及基于二噻吩并引達省單元為核，齊聚五元芳香雜環(huán)為橋連單元，末端為拉電子單元的A-D-A共軛分子及其制備方法，以及該類分子作為活性層電子給體或電子受體材料在有機太陽能電池（OPV)中的應(yīng)用?！?br>背景技術(shù)：
】[0002]有機太陽能電池擁有成本低、重量輕、可彎曲、可溶液加工并且可以大面積制備等優(yōu)點，因此在學(xué)術(shù)界受到廣泛的關(guān)注。近年來，聚合物和小分子太陽能電池發(fā)展迅速，并取得了顯著的成果（X.Zhan,D.Zhu,Conjugatedpolymersforhigh-efficiencyorganicphotovoltaics,Polym.Chem.,2010,I,409；Y.Chen,X.Wan,G.Long,Highperformancephotovoltaicapplicationsusingsolution-processedsmallmolecules,Acc.Chem.Res.,2013,46,2645；Y.-J.Cheng,S.-H.Yang,C.-S.Hsu,Synthesisofconjugatedpolymersfororganicsolarcellapplications,Chem.Rev.,2009,109,5868；Y.Li,MoleculardesignofphotovoltaicmaterialsforpolymersolarcelIs:towardsuitableelectronicenergylevelsandbroadabsorption,Acc.Chem.Res.,2012,45,723；Z.He,C.Zhong,X.Huang,W.Y.Wong,H.WujL.Chen,S.SujY.CaojSimultaneousenhancementofopen-circuitvoltage,short-circuitcurrentdensity,andfillfactorinpolymersolarcells,Adv.Mater.,2011,23,4636；Z.C.He,C.M.Zhong,S.J.SujM.Xu,H.B.WujY.CaojEnhancedpower-conversionefficiencyinpolymersolarcellsusinganinverteddevicestructure,Nat.Photonics,2012,6,591；S.H.Liao,H.J.JhuojY.S.Cheng,S.A.Chen,Fullerenederivative-dopedzincoxidenanofilmasthecathodeofinvertedpolymersolarcellswithlow-bandgappolymer(PTB7_Th)forhighperformance,Adv.Mater.,2013,25,4766；V.Gupta,A.K.K.KyawjD.H.Wang,S.Chand,G.C.Bazan,A.J.Heeger，Barium:anefficientcathodelayerforbuIk-heterojunctionsolarcells,Sci.Rep.,2013,3,1965；W.Li,A.FurIan,K.H.Hendriks,M.M.Wienk,R.A.J.Janssen,Efficienttandemandtriple-junctionpolymersolarcells.,J.Am.Chem.Soc.,2013,135,5529；J.Zhou,Y.ZuojX.Wan,G.Long,Q.Zhang,W.Ni,Y.Liu,Z.Li,G.He,C.Li,B.Kan,M.Li,Y.Chen,Solution-processedandhigh-performanceorganicsolarcellsusingsmallmoleculeswithabenzodithiopheneunit,J.Am.Chem.Soc.，2013,135,8484.)。到目前為止，經(jīng)過對分子結(jié)構(gòu)、器件結(jié)構(gòu)和加工工藝的優(yōu)化，基于聚合物給體或小分子給體與富勒烯受體共混制備的太陽能電池的光電轉(zhuǎn)化效率已突破10%。這顯示出有機太陽能電池的巨大應(yīng)用前景（Y.Liu,C.-C.Chen,Z.Hong,J.Gao,Y.Yang,H.Zhou,L.Dou,G.Li,Y.Yang,Solution-processedsmall-moleculesolarcells!breakingthe10%powerconversionefficiency,Sci.Rep.,2013,3；You,J.；Chen,C.C.；Hong,Z.；Yoshimura,K.；0hya,K.；Xu,R.；Ye,S.；Gao,J.；Li,G.；Yang,Y.10.2%Powerconversionefficiencypolymertandemsolarcellsconsistingoftwoidenticalsub-cells,Adv.Mater.,2013,25,3973；J.You,L.DoujK.Yoshimura,T.KatojK.OhyajT.Moriarty,K.Emery,C.-C.Chen,J.Gao,G.Li,Y.Yang,Apolymertandemsolarcellwith10.6%powerconversionefficiency，Nat.Commun.，2013,4,1446.)〇其中聚合物材料由于其吸收太陽光的范圍相對較寬，其光伏器件的光電轉(zhuǎn)化效率較高。通過對材料結(jié)構(gòu)及器件結(jié)構(gòu)的優(yōu)化，文獻報道的最高光電轉(zhuǎn)化效率已經(jīng)達到10.6%。但聚合物也有自身缺點，如：分子量分布的多分散性，批次間重復(fù)性較差，純化難等問題。相對于此，有機小分子半導(dǎo)體材料則表現(xiàn)出特定優(yōu)點，如：確定的分子結(jié)構(gòu)及分子量，高純度及批次穩(wěn)定等。因而，近來有機小分子太陽能電池研究漸趨于熱。[0003]相比于給體材料的迅速發(fā)展，受體材料則發(fā)展緩慢。在受體材料方面，以PC61BM和PC71BM為代表的富勒烯衍生物牢牢地占據(jù)著主導(dǎo)地位。這是因為PCBM擁有諸多優(yōu)點，如大的電子親和力、優(yōu)秀的各向同性的電子傳輸性能、并且能夠與共軛聚合物給體材料混合形成納米尺寸的相分離等（G.Yu，J.Gao,J.C.Hummelen，F(xiàn).Wudl，A.J.Heeger，Polymerphotovoltaiccells:enhancedefficienciesviaanetworkofinternaldonor-acceptorheterojunctions,Science,1995,270,1789；Y.He,Y.Li,Fullerenederivativeacceptorsforhighperformancepolymersolarcells,Phys.Chem.Chem.Physj2011,13,1970.T.Liu,A.Troisi,Whatmakesfullereneacceptorsspecialaselectronacceptorsinorganicsolarcellsandhowtoreplacethem,Adv.Maten，2013,25,1038.)。然而以PCBM為代表的富勒烯衍生物也存在著諸多缺點，如在可見光區(qū)吸收較弱、難于調(diào)控能級、還有提純較困難等（P.Sonar,J.P.F.Lim,K.L.Chan,Organicnon-fullereneacceptorsfororganicphotovoltaics,EnergyEnviron.Sci.，2011，4,1558.)。因此，合成新型的受體材料依然非常有必要。[0004]近年來，人們?yōu)榱颂鎿Q有機太陽能電池中的富勒烯受體，合成了一系列的新型小分子及聚合物非富勒烯受體材料。當(dāng)與不同的給體材料共混制備太陽能電池時，并且表現(xiàn)出了較好的性能（X.Zhan，Z.Tan，B.Domercq，Z.An，X.Zhang，S.Barlow，Y.Li,D.ZhujB.Kippelen,S.R.Marder,Ahigh-mobilityelectron-transportpolymerwithbroadabsorptionanditsuseinfield-effecttransistorsandall-polymersolarcells,JAmChemSocj2007,129,7246；E.Zhou,J.Cong,Q.Wei,K.Tajima,C.Yang，K.Hashimoto,Al1-polymersolarcellsfromperylenediimidebasedcopolymers!materialdesignandphaseseparationcontrol,Angew.Chem.；Int.Ed.,2011,50,2799；J.T.Y.CaojT.Lei,J.S.Yuan,J.Y.Wang,J.Pei,Dithiazolyl-benzothiadiazole-containingpolymeracceptors:synthesis,characterization,andall-polymersolarcells,PolymerChemistry,2013,4,5228；P.Cheng,L.Ye,X.G.Zhao,J.H.HoujY.F.Li,X.W.ZhanjBinaryadditivessynergisticallyboosttheefficiencyofall-polymersolarcellsupto3.45%,EnergyEnviron.Sci.,2014,7,1351；S.Fabiano,S.Himmelberger,M.Drees,Z.Chen,R.M.Altamimi,A.Salleo,M.A.LoijA.Facchetti,Chargetransportorthogonalityinall-Polymerblendtransistors,diodes,andsolarcells,Adv.EnergyMater.，2014,4,1301409;H.Huang,N.Zhou,R.P.Ortiz,Z.Chen,S.Loser,S.Zhang,X.Guo,J.Casado,J.T.LopezNavarrete,X.Yu,A.Facchetti,T.J.Marks,Alkoxy-functionalizedthienyl-vinylenepolymersforfield-effecttransistorsandall-polymersolarcells,Adv.Funct.Mater.,2014,DOI:10.1002/adfm.201303219；W.Li,W.S.Roelofs,M.Turbiez,M.M.Wienk,R.A.Janssen,PolymersolarcellswithdiketopyrrolopyrroIeconjugatedpolymersastheelectrondonorandelectronacceptor,AdvMater,2014,DOI:10.1002/adma.201305910；W.Yu,D.Yang,X.ZhujX.Wang,G.TujD.Fan,J.Zhang,C.Li,Controlofnanomorphologyinall-polymersolarcellsviaassemblingnanoaggregationinamixedsolution,ACSApplMaterInterfaces，2014,6,2350;E.Zhou,J.Cong,K.Hashimoto,K.Tajima,Controlofmiscibilityandaggregation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