CN104685650B - 用作有机电子器件的n型掺杂剂的环戊二烯的盐 - Google Patents
用作有机电子器件的n型掺杂剂的环戊二烯的盐 Download PDFInfo
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- CN104685650B CN104685650B CN201380049961.5A CN201380049961A CN104685650B CN 104685650 B CN104685650 B CN 104685650B CN 201380049961 A CN201380049961 A CN 201380049961A CN 104685650 B CN104685650 B CN 104685650B
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Abstract
本发明涉及一种有机电子传输层,其具有用于增加所述有机层的n型导电性的至少一种掺杂剂,其特征在于,所述掺杂剂选自根据式1的环戊二烯化合物的盐类所组成的组,其中取代基R1至R2独立选自包括以下的组:‑H、‑D、卤素、‑CN、‑NO2、‑OH、胺、醚、硫醚、烷基、环烷基、丙烯酸、乙烯基、烯丙基、芳烃、稠合芳烃和杂芳烃。
Description
技术领域
本发明涉及一种有机电子传导层(electronic transport layer),其具有用于增加所述有机层的n型导电性(n-conductivity)的至少一种掺杂剂,其特征在于,所述掺杂剂选自环戊二烯化合物的盐类所组成的组。
背景技术
符合市场需求的有效的有机电子元件的提供不仅要求选择高效的单个组件,还要求利用可实现廉价的大规模生产的生产技术。这特别适用于有机元件(organiccomponent),例如有机发光二极管(OLED)(其结构以示意性的形式示于图1中)、有机太阳能电池(图2以示意性形式示出)和有机场效应晶体管(如图3所示),其组成在过去的几年中已针对越来越高的性能而发生改变。
针对提高效率的开发工作的关键点在于建立更好的元件质量,这基本上可以通过提高所使用的有机电子传输层内的电荷载流子的迁移率(mobility)和密度来实现。
两种不同的方法被使用在有机电子器件中以增加导电性。第一,可通过在阴极和电子传输层之间插入中间层来增加电荷载流子的注入。第二,通过使用合适的供体的导电性有机基体材料的n型掺杂来实现电荷载流子密度的增加。在这种情况下,通过从气相或液相共生化(co-sublimation)同时将基体材料与掺杂剂沉积为层。
对于前一种方法通常使用LiF、CsF或(在近期的文献中)碳酸铯的薄的盐层,其降低了电子的逸出功(work function)。例如,Huang,Jinsong等人在Adv.Funct.Mater.2007,00,1-8中、Wu,Chih-I等人在APPLIED PHYSICS LETTERS 88,152104(2006)中以及Xiong,Tao等人在APPLIED PHYSICS LETTERS 92,263305(2008)中描述了碳酸铯的特性和效果。这些中间层显著改善了电子传输,但是这种改进对于高效的层来说是不充分的。
对于电子传输层的掺杂来说,通常情况是,使用具有HOMO(最高占据的分子轨道)高于基体材料的LUMO(最低未占分子轨道)的物质。其为将电子从掺杂剂传送至基体材料的先决条件,因此是其传导性提高的先决条件。此外,进一步优选引入其价电子具有非常低的逸出功或电离能(ionization energie)的物质。这也可以促进掺杂剂的电子的释放并且增加层的导电性。
例如,DE 103 38 406 A1提出了一种具有特定几何形状的导电的不带电荷的化合物用于有机半导体材料的掺杂,其中在所述掺杂剂被混合进有机半导体材料之后消除(elimination)氢自由基(hydrogen radical)、碳氧化物自由基(carbon oxide radical)、氮自由基、或羟基自由基,并且传输至少一个电子至所述半导体材料或从该材料传输至少一个电子。这些化合物的特征在于,所使用的掺杂剂是不带电荷的有机化合物。所提及的示例性化合物是经取代的或未经取代的碳环或杂环(homo-or heterocycle),其通过电子的释放或接收形成了芳香族的6-π体系(aromatic 6-πsystem)。这种方案的不利之处在于,对于从掺杂剂中消除氢来说,基体材料上的条件是非常严格的,并且使用在有机电子器件中常用的基体材料在极少数情况下才能满足上述条件。此外,例如所形成的氢自由基是极具反应性的,这会导致不可控的反应并最终损坏层或原件。
US 5,922,396 A描述了一种制造用于有机电子器件的多层结构的方法,所述多层结构包括n(电子)导电层(n(electron)-conductive layer)和p(电洞)导电层(p(hole)-conductive layer)。特别通过升华有机金属络合物来获得所述多层结构,该有机金属络合物在气相中形成自由基,并且之后以这种形式被沉积为电子传导层。
发明内容
因此,本发明所要解决的问题是提供适用于有机电子器件的有机层,其相比于现有技术具有改进的电学特性并且额外地可以以简单且价格低廉的方式来制造。
所述问题是通过权利要求1的特征来解决的。本发明优选的实施方式在从属权利要求中被反映。
相应地,在本发明的范围内,有机电子传导层(electron-conducting layer)具有用于增加所述有机层的n型导电性(n-conductivity)的至少一种掺杂剂,其特征在于,所述掺杂剂选自式1的环戊二烯化合物的盐类所组成的组:
其中取代基R1至R5各自独立地选自包括以下的组:-H、-D、卤素、-CN、-NO2、-OH、胺、醚、硫醚、烷基、环烷基、丙烯酰基(acryloyl)、乙烯基、烯丙基、芳烃(aromatic)、稠合芳烃(fused aromatic)和杂芳烃(heteroaromatic)。由于其化学性质,首先可将环戊二烯衍生物作为阴离子引入电子传导层,不受理论的束缚,通过以下机制释放电子至基体材料:
从而有助于增加层内的电荷载流子密度。本发明的环戊二烯阴离子,就像自由基(radical)那样,是共振稳定的(resonance-stabilized)并因而是化学稳定的。氧化还原反应自发进行并且不会产生任何不期望的副产物。在将本发明的掺杂剂掺入电子传输材料的情况下观察不到氢的消除,并且这也不是根据本发明的,因为氢自由基或其转化产物或由其重组而成的氢分子会损坏元件。本发明的取代模式(substitution pattern)相对于现有技术已知的电子传输材料产生了有利的掺杂剂HOMO/LUMO位置。
式1中的金属阳离子M+可选自包括碱金属、碱土金属、主族金属、过渡族金属、镧系金属和过渡金属的组。特别优选来自于上述在盐类化合物中形成稳定的带单价正电荷的阳离子的组的金属。所述阳离子的组与本发明的环戊二烯化合物配合产生可重复且易于蒸发(evaporable)的化合物,其形成了具有电子传输材料的均匀的层,这对于产生的层的可重现性和质量是有利的。
各个取代基R1至R5可独立地选自包括以下的组:-H、-D、卤素、-CN、-NO2、-OH、胺、醚、硫醚、烷基、环烷基、丙烯酰基、乙烯基、烯丙基、芳烃、稠合芳烃和杂芳烃。除非对于本领域技术人员来说是公知常识,否则所述取代基可被特别理解为以下内容:
卤素:Cl、F
烷基:直链或支链的C1至C5烷基
环烷基:C3-C8环烷基
稠合芳烃:C10-C40芳烃
杂芳烃:具有杂原子N、O的C3-C20芳烃
所述取代基R1至R5可在其基础结构中任意能够键结的位置处额外具有经取代的或未经取代的杂环。优选的是,所述取代基可选自经取代的和未经取代的杂环,例如,呋喃、噻吩、吡咯、噁唑、噻唑、咪唑、异噁唑、异噻唑、吡唑、吡啶、吡嗪、嘧啶、1,3,6-三嗪(1,3,6-triazine)、吡喃鎓、α-吡喃酮、γ-吡喃酮、苯并呋喃、苯并噻吩、吲哚、2H-异吲哚、苯并噻唑、2-苯并噻吩、1H-苯并咪唑、1H-苯并三唑、1,3-苯并噁唑、2-苯并呋喃、7H-嘌呤、喹啉、异喹啉、喹唑啉、喹喔啉、酞嗪、1,2,4-苯并三嗪(1,2,4-benzotriazine)、吡啶并[2,3-d]嘧啶(pyrido[2,3-d]pyrimidine)、吡啶并[3,2-d]嘧啶(pyrido[3,2-d]pyrimidine)、蝶啶、吖啶、吩嗪、苯并[g]蝶啶(benzo[g]pteridine)、9H-咔唑、和联吡啶,以及它们的衍生物。
现有技术已知的是,电子传输材料担负电子并进一步输送它们,优选的材料可选自:2,2′,2"-(1,3,5-苯三基)三(1-苯基-1H-苯并咪唑)、2-(4-联苯基)-5-(4-叔丁基苯基)-1,3-4-噁二唑、2,9-二甲基-4,7-二苯基-1,10-菲咯啉(BCP)、8-羟基喹啉锂(8-hydroxy-quinolinolatolithium)、4-(萘-1-基)-3,5-二苯基-4H-1-1,2,4-三唑、1,3-双[2-(2,2′-联吡啶-6-基)-1,3,4-噁二唑-5-基]苯、4,7-二苯基-1,10-菲咯啉(BPhen)、3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑、双(2-甲基-8-喹啉)-4-(苯基苯酚)铝(bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminum)、6,6′-双[5-(联苯-4-基)-1,3,4-噁二唑-2-基]-2,2′-联吡啶、2-苯基-9,10-二(萘吡啶-2-基)蒽、2,7-双[2-(2,2′-联吡啶-6-基)-1,3,4-噁二唑-5-基]-9,9-二甲基芴、1,3-双[2-(4-叔丁基苯基)-1,3,4-噁二唑-5-基]苯、2-(萘-2-基)-4,7-二苯基-1,10-菲咯啉、2,9-二(萘-2-基)-4,7-二苯基-1,10-菲咯啉、三(2,4,6-三甲基-3-(吡啶-3-基)苯基)硼烷(tris(2,4,6-trimethyl-3-(pyridin-3-yl)-phenyl)borane)、1-甲基2-(4-(萘-2-基)苯基)-1H-咪唑并[4,5-f][1,10]菲咯啉(1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)、苯基二芘基氧化膦(phenyl-dipyrenylphosphine oxide)、萘四甲酸二酐(naphthalenetetracarboxylic dianhydride)或其酰亚胺(imides)、苝四甲酸二酐(perylenetetracarboxylic dianhydride)或其酰亚胺、基于噻咯类的材料,其具有硅杂环戊二烯单元(silacyclopentadiene unit)或另外的杂环,如EP 2 092 041 B1所述。
在本发明的另一方面,有机电子传导层可包含掺杂剂,在这种情况下所述掺杂剂选自未经取代的或经取代的五芳基环戊二烯盐类(pentaarylcyclopentadiene salts)所组成的组。五芳基环戊二烯盐类是优选的,因为其在环戊二烯上的取代模式,特别优选的空间对称性使得化合物能被简单地升华。此外,五芳基环戊二烯阴离子和基体材料间的HOMO/LUMO比例使得能够产生高效的电子释放。不受理论的束缚,这可能是整个芳烃单位上的共振稳定作用(resonance stabilization)的结果。芳基组分可在其环状结构中的任意可被取代的位置处额外地担负(bear)如上所列出的另外的取代基。
在本发明的另一方面中,有机电子传导层可包含选自碱金属的组的金属阳离子M+,所述碱金属的组包括锂、钠、钾、铷和铯。这样的选择是特别有利的,因为碱金属在基体材料中的溶解性比其它金属的溶解性更好。结合本发明的阴离子,这在所述层内产生了特别均匀(homogeneous)的分布,并由此产生了整体均匀的层结构。
在一项实施方式中,有机电子传导层可包含选自包括铷和铯的重碱金属组的金属阳离子M+。这样的选择是特别有利的,因为特别的是,重碱金属在基体材料中的溶解性比其它碱金属的溶解性和轻碱金属的溶解性更好。此外,碱金属的重量级代表可使得化合物因金属阳离子的尺寸而具有特别优异的可蒸发性(evaporability)。
在优选的实施方式中,存在于电子传导层中的掺杂剂可以是五丙烯基环戊二烯基铯或铷(cesium or rubidium pentaarylcyclopentadienide)。额外地,特别优选使用五丙烯基环戊二烯基铯。
在本发明的另一项实施方式中,掺杂剂的有机部分可以以大于或等于-1且小于或等于0的氧化价(oxidation number)存在于有机电子传导层中。已发现,令人惊奇的是,包含具有所述阴离子的氧化还原范围的掺杂剂的层寿命更长。基体材料中的有机化合物没有被进一步氧化。同样地,可以通过选择合适的配体来调整所述掺杂剂的光吸收特性,从而调整所述层的光吸收特性。
此外,可以通过溶剂法或升华的方法将所述有机电子传导层施加至元件。本发明的化合物易于蒸发而无需改变结构,并且通过升华法或溶剂法与基体材料一起形成非常均匀的层。这对于可重现的层厚度来说是极为有利的,并有助于延长组件的使用寿命。
此外,在优选的实施方式中,存在于所述有机电子传导层中的环戊二烯化合物的盐具有大于或等于175g/mol且小于或等于2000g/mol的分子量,并且具有大于或等于120℃且小于或等于600℃的升华温度。不受理论的束缚,这样的分子量范围使得取代基具有足够的尺寸,从而使化合物具有足够的共振稳定性。相对地,大于2000g/mol的分子量会是不利的,因为盐类化合物的升华温度会作为质量增加的函数不成比例地增加。在处理的过程中,额外发现,升华温度大于或等于120℃且小于或等于1200℃的化合物可以从气相中以特别均匀的方式被沉积。这意味着可获得特别均匀的层。可以由经验公式很容易地计算出化合物的分子量并且由现有技术中已知的方法来确定升华温度。
在另一项优选的实施方式中,所使用的掺杂剂可以是五氰基环戊二烯铯(cesiumpentacyanocyclopentadienide)。
在本发明的另一方面,所述掺杂剂可以以大于或等于0.01%且小于或等于50%的层厚浓度(layer thickness concentration)存在于有机电子传导层中。此外,更有选的是,所述掺杂剂可以以大于或等于1.0%且小于或等于10%的层厚浓度存在于有机电子传导层中。层厚浓度描述了盐类衍生物的体积在整个电子传导层中所占的比例。例如,可使用层中阳离子的分布计算所述比例,可例如通过能量色散X射线结构分析法(EDX)或AAS(原子吸收光谱)来确定所述阳离子的分布。在所述掺杂剂形成电荷转移络合物(chargetransfer complexes)的情况下,可通过测量UV吸收来确定层厚浓度。
通过添加盐类掺杂剂可改善电子传导层的特性。掺杂剂能够释放电子至所述层,并由此促进了层的导电性的提高。已发现,令人惊讶的是,掺杂剂层厚浓度高于或低于上述特定范围会导致导电性变差。不受理论的束缚,较低的掺杂剂浓度导致电子注入导电层不充分,而较高的掺杂剂浓度会导致该层内电子传输组分的不足。两种情况下,电子传导层的导电性均不足以用于高效的有机元件。
在另一项实施方式中,所述掺杂剂可包含反应性取代基,其通过施用后的交联反应在电子传导层中的各个掺杂剂间形成共价键。在各个掺杂剂之间额外引入的共价键可促进电子传导层的机械稳定性。通过交联可增加所述层的机械和热稳定性,并由此可延长元件的使用寿命。各个掺杂剂的交联可通过外部触发来诱导,例如UV光,或例如通过热辐射。在溶剂法的情况下,例如可通过除去溶剂或化学反应引发剂来触发交联。
此外,在所使用的制造有机电子传导层的方法中,通过使用盐型环戊二烯化合物的溶剂法或升华的方法将所述有机电子传导层施加至元件。更优选地,通过气相沉积,更优选通过物理气相沉积(PVD)来制造电子传导区域。在该步骤中,掺杂剂可优选与电子传导层同时沉积。此处,可利用热能从不同的源中升华这两种物质。通过所述方法,获得了特别均质且均匀的层。可优选通过将电子传导层的组分和掺杂剂从溶剂沉积至基底的方式来进行溶剂法。这可以简化工艺体系并且使得生产更方便。
此外,可将制造有机电子传导层的方法应用在有机太阳能电池、有机晶体管、发光有机元件,有机发光二极管和/或有机发光电化学电池中。本发明的电子传导层的经改善的电学特性使得这些层特别适用于制备上述有机元件。
另外,可以通过所提供的方法来制造包含本发明的电子传导的有机层的有机电子元件。
附图说明
下文将使用附图对有机电子元件的结构加以详述。附图示出了:
图1示出了有机发光二极管(10)的结构的示意图。发光二极管由玻璃层(1)、氧化铟锡(ITO)层(2)、空穴注入层(3)、空穴传输层(HTL)(4)、发射层(EML)(5)、空穴阻挡层(HBL)(6)、电子传输层(ETL)(7)、电子注入层(8)和阴极层(9)形成;
图2示出了将光(21)转换成电流的具有PIN结构(20)的有机太阳能电池的结构的示意图。所述太阳能电池由氧化铟锡层(22)、p掺杂层(23)、吸收层(24)、n掺杂层(25)和金属层(26)组成;
图3示出了有机场效应晶体管(30)的可能的横截面的示意图。施加在基底(31)上的是栅电极(32)、栅极电介质(33)、源极和漏极接触(34+35)和有机半导体(36)。阴影区域表示接触掺杂是有利的地方。
具体实施方式
实施例:
I.五芳基环戊二烯的合成
五芳基环戊二烯的合成基本上可通过根据以下反应流程的两个不同的合成路径来进行:
第一反应路径I通过四芳基环戊二烯酮(tetraarylcyclopentadienone)作为起始物质来实现,而第二反应路径II则通过2,3,4,5-四芳基环戊-2-酮(2,3,4,5-tetraarylcyclopenten-2-one)作为起始物质来实现。
I.由四芳基环戊二烯酮出发的合成路径
由四芳基环戊二烯酮出发的五芳基环戊二烯的合成以Ziegler和Schnell(Ziegler et al.,Liebigs Ann.Chem.445(1925),266)等人的研究为基础并且在必要的过程步骤中被修改。
Ia)1,2,3,4,5-五苯基环戊-1,3-二烯-5-醇(1,2,3,4,5-
Pentaphenylcyclopenta-1,3-dien-5-ol)
在格氏反应(Grignard reaction)中,由四芳基环戊二烯酮和过量的芳基溴化镁(arylmagnesium bromide)出发,获得1,2,3,4,5-五芳基环戊-1,3-二烯-5-醇(1,2,3,4,5-pentaarylcyclopenta-1,3-dien-5-ol),在进一步的步骤中,并非如在Ziegler中所述的那样通过将溴化氢流引入醇在冰醋酸中的溶液来获得1,2,3,4,5-五芳基环戊-1,3-二烯-5-醇,而是通过醇与乙酰溴(acetyl bromide)在甲苯中反应来获得。该反应特别在使用叔醇,例如三苯基甲醇的情况下会很好地进行。
46.2g(0.12mol)四苯基环戊二烯酮与0.61mol苯基溴化镁在400ml乙醚中反应,得到1,2,3,4,5-五苯基环戊-1,3-二烯-5-醇(产率50.8g(87%)、熔点:177-179℃、燃点:175-176℃、C35H26O的元素分析:发现:C 90.98%、H5.59%,计算值:C 90.88%、H 5.66%)。
Ib)5-溴-1,2,3,4,5-五苯基环戊-1,3-二烯(5-Bromo-1,2,3,4,5-pentaphenyl-
cyclopenta-1,3-diene)
在消除溴化氢的情况下五芳基环戊-1,3-二烯-5-醇反应生成1,2,3,4,5-五芳基环戊-1,3-二烯-1-乙酸酯。在溴化氢的存在下,该酯是不稳定的。通过消除乙酸,获得1,2,3,4,5-五芳基环戊二烯基阳离子,其通过接收溴离子而稳定化。使用过量的乙酰溴的反应体系,反应定量地进行。
50.8g(0.11mol)1,2,3,4,5-五苯基环戊-1,3-二烯-5-醇悬浮在200ml甲苯中。在20分钟的时间内,于室温下逐滴加入74g(0.6mol)乙酰溴,之后使反应混合物在回流的情况下沸腾2小时。反应快结束时,另外逐滴加入2ml甲醇。在减压的条件下蒸馏除去过量的乙酰溴和甲苯。在加入100ml石油醚之后,剩余的油状物结晶。橙色的沉淀物被抽滤出来,并使用石油醚清洗并且干燥(熔点:183-185℃)。可替代的是,通过从甲苯中重结晶来获得分析级纯度的橙色产物。(产率:52.7g(91%)、熔点:189-190℃、燃点:188-189℃;C35H25Br的元素分析:发现:C 80.2%、H 4.8%;经计算:C 80.00%、H 4.8%)。
Ic)1,2,3,4,5-五苯基环戊-1,3-二烯(1,2,3,4,5-Pentaphenylcyclopenta-1,3-
diene)
接着,在乙醚中使用氢化锂铝来还原5-溴-1,2,3,4,5-五芳基环戊-1,3-二烯,获得五芳基环戊二烯烃(pentaarylcyclopentadiene hydrocarbon)(根据Houben-Weyl 4/1dReduktion II[Reduction II],Methoden der organischen Chemie[Methods of OrganicChemistry](1981)第397页)。
在搅拌的情况下,于11.5g(0.3mol)Li[AlH4]在150ml乙醚中的悬浮液中分批加入52.6g(0.1mol)5-溴-1,2,3,4,5-五苯基环戊-1,3-二烯在300ml乙醚中的悬浮液。所得的浅黄灰色悬浮液在回流的条件下另外沸腾2小时以完成还原反应。在冷却至室温之后,首先使用冰-水,再使用稀盐酸使过量的Li[AlH4]水解。然后使用旋转蒸发器从反应混合物中蒸馏出所有易挥发的有机组分。对浅黄色的粗产物进行抽滤并用水反复洗涤。为了进一步纯化,使用甲苯进行共沸干燥(dried azeotropically)、过滤然后重结晶(产率37.3g(84%)、熔点:253-256℃(依据批次)、燃点:244-246;C35H26的元素分析:发现:C 94.8%、H 5.8%;经计算:C 94.13%,H 5.87%;1H NMR(200MHz,CDCl3,TMS[ppm]):δ7.25-6.92(多峰,25芳香H),5.07(1酸H);13C NMR(宽带解耦(broadband-decoupled),50MHz,CDCl3,TMS[ppm]):146.5,144.0,136.2,135.8,130.1,129.0,128.5,128.4,127.8,127.6,126.7,126.5,126.3,62.7(s,sp3-C);MS-EI光谱对应于文献光谱RMSD 5094-9).
II.由2,3,4,5-四芳基环戊烯-2-酮(2,3,4,5-tetraarylcyclo-penten-2-one)出发的合成路径
根据Dielthey等人(Dielthey,W.,Quint,F.,J.Prakt.Chem.2(1930),139),由安息香(benzoin)和1,3-二苯基丙酮(二苄基酮)出发,获得2,3,4,5-四芳基环戊烯-2-酮作为缩合产物。2,3,4,5-四芳基环戊烯-2-酮与过量的芳基锂反应生成1,2,3,4,5-五芳基环戊-2,4-二烯-1-醇,其随后根据Rio等人(Rio,G.Sanz,Bull.Soc.Chim.France 12(1966)3375)通过消除水被转化,得到非常纯的五芳基环戊二烯。
IIa.1,2,3,4,5-五苯基环戊-1,3-二烯(1,2,3,4,5-Pentaphenylcyclopenta-1,
3-diene)
2,3,4,5-四苯基环戊烯-2-酮与过量的苯基锂反应生成1,2,3,4,5-五苯基环戊-2,4-二烯-1-醇。然后通过消除水形成1,2,3,4,5-五苯基环戊-1,3-二烯。这种方法也提供了非常纯净的产物。
通过Rio和Sanz的文献方法,在300ml乙醚中由37.8g(0.098mol)2,3,4,5-四苯基环戊烯-2-酮和0.5mol苯基锂(由7g(1mol)Li和78.5g(0.5mol)溴苯形成)制备1,2,3,4,5-五苯基环戊-1,3-二烯,并且以与方法I类似的方式纯化。在转化的过程中,1,2,3,4,5-五苯基环戊-2,4-二烯-1-醇自动转化成1,2,3,4,5-五苯基环戊-1,3-二烯。产率为34.9g(80%),并且产物与通过方法I制备的C5HPh5相同。
III.使用铯盐的实施例来制备环戊二烯化合物的盐
反复用己烷洗涤约100mg的元素铯(Fluka公司)以除去任何粘附的油。在减压的条件下干燥1mmol环戊二烯化合物并将其溶解在约20-40ml THF中。向所述溶液添加经净化的铯。氢被析出。搅拌悬浮液(约2-4小时)直至出现颜色或不再观察到氢的析出。过滤所述溶液以除去过量的铯。通过除去溶剂并且随后进行急速干燥(sharp drying),获得无色的环戊二烯化合物的铯盐。
IV.层的制备
IV.1)对比材料的制备
通过热蒸发在ITO(氧化铟锡=铟掺杂的氧化锡)(indium tin oxide=indium-doped tin oxide)电极上沉积200nm厚的电子传导层BCP(2,9-二甲基l-4,7-二苯基-1,10-菲咯啉)(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)。所使用的反电极为150纳米厚的铝层。
IV.2)包含五苯基环戊二烯基铯(cesium pentaphenylcyclopentadienide)作为掺杂剂的有机导电层的制备
在三个其它的实验中,相对于BCP(2,9-二甲基l-4,7-二苯基-1,10-菲咯啉)的蒸发速率以2重量%、5重量%和10重量%的浓度通过掺杂将五苯基环戊二烯基铯引入导电层。
在物理表征的过程中,对于经掺杂的有机元件的电流-电压特性来说,所得的结果是,经掺杂的层的电流密度远高于相同电压条件下的对比基底的电流密度。在掺杂度足够小的情况下,这种效果几乎与掺杂强度成比例。由此获得的结论是,增加的电流密度导致电荷载流子密度和/或迁移率的增加。
IV.3包含五(对甲苯基)环戊二烯基铷作为掺杂剂的有机导电层的制备
在另外三个实验中,相对于BCP的蒸发速率以2重量%、5重量%和10重量%的浓度通过掺杂引入五(对甲苯基)环戊二烯基铷。
在物理表征的过程中,对于经掺杂的有机元件的电流-电压特性来说,所得的结果是,经掺杂的层的电流密度远高于相同电压条件下的对比基底的电流密度。在掺杂度足够小的情况下,这种效果几乎与掺杂强度成比例。由此获得的结论是,增加的电流密度导致电荷载流子密度和/或迁移率的增加。
尽管通过优选的实施方式已对本发明进行了详述和说明,但是本发明不受所公开的实施例的限制,并且本领域技术人员在不离开本发明的保护范围的情况下可作出由其衍生的其它变化。
Claims (11)
1.有机电子传导层,其具有用于增加该有机电子传导层的n型导电性的至少一种掺杂剂,其特征在于,所述掺杂剂选自根据式1的环戊二烯化合物的盐类所组成的组:
其中取代基R1至R5各自独立地选自包括以下的组:-H、-D、卤素、-CN、-NO2、-OH、胺、醚、硫醚、烷基、环烷基、丙烯酰基、乙烯基、烯丙基、芳烃、稠合芳烃和杂芳烃,
其中所述有机电子传导层包含选自碱金属的组的金属阳离子M+,所述碱金属的组包括锂、钠、钾、铷和铯。
2.根据权利要求1所述的有机电子传导层,其中所述掺杂剂选自未经取代的或经取代的五芳基环戊二烯盐所组成的组。
3.根据权利要求1或2所述的有机电子传导层,其中所述有机电子传导层包含选自包括铷和铯的重碱金属组的金属阳离子M+。
4.根据权利要求1或2所述的有机电子传导层,其中所述掺杂剂的有机部分以大于或等于-1且小于或等于0的氧化价存在于所述有机电子传导层中。
5.根据权利要求1或2所述的有机电子传导层,其中通过溶剂法或升华法将所述有机电子传导层施加在元件上。
6.根据权利要求1或2所述的有机电子传导层,其中所述环戊二烯化合物的盐具有大于或等于175g/mol且小于或等于2000g/mol的分子量,并且具有大于或等于120℃且小于或等于600℃的升华温度。
7.根据权利要求1或2所述的有机电子传导层,其中所述掺杂剂以大于或等于0.01%且小于或等于50%的层厚浓度存在于所述有机电子传导层中。
8.制造根据权利要求1~7中任一项所述的有机电子传导层的方法,其中通过使用盐类环戊二烯化合物的溶剂法或升华的方法将所述有机电子传导层施加至元件。
9.根据权利要求8所述的方法用于制造应用在有机太阳能电池、有机晶体管或发光有机元件中的有机电子传导层的用途。
10.根据权利要求9所述的用途,其中所述有机电子传导层用于有机发光二极管和/或有机发光电化学电池中。
11.有机电子元件,其包括所制造的根据权利要求1~7中任一项所述的有机电子传导层。
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DE102015200699A1 (de) * | 2015-01-19 | 2016-07-21 | Siemens Aktiengesellschaft | Aminophosphazen-Basen als n-Dotierstoffe in der organischen Elektronik |
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