CN106432096B - 以顺式二苯乙烯/芴螺旋体衍生的化合物及其光电器件 - Google Patents

以顺式二苯乙烯/芴螺旋体衍生的化合物及其光电器件 Download PDF

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CN106432096B
CN106432096B CN201610631279.2A CN201610631279A CN106432096B CN 106432096 B CN106432096 B CN 106432096B CN 201610631279 A CN201610631279 A CN 201610631279A CN 106432096 B CN106432096 B CN 106432096B
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CN106432096A (zh
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陈建添
陈济中
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Nichem Fine Technology Co Ltd
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Abstract

本发明提供一种以顺式二苯乙烯/芴螺旋体衍生的化合物及其光电器件。所述顺式二苯乙烯/芴螺旋体衍生的化合物包括七元环结构段，所述的七元环结构段是由具有四键的桥接原子段与顺式二苯基乙烯段相连接而成，而所述的顺式二苯基乙烯段具有至少一独立的取代或未取代的三嗪基团、取代或未取代的嘧啶基团或取代或未取代的苯基基团取代基。所述化合物并具有介于156℃至202℃之间的玻璃转换温度、介于419℃至509℃之间的热裂解温度、可逆电子传输特性、以及良好的电荷载子平衡传输特性。并且，实验结果亦证实，以本发明的顺式二苯乙烯/芴螺旋体衍生物确实可作为有机发光二极管中电子传输层的材料。

Description

以顺式二苯乙烯/芴螺旋体衍生的化合物及其光电器件
技术领域
本发明是关于载子传输材料的相关领域，尤指一种以顺式二苯乙烯/芴螺旋体衍生的双极型化合物；其中，此双极型化合物可作为具有电洞阻挡功能的一种新颖电子传输材料，亦可作为主体发光材料。
背景技术
1987年，柯达公司的C.W.Tang与S.A.VanSlyke发表关于有机发光二极管(OrganicLight Emitting Device，OLED)的技术，Tang与VanSlyke利用真空蒸镀的方式，分别将电洞传输材料与电子传输材料，例如Alq3，镀覆于ITO玻璃之上，其后再蒸镀一层金属电极，如此，即完成具有自发光性、高亮度、高速反应、重量轻、厚度薄、低耗电、广视角、可挠性、以及可全彩化的有机发光二极管(OLED)的制备。
目前常规的有机发光二极管，通常会在有机发光二极管的阳极与阴极之间进一步增设其它功效层，例如：电子传输层与电洞传输层，通过方式增加有机发光二极管的电流效率或功率效率。例如图1所示的现有的有机发光二极管的结构，该有机发光二极管1’至少包括：阴极11’、电子注入层13’、发光层14’、电洞传输层16’、以及阳极18’。
有机发光二极管是利用电子与电洞再结合所产生的激子扩散到发光层而发光。根据理论推测，由电荷的再结合而引起的单重激发态与三重激发态的比例为1：3。因此，以小分子荧光材料作为发光材料时，能用于发光的比率仅为全部25％的能量，其余的75％的能量则在三重激发态经由非发光机制而损失掉，故一般荧光材料的内部量子效率的极限为25％。
研究发现，部分的电洞传输层16’是同时具有局限电子的功能，例如具有如下化学式1’及化学式2’所示的电洞传输材料，其中，化学式1’所表示的电洞传输材料为Tris(4-carbazoyl-9-ylphenyl)amine，中文名称为4,4’,4”-三(咔唑-9-基)三苯胺，简称TCTA。而化学式2’则为N,N’-Di(1-naphthyl)-N,N’-diphenyl-(1,1’-biphenyl)-4,4’-diamine的结构式，中文名称为N,N’-(1-萘基)-N,N’-二苯基-4,4’-联苯二胺，简称NPB。
[化学式1’]
Figure GDA0001740373700000021
[化学式2’]
Figure GDA0001740373700000022
近年来，为了有效提升配合磷光发光二极管的效能，有机发光二极管的制造商与研究人员是同步致力于具有电洞阻挡特性的电子传输材料的开发。目前商业化的电子传输材料例如分别由化学式3’-化学式7’所示的TmPyPb、TPBi、3TPYMB、BmPyPb，以及DPyPA。其中，TmPyPb为英文全名为3,3'-[5'-[3-(3-Pyridinyl)phenyl][1,1'：3',1"-terphenyl]-3,3"-diyl]bispyridine的简称(中文全名：3,3'-[5'-[3-(3-吡啶基)苯基][1,1'：3',1"-三联苯]-3,3"-二基]二吡啶)。TPBi则为英文全名为1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene的简称，中文全名为1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯。3TPYMB则为英文全名为Tris(2,4,6-triMethyl-3-(pyridin-3-yl)phenyl)borane的简称，中文全名为三[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷。BmPyPb则为英文全名为1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene的简称，中文全名为1,3-双(3,5-二吡啶-3-基苯基)苯。而DPyPA则为英文全名为9,10-bis(3-(pyridin-3-yl)phenyl)anthracene的简称，中文全名为9,10-二(3-(3-吡啶基)苯基)蒽。
Figure GDA0001740373700000023
Figure GDA0001740373700000031
然而，即使目前已然发展出多种不同的具有电洞阻挡特性的电子传输材料，应用这些电子传输材料的磷光发光二极管仍无法展现出具有优势的发光效率与生命周期，显示现有的具有电洞阻挡特性的电子传输材料仍具有缺陷必须予以克服；有鉴于此，本案的发明人极力加以研究发明，终于研发完成本发明的一种以顺式二苯乙烯/芴螺旋体衍生的双极型化合物，并具有三嗪基团、嘧啶基团或苯基基团的取代基。此双极型化合物可作为具有电洞阻挡功能的一种新颖电子传输材料，亦可作为主体发光材料。
发明内容
有鉴于上述课题，本发明的目的为提供一种以顺式二苯乙烯/芴螺旋体衍生(spirally-configured cis-stilbene/fluorene derivatives)的双极型化合物及包含所述化合物的光电器件。所述化合物包括三嗪基团(triazine)、嘧啶基团(pyrimidine)或苯基基团(phenyl)的取代基，且为顺式二苯乙烯/芴螺旋体衍生化合物。所述化合物并具有介于156℃至202℃之间的玻璃转换温度、介于419℃至509℃之间的热裂解温度、可逆电子传输特性、以及良好的电荷载子平衡传输特性。并且，实验结果亦证实，以本发明的顺式二苯乙烯/芴螺旋体衍生物确实可作为有机发光二极管中电子传输层的材料。
为达上述目的，本发明提供一种化合物，包括七元环结构段。所述的七元环结构段是由具有四键的桥接原子段与顺式二苯基乙烯(cis-stilbene)段相连接而成。而所述的顺式二苯基乙烯段具有至少一独立的取代或未取代的三嗪基团、取代或未取代的嘧啶基团或取代或未取代的苯基基团取代基。
本发明亦提供一种光电器件，包括第一电极、中间层以及第二电极。所述的第一电极、所述的中间层和所述的第二电极依序设置在基板上。所述的中间层包括化合物，所述的化合物包括七元环结构段，七元环结构段是由具有四键的桥接原子段与顺式二苯基乙烯段相连接而成。所述的顺式二苯基乙烯段具有至少一取代基，所述的取代基是独立的取代或未取代的三嗪基团、取代或未取代的嘧啶或取代或未取代的苯基基团。
在一实施例中，所述的具有四键的桥接原子段是选自由通式I-1-1到通式I-1-4所组成的群组。
Figure GDA0001740373700000041
其中A是碳原子或硅原子，R1是氢原子、叔丁(tert-butyl)基团或萘(naphthyl)基团。
在一实施例中，所述的化合物是应用于有机发光装置，作为电洞阻挡材料、电子传输材料及/或发光材料。
在一实施例中，所述的化合物由以下通式I表示：
Figure GDA0001740373700000042
其中R2是独立的能被一个或多个Y基取代的三嗪基团、嘧啶基团或苯基基团。当R2是三嗪基团时，每一个Y基是相同或不同的，Y基是氢原子、氰基团(cyano)、三氟甲基团(trifluoromethyl)或能被一个或多个Y’基取代的烷基团(alkyl)、烯基团(alkenyl)、芳香环基团(aromatic ring)或杂环基团(heteroaromatic ring)。当R2是嘧啶基团时，每一个Y基是相同或不同的，Y基是氰基团、三氟甲基团或能被一个或多个Y’基取代的烷基团、烯基团、芳香环基团或杂环基团。当R2是苯基基团时，每一个Y基是相同或不同的，Y基是氢原子或能被一个或多个Y’基取代的三嗪基团。其中每一个Y’基是相同或不同的，Y’基是氢原子、氰基团、二苯胺基团(diphenylamine)、芳香环基团、杂环基团、烷基团或烯基团。其中R3是独立的甲基团、苯基团、叔丁基团或两个R3以单键连接，由以下通式I-2表示：
Figure GDA0001740373700000051
其中R1是氢原子、叔丁基团或萘基团。
在一实施例中，在Y或Y’基中的芳香环基团或杂环基团是多环芳香烃基团(fusedaryl group)或多环异核芳香基团(fused heteroaryl group)。
在一实施例中，在Y或Y’基中的芳香环基团或杂环基团是苯基、1-萘基(1-naphthyl)、2-萘基(2-naphthyl)、噻吩(thiophenyl)、嘧啶(pyrimidinyl)、吡咯(pyrrolyl)、喹啉(quinolinyl)、三嗪(triazinyl)或吡啶(benzimidazolyl)基团。
在一实施例中，在Y或Y’基中的芳香环基团或杂环基团是咪唑(imidazolyl)、苯基(phenyl)、吡啶(pyridyl)、1H-吡咯并[2,3-B]吡啶(1H-pyrrolo[2,3-b]pyridine)或咔唑(carbazolyl)基团。
在一实施例中，在Y或Y’基中的烷基团或烯基团是直链(straight-chain)的、支链的(branched)或环状的(branched)烷基团或烯基团。
在一实施例中，当R2是独立的能被一个或多个Y基取代的三嗪基团时，R2是选自由通式II-1-1至通式II-1-19所组成的群组。
Figure GDA0001740373700000052
Figure GDA0001740373700000061
Figure GDA0001740373700000071
在一实施例中，当R2是独立的能被一个或多个Y基取代的嘧啶基团时，R2是选自由通式II-2-1至通式II-2-10所组成的群组。
Figure GDA0001740373700000081
在其中一实施例，当R2是独立的能被一个或多个Y基取代的苯基基团时，R2是选自由通式II-3-1至通式II-3-4所组成的群组。
Figure GDA0001740373700000082
在其中一实施例，所述的化合物的玻璃转换温度(Tg)的范围是介于156℃至202℃之间，热裂解温度(Td)的范围是介于419℃至509℃之间，氧化电位(oxidationpotentials)的范围是介于1.04V到1.16V之间，并且氧化还原电位(redox potentials)的范围是介于-1.75V到-1.93V之间。
在一实施例中，所述光电器件为有机发光二极管(OLED)，所述的中间层为电子传输层、电洞阻挡层及/或有机发光层。
承上所述，本发明的以顺式二苯乙烯/芴螺旋体衍生(spirally-configured cis-stilbene/fluorene derivatives)的双极型化合物及包含所述化合物的光电器件。所述化合物具有三嗪基团(triazine)、嘧啶基团(pyrimidine)或苯基基团(phenyl)的取代基，且为顺式二苯乙烯/芴螺旋体衍生化合物。并且，实验结果亦证实，以本发明的顺式二苯乙烯/芴螺旋体衍生物确实可作为有机发光二极管中具有电洞阻挡功能的电子传输层(hole-blocking type electron-transporters)的材料。并且，实验结果亦证实，以本发明的新颖电子传输材料作为电子传输层(Electron Transport Layer，ETL)的有机发光二极管，其外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、最大亮度(Lmax)、与组件寿命皆明显优于常规的有机发光二极管。此外，此顺式二苯乙烯/芴螺旋体衍生物亦可应用于有机发光二极管的中以作为主体发光材料。
附图说明
图1为一种现有的有机发光二极管的示意图。
图2为根据本发明的一较佳实施例的一种光电器件的示意图。
具体实施方式
以下将参照相关图式说明依据本发明较佳实施例的一种顺式二苯乙烯/芴螺旋体衍生的双极型化合物及有机发光装置，其中相同组件将以相同的参照符号加以说明。
本发明提供一种以顺式二苯乙烯/芴螺旋体衍生(spirally-configured cis-stilbene/fluorene derivatives)的双极型化合物，具有三嗪基团(triazine)、嘧啶基团(pyrimidine)或苯基基团(phenyl)的取代基，且可用于作为有机发光二极管的材料。所述顺式二苯乙烯/芴螺旋体衍生的双极型化合物是由顺式二苯乙烯系化合物(cis-Stilbenebased compound)以及芴系化合物(fluorene based compound)所构成的顺式二苯乙烯/芴螺旋体衍生物，具电洞阻挡特性。如前所述，所述顺式二苯乙烯/芴螺旋体衍生的双极型化合物主要可作为有机发光二极管(OLED)中的电子传输层(electron transport layer)、电洞阻挡层(hole blocking layer)及/或有机发光层(light emitting layer)，亦可作为太阳能电池中的载子传输层(carrier transport layer)。
依据本发明的一较佳实施例，为一种具有七元环结构段的化合物。如前所述，此化合物可作为有机发光二极管(OLED)中的电子传输层(electron transport layer)、电洞阻挡层(hole blocking layer)及/或有机发光层(light emitting layer)。所述的七元环结构段是由一具有四键的桥接原子段与一顺式二苯基乙烯段相连接而成。所述的顺式二苯基乙烯段具有至少一取代基，所述的取代基是独立的取代或未取代的三嗪基团、取代或未取代的嘧啶或取代或未取代的苯基基团。所述的具有四键的桥接原子段是选自由通式I-1-1到通式I-1-4所组成的群组。
Figure GDA0001740373700000101
其中A是碳原子或硅原子，R1是氢原子、叔丁(tert-butyl)基团或萘(naphthyl)基团。
此外，在一较佳实施方式中，所述的化合物由以下通式I表示：
Figure GDA0001740373700000102
其中R2是独立的能被一个或多个Y基取代的三嗪基团、嘧啶基团或苯基基团。当R2是三嗪基团时，每一个Y基是相同或不同的，Y基是氢原子、氰基团(cyano)、三氟甲基团(trifluoromethyl)或能被一个或多个Y’基取代的烷基团(alkyl)、烯基团(alkenyl)、芳香环基团(aromatic ring)或杂环基团(heteroaromatic ring)。当R2是嘧啶基团时，每一个Y基是相同或不同的，Y基是氰基团、三氟甲基团或能被一个或多个Y’基取代的烷基团、烯基团、芳香环基团或杂环基团。当R2是苯基基团时，每一个Y基是相同或不同的，Y基是氢原子或能被一个或多个Y’基取代的三嗪基团。其中每一个Y’基是相同或不同的，Y’基是氢原子、氰基团、二苯胺基团(diphenylamine)、芳香环基团、杂环基团、烷基团或烯基团。其中R3是独立的甲基团、苯基团、叔丁基团或两个R3以一单键连接，由以下通式I-2表示：
Figure GDA0001740373700000111
其中R1是氢原子、叔丁基团或萘基团。
此外，在一实施例中，在Y或Y’基中的芳香环基团或杂环基团可以是多环芳香烃基团(fused aryl group)或多环异核芳香基团(fused heteroaryl group)。举例而言，在Y或Y’基中的芳香环基团或杂环基团可以是苯基、1-萘基(1-naphthyl)、2-萘基(2-naphthyl)、噻吩(thiophenyl)、嘧啶(pyrimidinyl)、吡咯(pyrrolyl)、喹啉(quinolinyl)、三嗪(triazinyl)或吡啶(benzimidazolyl)基团。甚至，在Y或Y’基中的芳香环基团或杂环基团可以是咪唑(imidazolyl)、苯基(phenyl)、吡啶(pyridyl)、1H-吡咯并[2,3-B]吡啶(1H-pyrrolo[2,3-b]pyridine)或咔唑(carbazolyl)基团。
而在Y或Y’基中的烷基团或烯基团可以是直链(straight-chain)的、支链的(branched)或环状的(branched)烷基团或烯基团。
详细而言，当R2是独立的能被一个或多个Y基取代的三嗪基团时，R2是选自由通式II-1-1至通式II-1-19所组成的群组。
Figure GDA0001740373700000112
Figure GDA0001740373700000121
Figure GDA0001740373700000131
而当R2是独立的能被一个或多个Y基取代的嘧啶基团时，R2是选自由通式II-2-1至通式II-2-10所组成的群组。
Figure GDA0001740373700000132
Figure GDA0001740373700000141
而当R2是独立的能被一个或多个Y基取代的苯基基团时，R2是选自由通式II-3-1至通式II-3-4所组成的群组。
Figure GDA0001740373700000142
本发明的新颖电子传输材料的粗产物的制造步骤如下所述：
(1)以100mL的无水四氢呋喃(anhydrous tetrahydrofuran，THF)溶解5.2mL，30mM的2-溴联苯(2-bromobiphenyl)。
(2)将上述步骤(1)所得的产物静置于-78℃的环境中。
(3)将2.5M的四丁基锂(n-butyllithium)的己烷(hexane)溶液(30mM,12mL)逐滴加入上述步骤(2)所得的产物中，反应30分钟。
(4)以60mL的无水四氢呋喃溶解7.28g，20mM的3,7-双溴二卞环庚烯酮(3,7-dibromo-dibenzosuberenone)。
(5)将前述步骤(3)的产物逐滴加入前述步骤(4)所得的产物中。
(6)使用10mL的饱和碳酸氢钠(sodium bicarbonate)加入前述步骤(5)所得的产物进行淬息(quenching)反应，之后抽干四氢呋喃。
(7)使用二氯甲烷(dichloromethane)对前述步骤(6)所得的产物进行萃取，以得萃取液；
(8)将5g的硫酸镁(magnesium sulfate)加入该萃取液之中，接着依序干燥与过滤该萃取液。
以及，(9)将前述步骤(8)所得的产物进行回旋浓缩后，得到中间产物。
继续地，通过以下步骤可进一步获得该中间产物无色晶体：
(10)以60mL的醋酸(acetic acid)溶解该中间产物。
(11)将1mL，12N的浓盐酸(hydrochloric acid)加入前述步骤(10)所得的产物中。
(12)使用回流装置在120℃的环境中令前述步骤(11)所得的产物反应2小时。
(13)将前述步骤(12)所得的产物冷却至0℃。
(14)将60mL的正己烷(n-hexane)加入前述步骤(13)所得的产物中；
(15)使用抽滤漏斗过滤前述步骤(14)所得的产物，以获得过滤沉淀物。
(16)以正己烷清洗该过滤沉淀物3次，以获得固体物。
以及，(17)使用二氯甲烷/正己烷对该固体物进行再结晶，以获得无色晶体；其中，该无色晶体的化学结构如下列化学式1所示：
Figure GDA0001740373700000151
更进一步来说，通过上述步骤(10)至步骤(17)获得所述的无色晶体之后，便可通过施予各种反应法(例如，铃木偶联(Suzuki coupling)反应、布赫瓦尔德-哈特维希(Buchwald–Hartwig)反应，以及冯布劳恩(Rosemund-VonBarann)法)于该无色晶体，以进一步获得本发明的新颖电子传输材料的各种较佳实施例。其中，该新颖电子传输材料(即，顺式二苯乙烯/芴螺旋体衍生物)的较佳实施例的化学结构是如下列化学式II至化学式VI所示。
Figure GDA0001740373700000152
Figure GDA0001740373700000161
在上述的化学式II至化学式VII之中，R为氢原子或叔丁基(tert-butyl group)。X为氢原子或氰基(C—N group)。
更进一步地，前述化合物的其玻璃转换温度(Glass Transition Temperature，Tg)、分解温度(Decomposition Temperature，Td)、吸收光谱峰值(λmax)、以及光致发光光谱峰值(PL_λmax)整理于下列表1之中。由表1可知，本发明较佳实施例所提供的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，其玻璃转换温度是介于156℃至202℃之间，且该热裂解温度介于419℃至509℃之间；这表示本发明较佳实施例所提供的顺式二苯乙烯/芴螺旋体衍生的双极型化合物具有优良的热稳定性，并且在高电压与高电流的操作下不易裂解或产生结晶态。
表1
群组 T<sub>g</sub>(℃) T<sub>d</sub>(℃) λ<sub>max</sub>(nm) PLλ<sub>max</sub>(nm)
实施例1(CNN<sub>2</sub>SN<sub>2</sub>CN) 164 425 372 435,455
实施例2(ΦN<sub>2</sub>SN<sub>2</sub>Φ) 169 447 369 425,450
实施例3(CN’N<sub>2</sub>SN<sub>2</sub>CN’) 156 419 375 437,460
实施例4(Φ’N<sub>2</sub>SN<sub>2</sub>Φ’) 167 442 367 423,448
实施例5(N<sub>3</sub>SN<sub>3</sub>) 202 509 371 430,456
更进一步来说，利用循环伏安法(Cyclic Voltammetry，CV)可获得实施例1至实施例5的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的氧化电位(oxidation potential，E1/2 ox)与还原电位(redox potential，E1/2 red)。并且，由所测得的氧化电位与还原电位可进一步计算得到实施例1至实施例5的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的最高占有分子轨道能阶(high occupied molecular orbital energy level，EHOMO)与最低未占有分子轨道能阶(lowest unoccupied molecular orbital energy level，ELUMO)。其中，所获得的实施例1至实施例5的EHOMO与ELUMO整理于下列表2之中。由表2可知，实施例1至实施例5的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的最高占有分子轨道能阶(EHOMO)介于6.1eV与6.4eV之间，且最低未占有分子轨道能阶(ELUMO)介于3.2eV与3.4eV之间。这些化合物的氧化电位介于1.04V至1.16V之间，且这些化合物的还原电位是介于-1.75V至-1.93V之间。
表2
群组 E<sub>1/2</sub><sup>ox</sup>(V) E<sub>1/2</sub><sup>red</sup>(V) E<sub>g</sub>(eV) E<sub>HOMO</sub>(eV) E<sub>LUMO</sub>(eV)
实施例1(CNN<sub>2</sub>SN<sub>2</sub>CN) 1.15 -1.75 3.00 6.2 3.2
实施例2(ΦN<sub>2</sub>SN<sub>2</sub>Φ) 1.05 -1.91 2.99 6.2 3.2
实施例3(CN’N<sub>2</sub>SN<sub>2</sub>CN’) 1.16 -1.73 2.94 6.3 3.3
实施例4(Φ’N<sub>2</sub>SN<sub>2</sub>Φ’) 1.04 -1.93 2.99 6.1 3.2
实施例5(N<sub>3</sub>SN<sub>3</sub>) 1.08 -1.88 3.08 6.4 3.4
为了证实上述的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的确可用以作为有机发光二极管的电子传输层及/或电洞阻挡层，以下将设计多个实验组与对照组的有机发光二极管组件，并量测、比较这些有机发光二极管组件的驱动电压(Turn-on voltage，Von)、外部量子效率(External Quantum Efficiency，ηext)、电流效率(Current Efficiency，ηc)、功率效率(Power Efficiency，ηp)、最大亮度(Maximum Luminance，Lmax)。其中，所述的多个实验组与对照组的有机发光二极管组件整理于下列表3之中。
表3
Figure GDA0001740373700000171
Figure GDA0001740373700000181
于上述表3之中，1,4,5,8,9,11-六氮杂苯并菲-六氰基(1,4,5,8,9,11-Hexaazatriphenylene-hexacarbonitrile，HATCN)是作为HIL；4,4'-亚环己基二[N,N-二(4-甲基苯基)苯胺](4,4'-Cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine]，TAPC)是作为HT01。常规的电洞阻挡材料为、BmPyPb[英文全名：1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene；中文全名：1,3-双(3,5-二吡啶-3-基苯基)苯]、DPyPA[英文全名：9,10-bis(3-(pyridin-3-yl)phenyl)anthracene；中文全名：9,10-二(3-(3-吡啶基)苯基)蒽]、TPBi{英文全名：1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene；中文全名：1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯}、Alq3{英文全名：tris(8-hydroxyquinoline)aluminium(iii)；中文全名：三(8-羟基喹啉)铝}、以及ET01。其中，ET01的化学结构如下化学式2”所示；而绿色磷光材料化合物为掺杂有Ir(ppy)3的11-(4,6-二苯基-1,3,5-三嗪-2-基)-12-苯基-11,12-二氢吲哚并[2,3-a]咔唑(11-(4,6-diphenyl-1,3,5-triazin-2-yl)-12-phenyl-11,12-dihydroindolo[2,3-a]carbazole)，其化学式如下式(V)所示。
Figure GDA0001740373700000182
当然，于上述表3之中，Alq3、TPBi、BmPyPb、与ET01等材料也同时被应用作为有机发光二极的电子传输层。继续地，完成前述表3所列的有机发光二极管的量测之后，这些有机发光二极管组件的驱动电压(Von)、外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、最大亮度(Lmax)整理于下列表4的中。
表4
组件组别 λ<sub>max</sub>(nm) Von(V) η<sub>ext</sub>(％) η<sub>c</sub>/η<sub>p</sub>(％) L<sub>max</sub>(cd/m<sub>2</sub>)
实验组1a 516 2.3 14.4 52.5/65.7 143,500
实验组1b 516 2.2 13.3 51.2/45.5 92,835
实验组2a 516 2.1 13.5 52.0/61.5 139,800
实验组2b 516 2.3 13.0 47.4/63.6 96,120
实验组3a 516 2.3 14.0 50.4/37.2 122,000
对照组1A 516 2.5 6.3 22.8/18.0 142,100
对照组1B 516 3.0 10.2 37.8/24.0 40,700
对照组1C 516 3.0 6.9 24.7/22.0 37,640
实验组4 516 5.5 11.3 42.1/24.1 74,580
实验组5 516 4.8 11.9 39.5/24.7 41,200
对照组2 516 4.5 10.8 36.8/25.7 42,150
对照组3 516 5.5 7.84 27.6/15.8 17,700
由表4可以发现，相较于使用单一电洞传输层的对照组的有机发光二极管而言(即，对照组1A、1B、以及1C)，同样使用单一电洞传输层的实验组的有机发光二极管(即，实验组1a、1b、2a、2b，以及3a)显现出明显优良的外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、与最大亮度(Lmax)。特别是实验组1a(CNN2SN2CN)、实验组2b(CN’N2SN2CN’)以及实验组3a(N3SN3)有更佳的效果，其外部量子效率(ηext)介于13.5-14.4％，电流效率(ηc)介于50.4-52.5cd/A，功率效率(ηp)介于61.5-65.7lm/w，而最大亮度(Lmax)介于122,000-143,500cd/m2。
此外，相较于使用复合电洞传输层(双层)的对照组的有机发光二极管而言(即，对照组2与3)，使用单一电洞传输层的实验组的有机发光二极管(即，实验组1a至实验组3a)，同样显现出明显优良的外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、与最大亮度(Lmax)。更进一步地，使用复合电洞传输层的有机发光二极管(实验组4，CN’N2SN2CN’)，同样明显优于使用复合电洞传输层(双层)的对照组的有机发光二极管而言(即，对照组2与3)。
另外，实验亦同时进行绿色磷光有机发光二极管的寿命评估测试，其中，寿命评估测试的起始亮度为10,000cd/m2。寿命评估测试的结果显示实验组4及5的绿色磷光有机发光二极管的半衰寿命(LT50)分别为13,000及13,740小时。相对地，对照组1A与对照组3的绿色磷光有机发光二极管的半衰寿命(LT50)分别为1,000小时以及13,500小时。另外，若以TmPyPb取代对照组1A的绿色磷光有机发光二极管的中的BmPyPb，则对应的有机发光二极管的半衰寿命(LT50)也仅为210小时。
如此上述说明已经通过多组有机发光二极管的组件架构及其相关实验，验证了本发明的新颖电子传输材料的确可应用为发光二极管的电子传输材料；并且，经由上述可以得知本发明的新颖电子传输材料具有以下主要的优点：
(1)本发明的所提供的具电洞阻挡特性的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，是由顺式二苯乙烯系化合物(cis-Stilbene based compound)以及芴系化合物(fluorene based compound)所构成的顺式二苯乙烯/芴螺旋体衍生物，是具有介于156℃至202℃之间的玻璃转换温度、介于419℃至463℃之间的热裂解温度、可逆电子传输特性、以及绝佳的电荷载子平衡传输特性。
(2)并且，实验结果亦证实，以本发明的顺式二苯乙烯/芴螺旋体衍生的双极型化合物作为具有电洞阻挡功能的电子传输层(Electron Transport Layer，ETL)的有机发光二极管，其外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、最大亮度(Lmax)、与组件寿命皆明显优于常规的有机发光二极管。
此外，本发明亦提供另一较佳实施例，为一种光电器件。如图2所示，光电器件1包括第一电极11、中间层12以及第二电极13。第一电极11、中间层12和第二电极13依序设置在基板10上。中间层12包括一如前述较佳实施例所述的化合物。所述的化合物包括七元环结构段，七元环结构段是由具有四键的桥接原子段与顺式二苯基乙烯段相连接而成。所述的顺式二苯基乙烯段具有至少一取代基，所述的取代基是独立的取代或未取代的三嗪基团、取代或未取代的嘧啶或取代或未取代的苯基基团。所述化合物的其他特征，例如较佳的取代基及/或其电学特性，均与前述较佳实施例相同，在此不再重复说明。
此外，光电器件1可以是一有机发光二极管装置(OLED)，而中间层12可以是电子传输层、电洞阻挡层及/或有机发光层。更进一步地说，光电器件1可应用于有机发光装置、有机太阳能电池、有机薄膜晶体管(organic thin film transistor)、有机光传感器(organic photodetector)、平面显示器、计算机屏幕、电视、广告牌(billboard)、室内或室外照明用光源、室内或室外讯息用光源、抬头显示器(heads up display)、透明显示器、可挠性显示器、激光打印机、电话机、手机、平板计算机、膝上型计算机、数字相机、摄录像机(camcorder)、取景器(viewfinder)、微型显示器(micro-display)、移动载具(vehicle)、大型墙面广告牌(large area wall)、戏院或运动场用显示屏幕或是标示牌(sign)。
以下各实验例是用以举例说明本发明所提供的上述较佳实施例的顺式二苯乙烯/芴螺旋体衍生的双极型化合物及含有这些化合物的光电器件的诸项特性。而本发明所属技术领域的技术人员，当可由下述实验例更进一步明了上述的顺式二苯乙烯/芴螺旋体衍生的双极型化合物及含有这些化合物的光电器件的物理及化学特性。然此仅为举例说明之用，非用以限定本发明。
例1：中间产物B的合成方式
Figure GDA0001740373700000211
合成式I
如合成式I所示，5g纯度为99％的中间产物A(1当量，10毫摩尔(mmol))、5.587g双联频哪醇硼酸酯(bis(pinacolato)diboron，2.2当量，22毫摩尔(mmol))、5.899g乙酸钾(Potassium acetate，6当量，60毫摩尔(mmol))，以及146mg的[1,1'-双(二苯基膦)二茂铁]二氯化钯(II)(Pd(dppf)Cl2，0.02当量，0.2毫摩尔(mmol))溶解于200mL的1,4-二恶烷(1,4-dioxane)，并于-78℃下除去氧气。接着回温至室温，并且回流24小时。反应混合物用150mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(二氯甲烷：己烷，1：1)，过滤后进行回旋浓缩将溶剂抽干，并以100mL的甲醇清洗产物。以二氯甲烷/己烷溶液进行再结晶后，可得4.685g的中间产物B(产率79％)。光谱测试结果如下：Tm:207℃(DSC)；M.W.:594.35；1H NMR(400MHz,CDCl3)δ7.98(d,J＝7.8,2H),7.73(d,J＝7.6,2H),7.59(dd,J＝7.5,1.1,2H)7.39(s,2H),7.35(t,J＝7.6,2H),7.23(td,J＝7.6,1.2,2H),7.01(s,2H),1.19(s,24H)；13C NMR(100MHz,CDCl3)δ152.4,141.3,139.1,138.8,135.4,134.3,133.3,131.3,127.7,127.1,127.1,120.2,83.4,66.0,24.7；MS(EI,20eV)594.3(M+,68)；TLC Rf 0.35(acetone/hexanes,1/1)；HighResolution-MS calcd for C39H40B2O4:594.3113,found:594.3120。
例2A
Figure GDA0001740373700000221
合成式IIA
如合成式IIA所示，1.783g纯度为99％的中间产物B(1当量，3毫摩尔(mmol))、1.24g纯度为98％的2-溴嘧啶(2-bromopyrimidine，2.6当量，7.8毫摩尔(mmol))、1.658g乙酸钾(Potassium acetate，4当量，12毫摩尔(mmol))，以及146mg的四(三苯基膦)钯(Pd(PPh3)4，0.05当量，0.15毫摩尔(mmol))于氮气环境下溶解于110mL的乙二醇二甲醚(Dimethoxyethane，DME)及水溶液(DME：水，10：1)，并于-78℃下除去氧气。接着回流24小时。反应混合物用50mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(乙酸乙酯：二氯甲烷：己烷，1：15：15)，过滤后进行回旋浓缩将溶剂抽干，并以100mL的甲醇清洗产物。以二氯甲烷/正己烷溶液进行再结晶后，可得1.211g的化合物I。光谱测试结果如下：Tm:329℃,Tg:147℃,Td:383℃(DSC)；M.W.:498.58；1H NMR(400MHz,CDCl3)δ8.61(d,J＝4.8,4H),8.25(dd,J＝8.0,1.7,2H),8.17(d,J＝1.6,2H),8.07(d,J＝7.8,2H),7.77(d,J＝7.6,2H),7.50(d,J＝8.0,2H),7.41(td,J＝7.5,1.0,2H),7.31(td,J＝7.6,1.1,2H),7.11(s,2H),7.02(t,J＝4.8,2H)；13C NMR(100MHz,CDCl3)δ164.3,157.0,152.6,142.2,139.1,138.6,137.5,133.9,132.7,129.2,128.0,127.5,127.0,126.9,120.4,118.7,66.3；TLC Rf 0.27(EtOAc/dichloromethane/hexane,1/15/15)；HR-MS(ESI)Anal.Calcd for C35H22N4:499.1917,found:499.1926.；Anal.Calcd forC35H22N4:C,84.32；H,4.45；N,11.24.Found:C,83.961；H,4.28；N,11.206。
例2B
如合成式IIA所示，2.377g纯度为99％的中间产物B(1当量，4毫摩尔(mmol))、1.24g纯度为98％的2-溴5-氰基嘧啶(2-bromo-5-cyanopyrimidine，2.2当量，8.8毫摩尔(mmol))、2.211g碳酸钾(Potassium carbonate，4当量，16毫摩尔(mmol))，以及231mg的四(三苯基膦)钯(Pd(PPh3)4，0.1当量，0.2毫摩尔(mmol))于氮气环境下溶解于100mL的乙二醇二甲醚(Dimethoxyethane，DME)及水溶液(DME：水，10：1)除去氧气。接着回流24小时。反应混合物用150mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(乙酸乙酯：二氯甲烷：己烷，1：30：30)，过滤后进行回旋浓缩将溶剂抽干。以二氯甲烷/正己烷溶液进行再结晶后，可得1.570g的化合物II。光谱测试结果如下：Tm:312℃,Tg:171℃,Td:397℃(DSC)；M.W.:546.62；1H NMR(400MHz,CDCl3)δ8.78(d,J＝1.3,2H),8.02(d,J＝7.7,2H),7.98(dd,J＝8.0,1.7,2H),7.83–7.79(m,4H),7.60(d,J＝1.7,2H),7.52(d,J＝8.0,2H),7.45(td,J＝6.8,0.7,2H),7.33(dd,J＝8.0,1.0,2H),7.29(d,J＝8.6,2H),7.10(s,2H)；13C NMR(100MHz,CDCl3)δ159.5,152.3,142.3,139.6,139.0,138.3,137.1,133.9,133.3,128.5,128.1,127.7,126.8,126.3,120.7,119.4,116.9,107.6,66.2；TLC Rf 0.25(EtOAc/dichloromethane/hexane,1/30/30)；HR-MS(ESI)calcd for C39H23N4:547.1917,found:547.1922；Anal.Calcd for C39H22N4:C,85.69；H,4.06；N,10.25.Found:C,85.353；H,4.085；N,10.222。
例3A
Figure GDA0001740373700000231
合成式IIB
如合成式IIB所示，1.783g纯度为99％的中间产物B(1当量，3毫摩尔(mmol))、1.24g纯度为98％的2-苯-4-溴嘧啶(2-phenyl-4-bromopyrimidine，2.6当量，7.8毫摩尔(mmol))、1.658g碳酸钾(Potassium carbonate，4当量，12毫摩尔(mmol))，以及146mg的四(三苯基膦)钯(Pd(PPh3)4，0.05当量，0.15毫摩尔(mmol))于氮气环境下溶解于110mL的乙二醇二甲醚(Dimethoxyethane，DME)及水溶液(DME：水，10：1)，并于-78℃下除去氧气。接着回流24小时。反应混合物用50mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(乙酸乙酯：二氯甲烷：己烷，1：15：15)，过滤后进行回旋浓缩将溶剂抽干，并以100mL的甲醇清洗产物。以二氯甲烷/正己烷溶液进行再结晶后，可得1.978g的化合物V。光谱测试结果如下：Tm:349℃,Tg:166℃,Td:389℃(DSC)；M.W.:650.77；1H NMR(400MHz,CDCl3)δ8.69(s,4H),8.40(d,J＝3.6,2H),8.38(t,J＝2.4,2H),8.05(d,J＝8.0,2H),7.78(d,J＝7.6,2H),7.54(d,J＝8.0,2H),7.52(d,J＝1.6,2H),7.50–7.47(m,6H),7.44(td,J＝7.4,0.7,2H),7.34(td,J＝7.6,0.8,2H),7.08(s,2H)；13C NMR(100MHz,CDCl3)δ163.3,154.7,152.3,142.7,138.9,137.1,136.7,134.2,133.4,133.3,130.7,128.7,128.6,128.0,127.9,127.3,126.7,125.2,120.7,66.1；TLC Rf0.25(dichloromethane/hexane,1/1)；HR-MS(ESI)calcd for C47H30N4:651.2543,found:651.2556.；Anal.Calcd for C47H30N4:C,86.74；H,4.65；N,8.61.Found:C,86.643；H,4.749；N,8.572。
例3B
如合成式IIB所示，1.780g纯度为99％的中间产物B(1当量，3毫摩尔(mmol))、1.56g纯度为98％的2-(3-砒啶基)-4-溴嘧啶[2-(3-pyridyl)-4-bromopyrimidine，2.2当量，6.6毫摩尔(mmol))、1.660g碳酸钾(Potassium carbonate，4当量，12毫摩尔(mmol))，以及170mg的四(三苯基膦)钯(Pd(PPh3)4，0.05当量，0.15毫摩尔(mmol))于氮气环境下溶解于80mL的乙二醇二甲醚(Dimethoxyethane，DME)及水溶液(DME：水，10：1)，除去氧气。接着回流24小时。反应混合物用100mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(甲醇：二氯甲烷,1：30)，过滤后进行回旋浓缩将溶剂抽干。以二氯甲烷/正己烷溶液进行再结晶后，可得1.790g的化合物VI。光谱测试结果如下：Tm:332℃,Tg:171℃,Td:397℃(DSC)；M.W.:652.74；1H NMR(400MHz,CDCl3)δ9.60(s,2H),8.70(s,4H),8.64(dd,J＝7.9,1.7,2H),8.05(d,J＝7.7,2H),7.79(d,J＝7.6,2H),7.54(d,J＝7.8,2H),7.51(d,J＝7.9,2H),7.46(t,J＝7.3,2H),7.41–7.34(m,4H),7.25(s,2H),7.09(s,2H)；13C NMR(100MHz,CDCl3)δ161.5,154.8,152.2,151.4,149.7,142.8,139.0,136.9,135.2,133.9,133.5,133.4,132.7,131.5,128.8,127.9,127.4,126.6,125.4,123.4,66.1；TLC Rf 0.3(methanol/dichloromethane,1/30)；HR-MS(FD)Anal.Calcd for 652.2370,found:652.2351；Anal.Calcd for C45H28N6:C,82.80；H,4.32；N,12.87.Found:C,82.427；H,4.337；N,12.819。
例4
如合成式IIA所示，2.0809g的中间产物B(1当量，3.5毫摩尔(mmol))、2.0542g的2-氯-4,6-二苯基嘧啶(2-chloro-4,6-diphenylpyrimidine，2.2当量，7.7毫摩尔(mmol))、溶于17.5mL水中的4.832g乙酸钾(Potassium acetate，10当量，35毫摩尔(mmol))，以及150mg的[1,1'-双(二苯基膦)二茂铁]二氯化钯(II)(Pd(dppf)Cl2，0.05当量，0.18毫摩尔(mmol))于溶解于70mL的甲苯(Toluene)，接着加热至100℃，36小时。反应混合物用50mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(二氯甲烷：己烷，1：2)，可得1.2019g如化学式3所示的化合物。
Figure GDA0001740373700000251
化学式3
于化学式3中，Ar为苯基团(phenyl group)。光谱测试结果如下：Tm:398℃,Tg:195℃,Td:509℃(DSC)；M.W.:802；1H NMR(400MHz,CDCl3)δ8.61(d,J＝1.3Hz,2H),8.56(dd,J＝7.8,14,Hz,2H),8.18(d,J＝7.7Hz,2H),8.12(dd,J＝5.3,4.1Hz,1H),7.91(s,2H),7.86(d,J＝7.6Hz,2H),7.58-7.54(m,16H),7.86(t,J＝6.3Hz,2H),7.14(s,2H)；13C NMR(100MHz,CDCl3)164.1,163.2,153.4,142.0,139.3,138.5,137.8,137.2,133.8,132.7,130.7,129.6,128.7,127.7,127.6,127.2,127.0,120.5,109.4,66.6；TLC Rf 0.17(Chloroform/hexane,1/3)；High Resolution MS calcd for C59H38N4:802.3096,found:802.3070.。
例5
Figure GDA0001740373700000252
合成式III
如合成式III所示，3.006g的中间产物B(1当量，5毫摩尔(mmol))、4.009g的2-氯-4,6-二苯基-1,3,5-三嗪(2-chloro-4,6-diphenyl-1,3,5-triazine，3当量，15毫摩尔(mmol))、6.909g乙酸钾(Potassium acetate，10当量，50毫摩尔(mmol))，以及200mg的四(三苯基膦)钯(Pd(PPh3)4，0.03当量，0.17毫摩尔(mmol))溶解于100mL的甲苯(Toluene)。接着加热至100℃，48小时。反应混合物用50mL的二氯甲烷(dichloromethane)进行萃取三次，取有机层以硫酸镁干燥(MgSO4)。粗产物以管柱层析纯化(二氯甲烷：己烷，1：2)，可得2.012g如化学式5所示的化合物。
Figure GDA0001740373700000261
化学式5
于化学式5中，Ar为苯基团(phenyl group)。光谱测试结果如下：Tm:402℃,Tg:201℃,Td 497℃(DSC)；M.W.:804；1H NMR(400MHz,CDCl3)δ8.65(d,J＝1.6Hz,2H),8.58-8.55(m,5H),8.14(d,J＝8Hz,1H),7.89(d,J＝7.6Hz,1H),7.63-7.54(m,8H),7.42(dt,J＝7.6Hz,J＝0.8Hz,1H),7.16(s,1H)；13C NMR(100MHz,CDCl3)171.2,170.6,152.9,142.1,140.1,139.3,136.0,134.4,132.9,130.1,128.98,128.4,127,8,127.2,120.7,66.4；TLCRf 0.14(Chloroform/hexane,1/4)；MS(HR-FAB)805.6(FAB+,100)。
综上所述，本发明的以顺式二苯乙烯/芴螺旋体衍生(spirally-configured cis-stilbene/fluorene derivatives)的双极型化合物及包含所述化合物的光电器件。所述化合物具有三嗪基团(triazine)、嘧啶基团(pyrimidine)或苯基基团(phenyl)的取代基，且为顺式二苯乙烯/芴螺旋体衍生化合物。并且，实验结果亦证实，以本发明的顺式二苯乙烯/芴螺旋体衍生物确实可作为有机发光二极管中具有电洞阻挡功能的电子传输层(hole-blocking type electron-transporters)的材料。并且，实验结果亦证实，以本发明的新颖电子传输材料作为电子传输层(Electron Transport Layer，ETL)的有机发光二极管，其外部量子效率(ηext)、电流效率(ηc)、功率效率(ηp)、最大亮度(Lmax)、与组件寿命皆明显优于常规的有机发光二极管。此外，此顺式二苯乙烯/芴螺旋体衍生物亦可应用于有机发光二极管的中以作为主体发光材料。
以上所述仅为举例性，而非为限制性者。任何未脱离本发明的精神与范畴，而对其进行的等效修改或变更，均应包含于权利要求中。

Claims (4)

1.一种化合物，由以下通式I表示：
Figure FDF0000009887690000011
其中R2是三嗪基团或嘧啶基团；
其中当R2是三嗪基团时，R2是选自通式II-1-1：
Figure FDF0000009887690000012
其中当R2是嘧啶基团时，R2是选自由通式II-2-1至通式II-2-10所组成的群组：
Figure FDF0000009887690000013
及
其中R3是独立的甲基团、苯基团、叔丁基团或两个R3以单键连接，由以下通式I-2表示：
Figure FDF0000009887690000021
其中R1是氢原子、叔丁基团或萘基团；
其中，A是碳。
2.权利要求1所述的化合物应用于有机发光装置，作为电洞阻挡材料及/或电子传输材料的用途。
3.一种光电器件，其中，包括第一电极、中间层以及第二电极，所述的第一电极、所述的中间层和所述的第二电极依序设置在基板上，其中所述的中间层包括如权利要求1所述的化合物。
4.根据权利要求3所述的光电器件，其中，所述光电器件为有机发光二极管，所述的中间层为电子传输层及/或电洞阻挡层。
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10312459B2 (en) 2016-01-27 2019-06-04 Nichem Fine Technology Co., Ltd. Compound and organic electronic device using the same
TWI662013B (zh) 2016-03-24 2019-06-11 大陸商上海嶸彩光電材料有限公司 化合物及其有機電子裝置
US10454039B2 (en) * 2016-08-09 2019-10-22 Shanghai Nichem Fine Chemical Co., Ltd. Compound and organic electronic device using the same
WO2019165890A1 (en) * 2018-02-28 2019-09-06 The Hong Kong University Of Science And Technology Chiral aggregation-induced emission luminogens with delayed fluorescence for circularly polarized organic light-emitting diodes
CN112430239B (zh) * 2019-08-26 2022-03-22 广州华睿光电材料有限公司 基于七元环结构的化合物、高聚物、混合物、组合物及有机电子器件

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024149A (ja) * 2008-07-16 2010-02-04 Toyo Ink Mfg Co Ltd ７員環構造を有する化合物およびその用途
CN103833507A (zh) * 2013-12-25 2014-06-04 石家庄诚志永华显示材料有限公司 一系列有机电致发光材料及其制备方法与应用

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6229012B1 (en) * 1998-10-01 2001-05-08 Xerox Corporation Triazine compositions
KR100867494B1 (ko) * 2000-11-24 2008-11-06 도레이 가부시끼가이샤 발광 소자 재료 및 이를 이용한 발광 소자
US6686065B2 (en) 2001-12-12 2004-02-03 Canon Kabushiki Kaisha [5]-helicene and dibenzofluorene materials for use in organic light emitting devices
WO2004039786A1 (en) * 2002-10-30 2004-05-13 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
EP2251396B1 (de) * 2003-07-07 2014-11-19 Merck Patent GmbH Zur Emission befähigte organische Verbindungen und Elektronikbauteile diese enthaltend
KR101243919B1 (ko) 2006-01-27 2013-03-14 삼성디스플레이 주식회사 전도성 고분자 조성물 및 이를 채용한 유기 광전 소자
TWI549942B (zh) * 2010-08-26 2016-09-21 首威公司 Ｎ－苯基三咔唑類
KR101954980B1 (ko) 2011-11-03 2019-05-31 삼성디스플레이 주식회사 헤테로고리 화합물 및 이를 포함하는 유기 전계 발광 소자
CN103159745B (zh) * 2011-12-16 2016-01-20 昱镭光电科技股份有限公司 用于有机电激发光装置的化合物及有机电激发光装置
TWI485145B (zh) * 2012-10-26 2015-05-21 Ind Tech Res Inst Ｐ型有機半導體材料與光電元件
TWI466849B (zh) 2013-04-17 2015-01-01 Nat Univ Tsing Hua 用於有機發光二極體的光電材料及使用該光電材料的有機發光二極體元件
CN103468245B (zh) * 2013-08-16 2016-04-06 石家庄诚志永华显示材料有限公司 一种具有载流子传输能力的oled材料及其制备方法和应用
CN103936720B (zh) * 2013-12-12 2016-03-02 石家庄诚志永华显示材料有限公司 含有螺芴结构单元的化合物及其制备方法与应用
CN104387222B (zh) 2014-09-29 2017-02-15 山东大学 一类基于芴和萘的高稠环[6]螺烯化合物及其合成方法
TWI534141B (zh) * 2014-10-15 2016-05-21 彩豐精技股份有限公司 以順式二苯乙烯／芴螺旋體衍生的雙極型化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024149A (ja) * 2008-07-16 2010-02-04 Toyo Ink Mfg Co Ltd ７員環構造を有する化合物およびその用途
CN103833507A (zh) * 2013-12-25 2014-06-04 石家庄诚志永华显示材料有限公司 一系列有机电致发光材料及其制备方法与应用

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