CN110167911B - 用于光电子和光电化学器件的含烯胺基团的空穴传输有机分子 - Google Patents
用于光电子和光电化学器件的含烯胺基团的空穴传输有机分子 Download PDFInfo
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- CN110167911B CN110167911B CN201780057677.0A CN201780057677A CN110167911B CN 110167911 B CN110167911 B CN 110167911B CN 201780057677 A CN201780057677 A CN 201780057677A CN 110167911 B CN110167911 B CN 110167911B
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Abstract
Description
技术领域
本发明涉及含烯胺部分的空穴传输化合物,涉及有机空穴导体并且涉及包含这种化合物的空穴传输材料,涉及包含这种空穴传输材料或空穴传输化合物的光电子光电化学器件,特别是光伏器件、有机-无机钙钛矿膜或层状光伏器件、p-n异质结、染料敏化太阳能电池、有机太阳能电池和固态太阳能电池。本发明还涉及一种制备这种有机空穴导体、层和光电器件的方法。
背景技术
近几十年来,人们对可再生能源产生了浓厚的兴趣,并且可再生能源中中最有潜能的是太阳能。我们的星球每小时接收的能量的量等于我们的文明每年消耗的能量的量(G.Tamulaitis,G.Juska.Energy saving semiconducting technologies.Vilnius:Progretus,2008,第116-121页.ISBN9789955781134)。因此,光伏(PV)领域的技术进步可以潜在地解决当前的能量需求。在过去的二十年中广泛探索了使用薄膜第三代光伏器件将太阳能转换为电流。由具有有机/无机光收集器的介孔光电阳极、氧化还原电解质/固态空穴导体和反电极组成的夹层式/单片式PV器件已由于其易制造性、在材料选择方面的灵活性和低成本的有效生产而受到极大关注。
尽管有机-无机杂化钙钛矿(organic-neorganic perovskites)在十九世纪就已为人所知,但是目前它们已经在光伏和光电子领域引起了极大的关注(B.Saparov和D.B.Mitzi.Chem.Rev.2016,116,4558-4596)。近五年来,含有有机-无机杂化钙钛矿的PV器件的效率飙升并且达到了20%以上的值(C.Zuo,H.J.Bolink,H.Han,J.Huang,D.Cahen和L.Ding.Adv.Sci.2016,3,1500324。M.Saliba,S.Orlandi,T.Matsui,S.Aghazada,M.Cavazzini,J.P.Correa-Baena,P.Gao,R.Scopelliti,E.Mosconi,K.H.Dahmen,F.DeAngelis,A.Abate,A.Hagfeldt,G.Pozzi,M.Graetzel,M.K.Nazeeruddin,Nat.Energy2016,1,15017),并且目前记录的含钙钛矿的光伏器件的性能为22.1%(www.nrel.gov/ncpv/images/efficiency_chart.jpg,于2017年12月5日访问)。
空穴传输材料是高效PV器件所需的典型部件之一。这些材料负责光生载流子从吸收体向电极的传输。空穴传输材料应表现出足够的电荷传输特性、足够的能级(尤其是HOMO能级)和良好的热稳定性(Y.Shi,K.Hou,Y.Wang,K.Wang,H.C.Ren,M.Y.Pang,F.Chen,S.Zhang.J.Mater.Chem.A,2016,4,5415-5422)。而这些材料是整个光伏器件的薄弱点。尽管为致力于开发新型空穴传输材料进行了大量研究工作,但是该领域仍然以spiro-OMeTAD(2,2′,7,7′-四(N,N-二对甲氧基苯基氨基)-9,9′-螺二芴)作为有机空穴传输材料(HTM)。目前,使用化合物spiro-MeOTAD获得了具有固体空穴导体的染料敏化太阳能电池的最佳效率。不幸的是,这种HTM的合成工艺是一种漫长而复杂的工艺,需要使用昂贵的Pd催化剂、敏化剂(正丁基锂、格氏试剂)、侵蚀剂(Br2)和低温(-78℃)(T.P.I.Saragi,T.Spehr,A.Siebert,T.Fuhrmann-Lieker,J.Salbeck,Chem.Rev.,2007,107,1011–1065)。此外,为了确保最佳性能,必须经由升华来纯化spiro-MeOTAD,从而不可避免地增加了材料的成本。
进行spiro-MeOTAD取代的合成工作已经产生了几组在PV器件中表现出良好的电荷迁移率和相当的性能的HTM分子(WO2015161989,EP2937399,D.Bi,B.Xub,P.Gao,L.Sun,M.A.Hagfeldt,Nano Energy,2016,23,138–144),然而这些衍生物中的绝大多数仍然需要昂贵的催化剂和多步合成工艺。
可能的替代物之一可以是高迁移率有机聚合物,诸如聚吡咯、聚(3,4-乙烯二氧噻吩)、基于咔唑的聚合物、聚苯胺、聚(4-十一烷基-2,2'-联噻吩)、聚(3-辛基噻吩)、聚(三苯基二胺)和聚(N-乙烯基咔唑)。不幸的是,大多数所研究的聚合物的性能低于spiro-MeOTAD的性能。迄今为止已知的唯一优良材料是聚[双(4-苯基)(2,4,6-三甲基苯基)胺](W.S.Yang,J.H.Noh,N.J.Jeon,Y.C.Kim,S.Ryu,J.Seo,S.I.Seok,Science,2015,348,1234.),其实际应用受到高成本和可再现性问题的阻碍。
空穴传输材料的合成过程涉及无法商购获得的昂贵起始材料化合物,反应步骤的极低温度、复杂性、侵蚀剂和许多步骤(例如用于spiro-OMetTAD合成的5个步骤)。因此,该合成过程漫长、耗时且昂贵,并且引起不可忽视的环境影响。本发明致力于提供一种有效的太阳能电池,所述太阳能电池可以使用容易获得的或低成本的材料、使用基于工业上已知的制造步骤的短制造工艺、保持材料成本和材料的环境影响极低地以有效方式进行快速制备。
发明内容
本发明的目的是提供这样的新型空穴传输有机化合物,其具有合适能级并且在其合成后的纯化过程中不需要升华步骤,这是因为它是合成spiro-OMeTAD的情况并且表现为易于合成。
本发明还致力于提供这样的新型空穴传输材料,其为包含钙钛矿或有机染料或有机金属染料作为敏化剂或光吸收材料的光伏器件以及为另外的光电子器件有机发光二极管(OLED)、场效应晶体管(FET)提供了更高的功率转换效率(PCE)。
所述目的通过权利要求1-13中所述的全部特征实现。
本发明的主要目的是本发明式(I)的具有烯胺基团的新型化合物:
其中
n为1、2、3、4、5、6、7或8;
Q为包含至少一对共轭双键(-C=C-C=C-)的单环或多环体系,所述多环体系包含通过共价键结合在一起的稠合芳环或单环芳环或具有N、O、S、Se、Si杂原子的杂芳族体系。所述单环或多环体系被H、卤素、氰基、C1-C20氰基烷基、C1-C20烷基,C1-C20烷氧基,C1-C20烷氧基烷基、C1-C20卤代烷基、C1-C20卤代烷氧基烷基取代,其中所述氰基烷基、烷基、烷氧基、烷氧基烷基、卤代烷基、卤代烷氧基烷基、C4-C20芳基、C4-C20烷基芳基,C4-C20烷氧基芳基、C4-C20烯基芳基烷基、C4-C20烷氧基芳基烯基、C4-C20双烷氧基芳基烯基。
如果它们包含3个或更多个碳,则它们可以是直链、支链或环状的,其中卤素选自Cl、F、Br或I;
R是在每次出现时相同或不同地选自C1-C20烷基、C2-C20烯基、C4-C20芳基烯基、C4-C20芳基的取代基。所述芳基和芳基烯基可以未被取代或者被C1-C20烷基或C1-C20烷氧基取代,如果它们包含3个或更多个碳,则它们可以是直链、支链或环状的;
R1、R2、R3、R4彼此独立并且选自卤素、氰基、C1-C20氰基烷基、C1-C20烷基、C1-C20烷氧基、C1-C20烷氧基烷基、C1-C20卤代烷基、C1-C20卤代烷氧基烷基。如果它们包含3个或更多个碳,则它们可以是直链、支链或环状的,其中卤素选自Cl、F、Br或I。
根据另一实施方案,本发明式(I)的具有烯胺基团的空穴传输化合物选自但不限于根据式(1)至(44)中任一者的化合物:
在另一方面,本发明提供一种空穴传输材料,其包含至少一种具有空穴传输特性的分子,以及选自式(I)化合物的前述化合物中的两种或更多种化合物的组合。所述通式(I)化合物用于用作有机非聚合半导体。
更特别地,本发明提供选自至少一种通式(I)化合物的空穴传输材料。
在另一方面,本发明还提供一种光电子和/或光电化学器件,其包含式(I)的本发明化合物。
本发明的光电子和/或光电化学器件包含空穴传输材料,其中所述空穴传输材料包含式(I)化合物。
本发明的光电子和/或光电化学器件选自有机光伏器件、光伏固态器件、p-n异质结、有机太阳能电池、染料敏化太阳能电池、固态太阳能电池、光电晶体管、LED(发光二极管)或OLED(有机发光二极管)。
根据一个实施方案,本发明的光电子和/或光电化学器件,特别是光伏固态器件包括导电支撑层、表面增加支架结构、敏化剂或敏化剂层、空穴传输层和反电极和/或金属层。
在另一实施方案中,本发明的光电子和/或光电化学器件是光伏固态器件,其是包含有机-无机钙钛矿作为层形式的敏化剂的固态太阳能电池。
根据一个实施方案,本发明的光电子和/或光电化学器件是选自有机太阳能电池、染料敏化太阳能电池或固态器件的太阳能电池。
在一个实施方案中,光电子和/或光电化学器件的空穴传输层,特别是光伏固态器件的空穴传输层,由本发明的空穴传输材料制成,所述空穴传输材料包含至少一种选自式(I)化合物的小分子空穴传输材料。具体地,空穴传输材料包含至少一种式(I)化合物。
根据另一实施方案,光电子和/或光电化学器件,特别是光伏固态器件,包括包含本发明的空穴传输材料的空穴收集器层(hole collector layer),导电层,电子阻挡层,敏化剂层和集电体层(current collector layer),其中空穴收集器层被导电层覆盖;其中电子阻挡层位于导电层与敏化剂层之间,所述电子阻挡层与为金属或导体的集电体层接触。
根据另一实施方案,所述导电材料选自一种或多种导电聚合物或一种或多种空穴传输材料,所述一种或多种导电聚合物或一种或多种空穴传输材料可选自聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸酯)(PEDOT:PSS)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸酯):石墨烯纳米复合物(PEDOT:PSS:石墨烯)、聚(N-乙烯基咔唑)(PVK)和磺化聚(二苯胺)(SPDPA),优选选自PEDOT:PSS、PEDOT:PSS:石墨烯和PVK,更优选选自PEDOT:PSS。导电聚合物也可选自包括例如聚苯胺、聚吡咯、聚噻吩、聚苯、聚乙烯二氧噻吩、聚丙烯二氧噻吩,聚乙炔和上述两种或更多种的组合的聚合物。
导电支撑层优选地是基本上透明的。“透明”意指对可见光的至少一部分是透明的,优选对可见光的主要部分是透明的。优选地,导电支撑层是对所有波长或类型的可见光基本上透明的。此外,导电支撑层可以是对例如不可见光(诸如UV和IR辐射)透明的。
导电支撑层优选地用作和/或包括集电体,从而收集从光伏固态器件获得的电流。导电支撑层可包含选自铟掺杂的氧化锡(ITO)、氟掺杂的氧化锡(FTO)、ZnO-Ga2O3、ZnO-Al2O3、氧化锡,锑掺杂的氧化锡(ATO)、SrGeO3和氧化锌的材料,所述材料优选涂覆在透明基板(诸如塑料或玻璃)上。
在这种情况下,塑料或玻璃提供所述层的支撑结构,并且所列举的导电材料提供导电性。这种支撑层通常分别称为导电玻璃和导电塑料,因此它们是根据本发明优选的导电支撑层。根据一个实施方案,导电支撑层包括导电透明层,所述导电透明层可以选自导电玻璃和导电塑料。
根据本发明的太阳能电池和异质结的一个实施方案,表面增加支架结构是纳米结构化的和/或纳米多孔的。因此,支架结构优选地构造为纳米级。与导电支撑件的表面相比,所述支架结构的结构增加了有效表面。
根据一个实施方案,所述支架结构由金属氧化物制成和/或包含金属氧化物。例如,支架结构的材料选自半导体材料,诸如例如Si、TiO2、SnO2、Fe2O3、ZnO、WO3、Nb2O5、CdS、ZnS、PbS、Bi2S3、CdSe、CdTe、SrTiO3、GaP、InP、GaAs、CuInS2、CuInSe2,以及它们的组合。
根据一个实施方案,光伏固态器件的敏化剂层包含至少一种颜料,所述至少一种颜料选自有机颜料、无机颜料、有机金属颜料和有机-无机颜料,或者它们的组合。敏化剂优选是光吸收化合物或材料。优选地,敏化剂是颜料,并且最优选地敏化剂是有机-无机颜料。
敏化剂层可包含一种或多种由以下项组成的组的颜料:有机金属敏化化合物(花菁(telocyanine)衍生的化合物、紫菜碱衍生的化合物)、不含金属的有机敏化化合物(基于吡咯并吡咯二酮(DPP)的敏化剂)、无机敏化化合物(诸如量子点)、Sb2S3(硫化锑,例如呈薄膜形式)、有机颜料的聚集体,纳米复合物,特别地为有机-无机钙钛矿,以及前述内容的组合。出于本发明的目的,原则上可以使用任何类型的染料或敏化剂,包括不同类型的染料或相同类型的不同染料的组合。
根据一个实施方案,本发明的光伏固态器件的敏化剂层被一包含式(I)化合物的层覆盖。优选地,所述敏化剂层包含有机-无机钙钛矿。
根据一个实施方案,敏化剂或敏化剂层包含有机-无机钙钛矿,由有机-无机钙钛矿组成,或由有机-无机钙钛矿制成。所述有机-无机钙钛矿在一种钙钛矿颜料或混合的钙钛矿颜料或与其他染料或敏化剂混合的钙钛矿颜料的膜的条件下提供。
根据另一实施方案,除了有机-无机钙钛矿颜料外,敏化剂层还包含另外的颜料,所述另外的颜料选自有机颜料、有机金属颜料或无机颜料。
根据另一实施方案,本发明的光电子和/或光电化学器件是染料敏化太阳能电池(DSC),所述DSC包含式(I)化合物作为空穴传输材料,并且包含选自有机颜料、有机金属颜料或无机颜料或它们的组合的颜料作为敏化剂,如下文所定义。
有机金属敏化剂(染料或颜料)公开于例如EP0613466、EP0758337、EP0983282、EP1622178、WO 2006/038823、WO 2009/107100、WO 2010/055471、WO 2011/039715中,并且基于卟啉的化合物公开于PCT/IB2014/066581中和欧洲专利申请号EP13197269.7中。示例性有机染料(或颜料)是例如在WO2009/098643、EP1990373、WO 2007/100033中公开的那些。有机染料还被用于欧洲专利申请号EP 11161954.0中和PCT/IB2011/054628中。在PCT/IB2013/056648中和在欧洲专利申请号EP12182817.2中公开了不含金属的有机敏化剂(颜料或染料),诸如基于DPP的化合物。
出于该说明书的目的,术语“钙钛矿”是指“钙钛矿结构”,而不是特指钙钛矿材料CaTiO3。出于本说明书的目的,“钙钛矿”涵盖并且优选地涉及具有与钛酸钙相同类型的晶体结构并且材料中的二价阳离子被两个单独的一价阳离子取代的任何材料。钙钛矿结构具有通用化学计量AMX3,其中“A”和“M”是阳离子并且“X”是阴离子。“A”和“M”阳离子可以具有多种电荷,并且在原始的钙钛矿矿物(CaTiO3)中,A阳离子是二价的并且M阳离子是四价的。
在本发明的光电子和/或光电化学器件的另一实施方案中,有机-无机钙钛矿层材料包含式(II)的钙钛矿结构:
AMX3 (II)
其中
-A是碱金属离子,优选Li+、Na+、K+、Rb+、Cs+;铵或甲脒(formamidium)离子,其中一个或多个氢被烷基或酰基取代。所述铵离子包括单烷基铵离子、二烷基铵离子、三烷基铵离子和四烷基铵离子,其中一个或多个氢被烷基取代。优选地,取代基是烷基或独立地选自C1-C6的基团,优选为甲基或乙基。所述铵离子包括脒(amidinium)离子、N-烷基脒离子和亚氨基脒(imidinium)离子,其中一个或多个氢被烷基取代。优选地,脒离子或亚氨基脒离子选自C1-C6甲酰胺基团,优选为甲脒基团或乙脒(acetamidium)基团。有机阳离子A中的氢原子可以被选自F、Cl、I和Br的卤素取代,优选被F或Cl取代。
优选地,A是Cs+或甲基铵离子(MA+),或甲脒离子(FA+)。
-M是选自由以下项组成的组的二价金属阳离子:Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+、Eu2+或Yb2+;优选地为Pb2+、Sn2+。
-X是单价阴离子,独立地选自由以下项组成的组:Cl-、Br-、I-、NCS-、CN-和NCO-;优选地为Cl-、Br-、I-。X可以相同或不同。
根据优选的实施方案,有机-无机钙钛矿的示例是:甲基铵卤化铅,例如甲基铵碘化铅(CH3NH3PbI3);甲基铵混合卤化铅,例如CH3NH3PbClI2;甲脒卤化铅,例如HC(NH2)2PbI3、HC(NH2)2PbBr3或HC(NH2)2PbCl2I;碘化铯铅(CsPbI3)、碘化铯锡(CsSnI3)。
在本发明的光电子和/或光电化学器件的另一实施方案中,有机-无机钙钛矿层材料包含混合钙钛矿结构,其中A是如上所定义的两种或更多种阳离子的混合物,X是如上所定义的两种或更多种阴离子的混合物。优选地,A是两种阳离子的混合物,M是Pb并且X是两种阴离子的混合物。式(II)可以表示为下式(III):
A1 1-yA2 yPbX1 3-zX2z (III)
其中:
A1和A2是如上面针对A所定义的有机一价阳离子;
X1和X2可以是选自由以下项组成的组的相同或不同的一价阴离子:Cl-、Br-、I-、NCS-、CN-和NCO-;
y在0.1与0.9之间的区间内;
z在0.2与2之间的区间内。
附图说明
图1示出了太阳能电池的电流-电压曲线,在所述太阳能电池中对应于化合物V-950和spiro-OMeTAD的化合物(1)被探索作为空穴传输材料。
图2示出了太阳能电池的入射光子电流转化效率(IPCE)曲线,在所述太阳能电池中对应于化合物V-950和spiro-OMeTAD的化合物(1)被探索作为空穴传输材料。
具体实施方式
通式(I)化合物的一般合成方案。
在催化剂(+/-)10-樟脑磺酸(CSA)的存在下、在甲苯回流下,经由2,2-双(4-甲氧基苯基)乙醛(T.Kodera,K.Torizuka(Mitsubishi Paper Mills,Ltd.),日本公开特许公报JP 11043458,1999)与伯胺例如3-氨基-9-乙基-9H-咔唑(Sigma-Aldrich)或杂环的仲胺之间的缩合反应来合成对应于通式(I)的含烯胺基团(-N-C=C)的空穴传输化合物(图1)。使用Dean-Stark设备来缩短反应时间,这是上述方法与文献(Synthetic Metals,第158卷,2008,993)中描述的一种方法的主要区别。根据此方法(方案1)合成化合物1-5:
方案1.空穴传输材料1-5的合成路线
在催化剂(+/-)10-樟脑磺酸(CSA)的存在下并使用Dean-Stark设备,经由2,2-双(4-甲氧基苯基)乙醛与例如芳族胺4-氨基三苯胺(TCI Europe N.V.)之间的缩合来合成含烯胺基团并且对应于通式(I)的空穴传输化合物6(方案2):
方案2.空穴传输材料6的合成路线
众所周知,增大π共轭体系的大小导致更好的电荷传输特性,因此;除了单烯胺1-6之外,具有增大的π共轭体系的二胺7和8也从3,6-二氨基-9H-丁基咔唑和3,6-二氨基-9H-(2-乙基己基)咔唑合成,即从具有若干氨基的9-烷基-9H-咔唑合成方案3)。
方案3.空穴传输材料7和8的合成路线
实施本发明的方式
关于真实实施方案的实施例的信息提供如下,描述了本发明化合物(1-8)的制备方式及其性能。提供此信息是出于说明目的,而不是限制本发明的范围。
实施例1
9-乙基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案1,化合物1或V-950):
将3-氨基-9-乙基咔唑(250mg,1.19mmol)溶于甲苯(5ml+Dean-Stark设备的体积),加入(+/-)10-樟脑磺酸(276mg,1.19mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(915mg,3.57mmol),并使用Dean-Stark设备继续反应另外2小时。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物溶于温乙醇中;将形成的晶体滤出,用冷乙醇洗涤,并从甲苯:乙醇(1:2)的混合物中重结晶。将获得的晶体在40℃下真空干燥,得到1,为黄色晶体(590mg,64%);熔点为226-228℃。
1H NMR(700MHz,DMSO-d6,δ):8.15(d,J=7.8Hz,1H,5-H,Ht),7.80(s,1H,4-H,Ht),7.58-7.54(m,2H,1,2-H,Ht),7.44-7.40(m,1H 6-H,Ht),7.24(d,J=7.0Hz,1H,8-H,Ht),7.11-7.08(m,1H,7-H,Ht),6.96(d,J=8.8Hz,4H,p-Ph),6.88(d,J=9.0Hz,4H,p-Ph),6.67(d,J=9.0Hz,4H,p-Ph),6.44(d,J=8.8Hz,4H,p-Ph),5.79(s,2H,NCH),4.42(kv,J=7.0Hz,2H,NCH2),3.79(s,6H,OCH3),3.70(s,6H,OCH3),1.31(t,J=7.0Hz,3H,CH3).
13C NMR(176MHz,DMSO-d6δ):159.1,139.1,136.4,134.5,132.6,132.3,130.7,129.3,128.7,127.6,126.3,123.43,122.33,121.37,118.76,117.16,114.35,114.24,113.53,110.14,109.47,108.72,55.1(OCH3),55.51(OCH3),37.46(CH2),14.15(CH3)。
元素分析:计算的%:C 80.44,H 6.16,N 4.08。C46H42N2O4.实测的%:
C 80.17,H 6.02,N 3.91。
实施例2
9-丁基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案1,化合物2或V-1013):
将3-氨基-9-丁基咔唑(1g,4.2mmol)溶于甲苯(18ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(2.69g,10.5mmol),并使用Dean-Stark设备继续反应另外1小时。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用THF:正己烷/v:v,1:49纯化,并从乙醇中重结晶。将获得的晶体在40℃下真空干燥,得到2,为黄色晶体(1.65g,55%)。
1H NMR(400MHz,CDCl3δ):8.05(d,J=8.9Hz,1H,5-H,Ht),7.81(s,1H,4-H,Ht),7.44(t,J=7.2Hz,1H,6-H,Ht),7.39-7.33(m,1H,8-H,Ht),7.33(t,J=7.5Hz,2H,1,2-H,Ht),7.17(t,J=7.4Hz,1H,7-H,Ht),7.07(d,J=8.7Hz,4H,p-Ph),6.83(d,J=8.7Hz,4H,p-Ph),6.67(d,J=8.7Hz,8Hz,4H,p-Ph),6.54(d,J=8.7Hz,4H,p-Ph),5.89(s,2H,NCH),4.30(t,J=7.2Hz,2H,NCH2),3.85(s,6H,OCH3),3.77(s,6H,OCH3),1.88-1.82(m,2H,NCH2),1.55(s,2H,NCH2CH2),1.44-1.39(m,2H,NCH2CH2CH2),0.96(t,J=7.2Hz,3H,CH3)。
13C NMR(75MHz,CDCl3δ):159.0,158.7,141.2,139.2,136.9,134.9,133.2,130.8,129.8,128.9,127.9,125.9,123.7,122.6,120.9,118.5,116.9,114.6,114,113.2,109.1,108.8,55.6(OCH3),55.4(OCH3),43.1(CH2),31.4(CH2),20.7(CH2),14.1(CH3)。
元素分析:计算的%:C 80.64,H 6.49,N 3.92。C48H46N2O4。实测的%:C 80.44,H6.29,N 3.72。
实施例3
9-己基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案1,化合物3或V-1001):
将3-氨基-9-己基咔唑(1g,3.8mmol)溶于甲苯(18ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(2.41g,9.4mmol),并使用Dean-Stark设备继续反应另外1小时。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用丙酮:正己烷/v:v,1:49纯化,并从乙醇中重结晶。将获得的晶体在40℃下真空干燥,得到3,为黄色晶体(1.56g,55%)。
1H NMR(400MHz,CDCl3δ):8.07(d,J=7.7Hz,1H,5-H,Ht),7.8(s,1H,4-H,Ht),7.38(d,1H,J=8.2Hz,1H,7-H,Ht),7.33(t,J=3.6Hz,2H,6-H,Ht),7.12-7.19(m,1H,8-H,Ht),7.07(t,J=5.7Hz,4H,p-Ph),6.84(t,J=5.8Hz,4H,p-Ph),6.65-6.68(m,4H,p-Ph),6.53-6.56(m,4H,p-Ph),5.89(s,2H,NCH),4.8(t,J=7.2Hz,2H,NCH2),3.84(s,6H,OCH3),3.77(s,6H,OCH3),1.85-1.89(m,2H,NCH2CH2),1.37-1.41(m,2H,NCH2CH2CH2),1.29-1.33(m,4H,NCH2CH2CH2CH2CH2),0.88(t,J=7.0Hz,3H,CH3)。
13C NMR(100MHz,CDCl3δ):159.0,158.7,141.2,139.2,136.2,134.9,133.2,130.8,129.8,128.9,127.9,125.9,123.7,122.6,120.9,118.6,116.9,114.6,114.0,113.2,109.1,108.7,55.6(OCH3),55.4(OCH3),43.4(CH2),31.8(CH2),29.1(CH2),27.1(CH2),22.7(CH2),14.2(CH3)。
元素分析:计算的%:C 80.83,H 6.78,N 3.77。C50H50N2O4。实测的%:C 80.63,H6.68,N 3.57。
实施例4
9-(2-乙基己基)-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案1,化合物4或V-1000):
将3-氨基-9-(2-乙基己基)咔唑(1g,3.4mmol)溶于甲苯(17ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(2.18g,8.5mmol),并使用Dean-Stark设备继续反应另外1小时。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用丙酮:正己烷/v:v,1:49纯化,并从乙醇中重结晶。将获得的晶体在40℃下真空干燥,得到4,为黄色晶体(1.45g,57%)。
1H NMR(400MHz,CDCl3δ):8.06(d,J=7.8Hz,1H,5-H,Ht),7.81(s,1H,4-H,Ht),7.7(t,J=7.7Hz,1H,6-H,Ht),7.36-7.34(m,1H,8-H,Ht),7.33-7.31(m,2H,1,2-H,Ht),7.17(t,J=7.4Hz,1H,7-H,Ht),7.07(d,J=8.4Hz,4H,p-Ph),6.84(d,J=8.4Hz,4H,p-Ph),6.67(d,J=8.4Hz,4H,p-Ph),6.54(d,J=8.4Hz,4H,p-Ph),5.89(s,2H,NCH),4.18-4.11(m,2H,NCH2),3.85(s,6H,OCH3),3.77(s,6H,OCH3),2.08-2.05(m,1H,NCH2CH),1.44-1.32(m,6H,NCH2(CH2)3),1.32-1.27(m,2H,NCH2CHCH2),0.93(t,J=7.3Hz,3H,CH2CH3),0.89(t,J=7.3Hz,3H,CH2CH3)。
13C NMR(100MHz,CDCl3,δ):159.0,158.7,141.7,139.2,137.4,134.9,133.2,130.8,129.8,128.9,127.9,125.8,123.6,122.6,120.9,118.6,116.9,114.6,114.0,113.2,109.4,109.1,108.7,55.6(OCH3),55.4(OCH3),47.7(CH),39.7(CH2),31.2(CH2),29.0(CH2),24.5(CH2),23.2(CH2),14.2(CH3),11.1(CH3)。
元素分析:计算的%:C 81.01,H 7.06,N 3.63。C52H54N2O4。实测的%:C80.81,H6.84,N 3.43。
实施例5
9-丁基-6-(叔丁基)-3-{N,N-[2,2–双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案1,化合物5或V-1004):
将3-氨基-6-(叔丁基)-9-丁基咔唑(1g,3.4mmol)溶于甲苯(17ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(2.18g,8.5mmol),并使用Dean-Stark设备继续反应另外30min。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用THF:正己烷/v:v,1:24纯化,并从20%的THF溶液中沉析到20倍过量的甲醇中。将获得的物质在40℃下真空干燥,得到5,为黄色无定形粉末(1.45g,57%)。
1H NMR(400MHz,CDCl3δ):8.09(d,J=1.7Hz,1H,5-H,Ht),7.81(s,1H,4-H,Ht),7.54-7.50(m,1H,6-H,Ht),7.33-7.27(m,3H,Ht),7.26(s,1H,7-H,Ht),7.08(d,J=8.8Hz,4H,p-Ph),6.84(d,J=8.8Hz,4H,p-Ph),6.68(d,J=8.8Hz,4H,p-Ph),6.55(d,J=8.8Hz,4H,p-Ph),5.90(s,2H,NCH),4.27(t,J=7.0Hz,2H,NCH2),3.85(s,6H,OCH3),3.78(s,6H,OCH3),1.43(s,9H,C(CH3)3),1.47-1.39(m,2H,CH2),0.96(t,J=7.3Hz,3H,CH3)。
13C NMR(100MHz,CDCl3δ):159.0,158.7,141.7,139.5,139.4,138.9,137.4,134.9,133.2,130.8,129.6,129.5,128.9,128.1,123.8,122.3,117.2,116.6,114.0,113.2,109.0,108.7,108.2,55.6(OCH3),55.4(OCH3),43.1(CH2),34.9(CH2),32.2(CH2),31.5(CH3),23.8(CH3),20.8(CH3),14.1(CH3)。
元素分析:计算的%:C 81.01,H 7.06,N 3.63。C52H54N2O4。实测的%:C 80.81,H6.86,N 3.43。
实施例6
4-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}三苯胺(参见方案2,化合物6或V-1012):
将4-氨基三苯胺(1g,3.8mmol)溶于甲苯(18ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(2.46g,9.6mmol),并使用Dean-Stark设备继续反应另外30min。在反应完成后,将(TLC,THF:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用THF:正己烷/v:v,1:24纯化,并从20%的THF溶液中沉析到20倍过量的甲醇中。将获得的物质在40℃下真空干燥,得到6,为黄色无定形粉末(1.6g,58%)。
1H NMR(400MHz,CDCl3,δ):7.31-7.22(m,4H,Ar),7.15-6.93(m,14H,Ar),6.88(d,J=8.3Hz,4H,p-Ph),6.67(d,J=8.3Hz,4H,p-Ph),6.53(d,J=8.3Hz,4H,p-Ph),5.83(pl.s,2H,NCH),3.89(s,6H,OCH3),3.78(s,6H,OCH3)。
13C NMR(100MHz,CDCl3,δ):158.9,158.6,148.1,141.8,134.4,132.7,136.7,130.2,129.1,128.8,126.4,123.2,122.0,117.9,114.4,113.8,113.0,99.9,55.4(OCH3),55.2(OCH3)。
元素分析:计算的%:C 81.50,H 6.02,N 3.80。C50H44N2O4。实测的%:C 81.20,H5.82,N 3.48。
实施例7
9-丁基-3,6-双{N3,N3,N6,N6-四(2,2–双[4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(参见方案3,化合物7或V-1020):
9-丁基咔唑-3,6-二胺(1g,4.8mmol)溶于甲苯(21ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(5.04g,19.7mmol),并使用Dean-Stark设备继续反应另外1h。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用丙酮:正己烷/v:v,3:22纯化,并从20%的THF溶液中沉析到20倍过量的甲醇中。将获得的物质在40℃下真空干燥,得到7,为黄色无定形粉末(3.2g,55%)。
1H NMR(400MHz,CDCl3δ):7.76(s,2H,4,5-H,Ht),7.35-7.26(m,4H,1,2,7,8-H,Ht),7.06(d,J=8.7Hz,8H,p-Ph),6.82(d,J=8.2Hz,8H,p-Ph),6.63(d,J=8.2Hz,8H,p-Ph),6.49(d,J=8.7Hz,8H,p-Ph),5.86(s,4H,=CH),4.27(s,2H,NCH2),3.84-3.81(m,12H,OCH3),3.77-3.74(m,12H,OCH3),1.87-1.83(m,2H,N CH2CH2),1.44-1.39(m,2H,NCH2CH2CH2),0.96(t,J=7.3Hz,3H,CH3)。
13C NMR(100MHz,CDCl3δ):158.9,158.6,147.9,143.7,134.9,133.2,130.8,128.9,126.7,117.6,113.9,113.1,111.5,109.0,89.6,84.5,55.6(OCH3),55.4(OCH3),23.0(CH2),20.7(CH2),16.7(CH2),14.1(CH2)。
元素分析:计算的%:C 79.64,H 6.27,N 3.48。C80H75N3O8。实测的%:C 79.44,H6.07,N 3.28。
实施例8
9-(2-乙基己基)-3,6-双{N3,N3,N6,N6-四(2,2–双[4-甲氧基苯基)乙烯基]-氨基}-9H-咔唑(参见方案3,化合物8或V-1021):
将9-(2-乙基己基)咔唑-3,6-二胺(1g,3.2mmol)溶于甲苯(17ml),加入(+/-)10-樟脑磺酸(1g,4.3mmol),并将反应混合物回流20min。然后加入2,2-双(4-甲氧基苯基)乙醛(4.1g,16mmol),并使用Dean-Stark设备继续反应另外1.5h。在反应完成后,将(TLC,丙酮:正己烷/v:v,1:4)反应混合物用乙酸乙酯萃取,将有机层用无水Na2SO4干燥,过滤并真空去除有机溶剂。将残余物通过柱色谱法使用丙酮:正己烷/v:v,3:22纯化,并从20%的THF溶液中沉析到20倍过量的甲醇中。将获得的物质在40℃下真空干燥,得到8,为黄色无定形粉末(2g,49%)。
1H NMR(400MHz,CDCl3δ):7.76(s,2H,4,5-H,Ht),7.35-7.26(m,4H,1,2,7,8-H,Ht),7.06(d,J=8.6Hz,8H,p-Ph),6.82(d,J=8.3Hz,8H,p-Ph),6.67-6.60(m,8H,p-Ph),6.49(d,J=8.6Hz,8H,p-Ph),5.86(s,4H,=CH),4.11(d,J=8.3Hz,2H,NCH2),3.84(s,12H,OCH3),3.74(s,12H,OCH3),2.04(s,1H,NCH2CH),1.45-1.26(m,8H,NCH2CH(CH2)4),0.91(m,6H,(CH3)2)。
13C NMR(100MHz,CDCl3δ):158.9,158.6,144.2,143.6,140.6,134.9,133.2,130.9,129.6,128.9,128.0,123.2,119.7,117.7,117.6,115.1,114.6,113.9,113.1,109.3,89.5,55.6(OCH3),55.4(OCH3),47.7(CH),39.6(CH2),32.8(CH2),31.1(CH2),29.0(CH2),23.3(CH2),14.3(CH3),11.0(CH3)。
元素分析:计算的%:C 79.91,H 6.63,N 3.33。C84H83N3O8。实测的%:C 79.71,H6.43,N 3.13。
实施例9
电离电位测量
通过空气中的电子光发射法测量式(1)至(8)化合物的层的固态电离电位(Ip)(E.Miyamoto,Y.Yamaguchi,M.Masaaki,Electrophotography,1989,第28卷,第364页)。通过将材料溶于THF中并将其涂覆在预涂有约0.5μm厚的甲基丙烯酸甲酯与甲基丙烯酸的共聚物粘合剂层的Al板上来制备用于电离电位测量的样品。传输材料层的厚度为0.5-1μm。在真空中进行光电发射实验,高真空是这些测量的主要要求之一。如果真空不够高,则样品表面氧化和气体吸附会影响测量结果。然而,在我们的情况下,所研究的有机材料对氧足够稳定,因此测量可以在空气中进行。将样品用来自具有氘灯的石英单色仪的单色光照射。入射光束的功率为(2-5)·10-8W。向样品基板供应-300V的负电压。将具有用于照射的4.5×15mm2狭缝的反电极置于距离样品表面8mm处。将反电极连接到BK2-16型静电计的输入端,所述静电计以开放输入方式(open input regime)工作、用于光电流测量。10-15-10-12A强光电流在照射下在电路中流动。光电流I强烈地依赖于入射光光子能量hυ。将I0.5=f(hν)依赖性绘制成曲线图。通常,光电流对入射光量子能量的依赖性通过在阈值附近I0.5与hν之间的线性关系很好地描述。将该依赖性的线性部分外推到hν轴,并且将Ip值确定为截取点处的光子能量。Ip结果呈现在表1中。
实施例10
空穴漂移迁移率测量
通过将合成的化合物1-8的溶液旋涂在具有导电Al层的聚酯膜上来制备用于空穴迁移率测量的样品。将THF用于化合物1-6,以及将氯化苯用于化合物7和8。层厚度在5-10μm的范围内。通过静电复印飞行时间(xerographic time of flight,XTOF)技术来测量空穴漂移迁移率(Vaezi-Nejad,S.M.,Int.J.Electronics,1987,62,第3期,361-384)。通过正电晕充电产生电场。通过用氮激光脉冲照射来在层表面处产生电荷载流子(脉冲持续时间为2ns,波长为337nm)。因脉冲照射导致的层表面电位降低高达照射前初始电位的1-5%。连接到宽频带静电计的电容探针测量表面电位下降的速度dU/dt。通过双对数尺度的dU/dt瞬态曲线上的扭结(kink)来确定传输时间tt。按照公式μ=d2/U0tt计算漂移迁移率,其中d是层厚度,U0——照射时的表面电位。所述μ结果呈现在表1中。
表1.空穴传输化合物1-8和spiro-OMeTAD的电离电位(Ip)和电荷迁移率值(μ)
所有合成化合物的估计Ip值在4.93eV-5.11eV的范围内,并且非常接近spiro-OMeTAD的值(5.0eV)。所测量的合成化合物1-6和8的电荷迁移率值也与所测量的spiro-OMeTAD的值可比,而化合物7(V-1020)的电荷迁移率在弱电场下增大约一个数量级(μ0=1.2×10-4cm2V-1S-1)。
实施例11
对应于化合物V-950的式(1)化合物的光伏表征
按照文献(T.J.Jacobsson,J.P.Correa-Baena,M.Pazoki,M.Saliba,K.Schenk,M.和A.Hagfeldt.Energy Environ.Sci.,2016,9,1706-1724)中描述的工艺,使用介孔TiO2光阳极和Au阴极(FTO/致密TiO2/介孔致密TiO2/混合钙钛矿/V-950/Au)在混合的基于钙钛矿的太阳能电池中测试空穴传输器V-950的性能。使用阳离子(甲基氨(MA)、甲脒(FA))和阴离子(I、Br)的混合物来制备混合钙钛矿。
在AM 1.5G照射下,所获得的器件显示出的最大PCE为17.8%。所测得的填充因数为0.74,电流密度(JSC)为22.5mA/cm2,并且开路电压(VOC)为1.07V(图1)。高JSC表明光生电荷载流子被有效地提取,并且高VOC显示在钙钛矿价带与V-950的HOMO之间可能存在良好的能级排列(energy level alignment)。该高VOC还表明注入的空穴与来自钙钛矿封盖层或TiO2的电子之间的复合重组。对应于化合物V-950和spiro-OMeTAD的化合物(1)的电流密度-电压(J-V)特征呈现在图1中。作为波长的函数的器件的入射光子电流转换效率(IPCE)(图2)表明,具有V950作为HTM的器件表现出从覆盖整个可见光区域的400nm至700nm下的IPCE高于90%。
器件特性表明,所研究的HTM的性能与spiro-OMeTAD相当。
Claims (11)
1.一种通式(I)化合物,其特征在于:
其中,n为1、2、3、4、5、6、7或8;
其选自以下化合物中的任一者:
9-乙基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(1);
9-丁基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(2);
9-己基-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(3);
9-(2-乙基己基)-3-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(4);
9-丁基-6-(-丁基)-3-{N,N-[2,2–bis(4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(5);
4-{N,N-双[2,2-双(4-甲氧基苯基)乙烯基]氨基}三苯胺(6);
9-丁基-3,6-双{N3,N3,N6,N6-四(2,2–双[4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(7);
9-(2-乙基己基)-3,6-双{N3,N3,N6,N6-四(2,2–双[4-甲氧基苯基)乙烯基]氨基}-9H-咔唑(8)。
2.根据权利要求1所述的通式(I)化合物,其特征在于:其用作光伏器件中的非聚合空穴传输材料。
3.一种包含至少一种小分子空穴传输材料的空穴传输材料,其特征在于:所述至少一种小分子空穴传输材料选自根据权利要求1或2所述的通式(I)化合物中的一者。
4.一种包含根据权利要求1或2所述的通式(I)化合物的光伏器件。
5.根据权利要求4所述的包含所述的通式(I)化合物的光伏器件,其特征在于:其中空穴传输材料包含通式(I)化合物。
6.根据权利要求4-5中任一项所述的光伏器件,其特征在于:其选自有机光伏器件、光伏固态器件、p-n异质结、有机太阳能电池、染料敏化太阳能电池和固态太阳能电池。
7.根据权利要求6所述的光伏器件,其特征在于:其是包含有机-无机钙钛矿作为层形式的敏化剂的固态太阳能电池。
8.根据权利要求7所述的光伏器件,其特征在于:其是包含有机-无机钙钛矿作为层形式的敏化剂并且被层形式的根据权利要求1或2所述的式(I)化合物覆盖的固态太阳能电池。
9. 根据权利要求7所述的光伏器件,其特征在于:其中所述有机-无机钙钛矿层材料包含式(II)的钙钛矿结构:
AMX3 (II)
其中,A为Li+、Na+、K+、Rb+、Cs+;或铵离子或甲脒离子,铵离子或甲脒离子中一个或多个氢被烷基或酰基取代;M选自由以下项组成的组的二价金属阳离子:Cu2+、Ni2+、Co2+、Fe2+、Mn2 +、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+、Eu2+或Yb2+;X独立地选自由以下项组成的组:Cl-、Br-、I-、NCS-、CN-和NCO-。
10. 根据权利要求7所述的光伏器件,其特征在于:其中所述有机-无机钙钛矿层材料包含下式(III)的混合钙钛矿结构:
A1 1-yA2 yPbX1 3-zX2z (III)
其中:
A1和A2是针对权利要求9所述的A所定义的有机一价阳离子;
X1和X2选自由以下项组成的组的相同或不同的一价阴离子:Clˉ、Brˉ、Iˉ、NCSˉ、CNˉ和NCOˉ;
y在0.1与0.9之间的区间内;
z在0.2与2之间的区间内。
11.权利要求1或2所述的化合物在根据权利要求4至10中任一项所述的光伏器件中作为空穴传输材料的用途。
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PCT/IB2017/055587 WO2018051278A2 (en) | 2016-09-19 | 2017-09-15 | Hole transporting organic molecules containing enamine groups for optoelectronic and photoelectrochemical devices |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808505A (en) * | 1986-04-08 | 1989-02-28 | Minolta Camera Kabushiki Kaisha | Photosensitive member with enamine charge transport material |
US5098810A (en) * | 1989-05-27 | 1992-03-24 | Japat Ltd. | Electrophotographic photoreceptors |
JP2000159732A (ja) * | 1998-11-24 | 2000-06-13 | Sharp Corp | トリ−(p−N−エナミン置換−アミノフェニル)ベンゼン化合物および有機電界発光素子 |
CN1469177A (zh) * | 2002-07-17 | 2004-01-21 | ϣ | 用于改善电泳显示器性能的方法和组合物 |
WO2016139570A1 (en) * | 2015-03-02 | 2016-09-09 | Ecole Polytechnique Federale De Lausanne (Epfl) | Small molecule hole transporting material for optoelectronic and photoelectrochemical devices |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0789222B2 (ja) * | 1986-04-08 | 1995-09-27 | ミノルタ株式会社 | 感光体 |
JPS63231354A (ja) * | 1987-03-20 | 1988-09-27 | Fujitsu Ltd | 電子写真感光体 |
JPS63262657A (ja) * | 1987-04-21 | 1988-10-28 | Asahi Chem Ind Co Ltd | 電子写真感光体 |
JP2653080B2 (ja) * | 1988-01-29 | 1997-09-10 | ミノルタ株式会社 | 感光体 |
JP2973467B2 (ja) * | 1990-03-20 | 1999-11-08 | 日立化成工業株式会社 | エナミン誘導体,その前駆体及びそれらの製造法並びに該エナミン誘導体を含有してなる電子写真感光体 |
GB9217811D0 (en) | 1992-08-21 | 1992-10-07 | Graetzel Michael | Organic compounds |
DE69415350T2 (de) | 1994-05-02 | 1999-07-01 | Ecole Polytechnique Federale De Lausanne (Epfl), Lausanne | Phosphonierte polypyridyl-verbindungen und ihre metall-komplexe |
JP3418510B2 (ja) * | 1996-11-25 | 2003-06-23 | シャープ株式会社 | 有機電界発光素子 |
US6245988B1 (en) | 1997-05-07 | 2001-06-12 | Ecole Polytechnique Federale De Lausanne | Metal complex photosensitizer and photovoltaic cell |
JPH1143458A (ja) | 1997-07-29 | 1999-02-16 | Mitsubishi Paper Mills Ltd | ジアリールアセトアルデヒド類とその誘導体の合成方法及び新規なエナミン化合物 |
JP3580691B2 (ja) * | 1998-03-10 | 2004-10-27 | シャープ株式会社 | テトラ置換ジアミン化合物、該化合物を用いた有機電界発光素子及び有機感光体 |
JPH11335336A (ja) * | 1998-05-25 | 1999-12-07 | Sharp Corp | トリス[4−(n−エナミン)フェニル]アミン化合物及び該化合物を用いた有機電界発光素子 |
JP2000007625A (ja) * | 1998-06-18 | 2000-01-11 | Sharp Corp | トリス(p−N−エナミン置換−アミノフェニル)アミン化合物及び有機電界発光素子 |
US6359211B1 (en) | 1999-06-17 | 2002-03-19 | Chemmotif, Inc. | Spectral sensitization of nanocrystalline solar cells |
JP3685482B2 (ja) * | 2001-01-30 | 2005-08-17 | 京セラミタ株式会社 | 電子写真感光体 |
EP1622178A1 (en) | 2004-07-29 | 2006-02-01 | Ecole Polytechnique Federale De Lausanne (Epfl) | 2,2 -Bipyridine ligand, sensitizing dye and dye sensitized solar cell |
WO2006038823A1 (en) | 2004-10-08 | 2006-04-13 | Massey University | Beta-substituted porphyrins |
JP5106381B2 (ja) | 2006-03-02 | 2012-12-26 | 日本化薬株式会社 | 色素増感光電変換素子 |
JP2008226582A (ja) * | 2007-03-12 | 2008-09-25 | Konica Minolta Business Technologies Inc | 光電変換素子及び太陽電池 |
CN101240117B (zh) | 2008-02-04 | 2010-11-10 | 中国科学院长春应用化学研究所 | 纯有机染料和由其制备的染料敏化太阳能电池 |
CN101235214B (zh) | 2008-02-27 | 2012-07-04 | 中国科学院长春应用化学研究所 | 有机钌染料及染料敏化太阳能电池 |
US8962977B2 (en) | 2008-11-11 | 2015-02-24 | Ecole Polytechnique Federale De Lausanne (Epfl) | Photoelectric conversion devices comprising novel ligands and sensitizers |
EP2301932A1 (en) | 2009-09-29 | 2011-03-30 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Novel ligands for sensitizing dyes of dye-sensitized solar cells |
EP2511924A1 (en) | 2011-04-11 | 2012-10-17 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Transition metal complexes as redox couples for electrochemical and optoelectronic devices |
WO2013057538A1 (en) | 2011-10-18 | 2013-04-25 | École Polytechnique Fédérale De Lausanne (Epfl) | Compounds for electrochemical and/or optoelectronic devices |
EP2703468A1 (en) | 2012-09-03 | 2014-03-05 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Diketopyrrolopyrole (DPP)-based sensitizers for electrochemical or optoelectronic devices |
EP2883915A1 (en) | 2013-12-13 | 2015-06-17 | Ecole Polytechnique Federale de Lausanne (EPFL) | Porphyrin based sensitizer for dye-sensitized solar cell |
EP2937399A1 (en) | 2014-04-22 | 2015-10-28 | Basf Se | Hole-transport materials for organic solar cells or organic optical sensors |
-
2016
- 2016-09-19 LT LT2016515A patent/LT6540B/lt unknown
-
2017
- 2017-09-15 EP EP17805256.9A patent/EP3515884A2/en active Pending
- 2017-09-15 WO PCT/IB2017/055587 patent/WO2018051278A2/en unknown
- 2017-09-15 US US16/334,352 patent/US11329229B2/en active Active
- 2017-09-15 CN CN201780057677.0A patent/CN110167911B/zh active Active
- 2017-09-15 JP JP2019536347A patent/JP2019530746A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808505A (en) * | 1986-04-08 | 1989-02-28 | Minolta Camera Kabushiki Kaisha | Photosensitive member with enamine charge transport material |
US5098810A (en) * | 1989-05-27 | 1992-03-24 | Japat Ltd. | Electrophotographic photoreceptors |
JP2000159732A (ja) * | 1998-11-24 | 2000-06-13 | Sharp Corp | トリ−(p−N−エナミン置換−アミノフェニル)ベンゼン化合物および有機電界発光素子 |
CN1469177A (zh) * | 2002-07-17 | 2004-01-21 | ϣ | 用于改善电泳显示器性能的方法和组合物 |
WO2016139570A1 (en) * | 2015-03-02 | 2016-09-09 | Ecole Polytechnique Federale De Lausanne (Epfl) | Small molecule hole transporting material for optoelectronic and photoelectrochemical devices |
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JP2019530746A (ja) | 2019-10-24 |
US11329229B2 (en) | 2022-05-10 |
WO2018051278A2 (en) | 2018-03-22 |
US20190229272A1 (en) | 2019-07-25 |
CN110167911A (zh) | 2019-08-23 |
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