应用电化学 课件Electrochemical Route to Fabricate Film-Like Conjugated Microporous Polymers

ElectrochemicalRoutetoFabricateFilm-LikeConjugatedMicroporousPolymersandApplicationforOrganicElectronicsFenghongLi,FeiHuang,andYuguangMa（吉林大学，华南科大，长春应化所）Adv.Mater.2013,25,3443–3448(IF14.8)(Communication)文献讲评Received:February22,2013Revised:March29,2013Publishedonline:May21,2013发现问题，启发思路，发现有意义的方向或课题具体结果、方法、讨论以及写作，提供哪些参考？文献评述内容研究背景和意义研究领域存在的问题描述研究意义（重要之处？为什么有人感兴趣？）研究方法研究思想（工作（论文）设计思路）如何做?(实验手段、方法、技术(仪器))实验结果与理论推证（图、表、公式）讨论和分析（现象或规律描述、解释）主要结果创新点（或亮点、卖点）研究水平评价启示（及收获）研究背景和意义研究领域：MP,有机电子器件需要解决的问题（背景性问题，研究意义）：立题（问题的引出）为什么感兴趣？研究内容：从题目，关键词来看，吸引眼球ElectrochemicalRoutetoFabricateFilm-LikeConjugatedMicroporousPolymers(CMPs)

andApplicationforOrganicElectronics研究的问题和结果：研究领域存在的问题和主要结果AnimportantadvanceinthisareawouldbetodevelopsolutionprocessableCMPs,inordertoaccessthinfilmsfordevices.基本思路材料体系设计：CMP结构制备方法：电化学制备，关键是制膜应用：有机电子器件（太阳能电池，PLED）研究方法设计思想（或依据）：Cz：适宜电聚合（highlyelectroactive，氧化偶联聚合）

TPT核：guaranteesthegrowthofa3Dmolecularnetwork材料体系设计tetraphenylmethanecore+fourperipheralcarbazolegroups

precursorTPTCz结构特点：制备方法——Electropolymerization(EP)为什么采用EP？AfewapproachestofabricateCMPfilms：surface-initiatedsynthesis,layer-by-layercross-linking,andhyperbranchedsolubleCMPsEP：anespeciallyusefulmethodforthepreparationofelectroactiveandconductingpolymerfilms应用polymersolarcells(PSCs)polymerlight-emittingdiodes(PLEDs)发现功能特性，探索有意义的应用具体实验方法合成电聚合multicycledcyclicvoltammetry(CV)inthepotentialrangeof–0.8to0.97V

问题：参数控制？有待学习第一次：potentialrangesof-0.8Vto0.97V,再扫0Vto1.05V，scanrateof50mVs-1表征和性能测试Previousstudieshaveshownthatthecarbazolestransformintocationicradicalsduringoxidationandthencoupleseffectivelywitheachothertoformdimericcarbazolecations.主要结果电聚合反应CV结果分析Thecurrentofeachcyclerisesgraduallywithincreasedscancycle,demonstratingthegrowthofthefilmontheelectrode.theonsetoxidativepotentialat0.93V,attributedtotheoxidationofcarbazole>0.93V,theanodecurrentincreasedrapidly,indicatingmorecarbazolesoxidizednegativescan,reductivepeakof0.71V,assignedtothereductionofthedimericcarbazolecation.thesecondscan,anewpeakappearsat0.80V,duetotheoxidationoftheformeddimericcarbazolesThehighreactivityandcompletecouplingreactionofthecarbazolesarethekeyfactorstofabricateastructurallywell-definedCMPfilm,whichistheessenceofournovelstrategytofabricateCMPfilms.structuralanalysis(UV-vis,XPS,FTIR)oftheEPfilmsdemonstratedthattherewereonlydimericcarbazolesintheEPfilms

thecurrentascribedtothedimericcarbazoledecreasedtoacertainvaluewithincreasingscancycle,whichindicatedthattheEPprocesswascompleteandnosubsequentEPprocessoccurred.theobtainedEPfilmneverdissolvedinanyorganicsolvents,whichisadirectreflectionofitshighlycross-linkedstructureincontrastwiththehighsolubilityoftheprecursorinchloroform.主要结论电聚合：高效、完全依据？（补充材料）意义？（反应完全）为什么？（有待研究）CV质疑？（有待研究）交联反应证据的充分性？二聚体就不溶？如何交联？成膜膜表征high-resolutiontransmissionelectronmicroscopy(HRTEM)Uniformmicropores：d<1nmDFTmodeling：0.9Presently,itisimpossibletocharacterizetheporepropertiesofthethinfilmsby(BET)measurements,becausethecollectionofadequatesamplesisverydifficult.方法参考比表面积大（推测）：Recently,Chenetal.reportedaCMPmaterialthroughachemicalcouplingofthecarbazolederivativeTCB,whichshowedahighBETsurfacearea(upto2220cm−1)anduniformporedistribution.Thus,aninherentlylargeBETsurfaceareacanbeprefiguredinourCMPfilm.XRD：amorphous膜厚控制与形态ThethicknessofCMPfilmscanbecontrolledpreciselybyadjustingthescancyclesandtheoxidativepotentials.可获得free-standingfilm：膜厚大于150nmAFM：smoothmorphologyTothebestofourknowledge,thisisthefirsttimeaCMPthinfilmhasbeenobtainedwithsuchauniformandsmoothmorphology.膜电化学性质可电化学掺杂Thedopinglevelisobviouslyhigherthanthatofadopedpolycarbazolereportedpreviously,whichdemonstratesthatthemicroporousstructurehelpsthecounterionstodopeintothenetworkeasily.SuchelectrochemicaldopingisfoundtoadjusttheelectricalpropertiesoftheCMPfilmseffectively,suchasworkfunction(WF)andconductivity.掺杂度可控dopinglevel(moleratioofClO4

−toTPTCz,testedbyXPS)：

19%(lightdoping),47%(moderatedoping),and62%(heavydoping)意义：功函（WF、逸出功）：使电子从固体表面中逸出所必须提供的最小能量如果拥有能量比功函数大的光子被照射到固体上，则光电发射将会发生功能应用数据比较：WFCONDUCTIVITYDopedCMPfilm5.2546undopedCMPfilm4.869PEDOT:PSS5.0527TheenhancedWFandconductivityofthedopedCMPfilmindicatesthatitismorecompetentasananodeinterlayercomparedtoPEDOT:PSS.掺杂和未掺杂的CMP膜均有较好导电性？没有解释涉及：（1）导电机理；（2）掺杂机制和影响疑问：polymersolarcells(PSCs)ITO/PEDOT:PSS(30nm)/CMPfilm(≈10nm)/PCDTBT:PC71BM(90nm)/LiF(0.5nm)/Al(100nm)ITO/PEDOT:PSS(30nm)/CMPfilms(≈10nm)/P-PPV(75nm)/CsF(1.3nm)/Al(100nm)

PLEDForeachtype,over200devicesweremadefromover20individualfilms.不容易！器件测试结果PSCsPLEDluminousefficiencyof20.7cdA−1,apeaklevelinthegreen-emittingPLEDs评价选题意义：针对领域中重要问题——加工性有突破：制备了形态良好的膜取得了好的结果：如控制膜厚的方法；有机电子器件结果分析讨论合理，数据可信，论文规范工作系统：合成、制膜、表征、器件、性能等主要创新点：制备CMP膜新方法：电化学聚合

CMP膜应用于PSC、PLED有很好的效果研究水平：启示

问题不同单元电聚合的差异？如咔唑和噻吩比较，用噻吩电聚合复杂和难控制？为什么？需要进一步查阅文献Pironetal.[8]论文中提到几种CMP膜制备方法，如surface-initiatedsynthesis,layer-by-layercross-linking,hyperbranchedsolubleCMPs，这些方法的特点？EP比较优势？CV条件如何确定？如第一次：potentialrangesof-0.8Vto0.97V,再扫0Vto1.05V，scanrateof50mVs-1？

涉及CV原理和电聚合机理Thecurrentofeachcyclerisesgraduallywithincreasedscancycle,dem