CN106432091B - 二苯并咪唑稠合顺式二苯乙烯/芴螺旋体化合物及光电器件 - Google Patents

二苯并咪唑稠合顺式二苯乙烯/芴螺旋体化合物及光电器件 Download PDF

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CN106432091B
CN106432091B CN201610631678.9A CN201610631678A CN106432091B CN 106432091 B CN106432091 B CN 106432091B CN 201610631678 A CN201610631678 A CN 201610631678A CN 106432091 B CN106432091 B CN 106432091B
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CN106432091A (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

本发明提供一种二苯并咪唑稠合顺式二苯乙烯/芴螺旋体化合物及光电器件。该二苯并咪唑稠合顺式二苯乙烯/芴螺旋体化合物包括七元环结构段以及咪唑段。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；所述的咪唑段是连接所述的顺式二苯基乙烯段。所述化合物并具有介于154℃至194℃之间的玻璃转换温度、介于426℃至443℃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具有电洞阻挡功能的电子传输层的材料。

Description

二苯并咪唑稠合顺式二苯乙烯/芴螺旋体化合物及光电器件
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是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，通过这种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所示的常规的有机发光二极管的结构，该有机发光二极管1’是至少包括：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’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’]
[化学式2’]
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。
[化学式7’]
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二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，并具有氰基芳基(cyanoaryl)及氰基杂芳基(cyano-heteroaryl)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二苯并咪唑稠合(diphenylimidazole-fused)的顺式二苯乙烯/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。所述化合物包括氰基芳基(cyanoaryl)及氰基杂芳基(cyano-heteroaryl)的取代基，且为二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生化合物。所述化合物并具有介于154℃至194℃之间的玻璃转换温度、介于426℃至443℃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，包括七元环结构段以及咪唑段。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；所述的咪唑段是连接所述的顺式二苯基乙烯段。
依据上述目的，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以及咪唑段。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；所述的咪唑段是连接所述的顺式二苯基乙烯段。
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。
其中A是碳原子或硅原子，R1是氢原子、叔丁(tert-butyl)基团或萘基(naphthyl)团。
在一实施例中，所述的七元环结构段及/或所述的咪唑段具有至少一取代基，所述的取代基是独立的氢原子、卤素原子(halogen atom)、氰基团(cyano group)、取代或未取代的三氟甲基团(trifluoromethyl group)、取代或未取代的磷氧基团(phosphine oxidegroup)、取代或未取代的胺基团(amine group)、取代或未取代的芳香环基团(aromaticring group)、取代或未取代的杂环基团(heteroaromatic ring group)、取代或未取代的烷基团(alkyl group)或取代或未取代的烯基团(alkenyl group)。
在一实施例中，所述的化合物是应用于有机发光装置，作为电洞阻挡材料及/或电子传输材料。
在一实施例中，所述的化合物由以下通式I表示：
其中A是碳原子或硅原子，R2是各自独立的氢原子、能被一个或多个Y基取代的磷氧基团(phosphine oxide group)、胺基团(amine group)、芳香环基团(aromatic ringgroup)、杂环基团(heteroaromatic ring group)、烷基团(alkyl group)或烯基团(alkenyl group)。其中R4与R5是相同或不同的，R4与R5是独立的能被一个或多个Y基取代的芳香环基团、杂环基团、烷基团或烯基团。而每一个Y基是相同或不同的，Y基是氢原子、卤素原子、氰基团、能被一个或多个Y’基取代的三氟甲基团、磷氧基团、烷基团、烯基团、芳香环基团或杂环基团。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、芳香环基团、杂环基团、烷基团或烯基团。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：
其中R1是氢原子、叔丁基团或萘基团。
在一实施例中，在R2、R4、R5、Y或Y’基中的芳香环基团(fused aryl group)或杂环基团是多环芳香烃基团或多环异核芳香基团(fused heteroaryl group)。
在一实施例中，在R2、R4、R5、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)、吡啶(benzimidazolyl)或苯并咪唑(benzimidazole)基团。
在一实施例中，在R2、R4、R5、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R2、R4、R5、Y或Y’基中的烷基团或烯基团是独立的直链(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，R2是选自由通式II-1-1至通式II-1-57所组成的群组，其中n为1或2。
在一实施例中，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、电洞阻挡层及/或有机发光层。
根据上述目的，本发明亦提供一种合成方法，用以合成以化学式B所示的化合物，所述合成方法包括以下步骤：将化学式B-1所示的化合物与化学式B-2所示的化合物进行反应，以形成如化学式B所示的化合物。
承上所述，本发明的以二苯并咪唑稠合的(diphenylimidazole-fused)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。所述化合物具有氰基芳基(cyanoaryl)及氰基杂芳基(cyano-heteroaryl)的取代基，且为二苯并咪唑稠合的顺式二苯乙烯/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。所述化合物并具有介于154℃至194℃之间的玻璃转换温度、介于426℃至443℃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，以本发明的二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生化合物确实能够作为有机发光二极管中具电洞阻挡功能(hole-blocking type)的电子传输层(Electron Transport Layer，ETL)。此外，实验结果进一步证实，这些具有本发明的二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生化合物的有机发光二极管，其的外部量子效率(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，此二苯并咪唑稠合的顺式二苯乙烯/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为一种常规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，其中相同的组件将以相同的参照符号加以说明。
本发明提供一种以二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，具有氰基芳基及氰基杂芳基的取代基，且可用于作为有机发光二极管的材料。所述二苯并咪唑稠合的顺式二苯乙烯/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，具电洞阻挡特性。如前所述，所述二苯并咪唑稠合的顺式二苯乙烯/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 transportlayer)。
依据本发明的一较佳实施例，为一种化合物，包括七元环结构段以及咪唑段。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、电洞阻挡层及/或有机发光层。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；所述的咪唑段是连接所述的顺式二苯基乙烯段。此外，七元环结构段及/或所述的咪唑段可优选地具有至少一取代基，所述的取代基可以是独立的氢原子、卤素原子(halogen atom)、氰基团(cyano group)、取代或未取代的三氟甲基团(trifluoromethyl group)、取代或未取代的磷氧基团(phosphine oxide group)、取代或未取代的胺基团(amine group)、取代或未取代的芳香环基团(aromatic ring group)、取代或未取代的杂环基团(heteroaromaticring group)、取代或未取代的烷基团(alkyl group)或取代或未取代的烯基团(alkenylgroup)。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。
其中A是碳原子或硅原子，R1是氢原子、叔丁(tert-butyl)基团或萘基(naphthyl)团。
此外，在一较佳实施态样中，所述的化合物由以下通式I表示：
(通式I)其中A是碳原子或硅原子，R2是各自独立的氢原子、能被一个或多个Y基取代的磷氧基团(phosphine oxide group)、胺基团(amine group)、芳香环基团(aromaticring group)、杂环基团(heteroaromatic ring group)、烷基团(alkyl group)或烯基团(alkenyl group)。其中R4与R5是相同或不同的，R4与R5是独立的能被一个或多个Y基取代的芳香环基团、杂环基团、烷基团或烯基团。而每一个Y基是相同或不同的，Y基是氢原子、卤素原子、氰基团、能被一个或多个Y’基取代的三氟甲基团、磷氧基团、烷基团、烯基团、芳香环基团或杂环基团。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、芳香环基团、杂环基团、烷基团或烯基团。R3是独立的甲基团、苯基团、叔丁基团；或两个R3以单键连接而由以下通式I-2表示：
其中R1是氢原子、叔丁基团或萘基团。
此外，在一实施例中，在R2、R4、R5、Y或Y’基中的芳香环基团(fused aryl group)或杂环基团可以是多环芳香烃基团或多环异核芳香基团(fused heteroaryl group)。或者，在R2、R4、R5、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)、吡啶(benzimidazolyl)或苯并咪唑(benzimidazole)基团。进一步来说，在R2、R4、R5、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。
另外，在R2、R4、R5、Y或Y’基中的烷基团或烯基团则可以是独立的直链(straight-chain)的、支链的(branched)或环状的(branched)烷基团或烯基团。
详细而言，R2可以是通式II-1-1至通式II-1-57所示的取代基中任一个，其中n为1或2。
本发明的以二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的粗产物的制造步骤是如下所述：
(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11.13g，20mM二苯并咪唑稠合的3,7-双溴二卞环庚烯酮(diphenylimidazole-fused,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的无色晶体：
(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是如下列化学式1所示：
[化学式1]
化学式1所示的化合物的光谱测试结果如下：(R＝H):m.p.322.11℃(DSC)；M.W.:690.03；1H NMR(500MHz,CDCl3)8.31(d,J＝8.3,1H),7.82(d,J＝7.8,2H),7.51(dd,J＝8.4,1.9,1H),7.46(m,4H),7.34(m,8H),7.19(d,J＝2.0,1H),7.04(s,2H),6.93(dd,J＝8.4,2.0,1H),6.60(d,J＝8.4,1H)；13C NMR(125MHz,CDCl3)148.96,144.72,143.22,136.93,132.27,131.66,130.92,130.82,130.49,130.20,129.86,129.50,129.30,128.86,128.71,128.24,127.54,127.29,121.96,121.73,120.71,65.85；HR-MS calcd for C40H24Br2N2:690.0306,found:690.0309；Anal.Calcd for C40H24Br2N2:C,69.38,H,3.49,N,4.05found:C,68.97,H,3.62,N,3.97；TLC Rf 0.21(EtOAc/hexane,1/8)。
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)于上述化学式1所示的中间产物，以进一步获得本发明的二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的各种较佳实施例。其中，该新颖电子传输材料(即，二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生物)的较佳实施例的化学结构如下列化学式2、化学式3、化学式4及化学式5所示。
在上述的化学式2至化学式5之中，R为氢原子，n可为1或2。以化学式2所示的化合物(n＝1)为例示，其光谱测量结果如下：Tm 326℃(DSC))；Tg:194℃；M.W.:736.88；1H NMR(400MHz,CDCl3)δ8.55(d,J＝8.0Hz,1H),7.81(d,J＝7.4Hz,2H),7.63-7.49(m,10H),7.46-7.31(m,15H),7.24(d,J＝1.8Hz,2H),7.10(d,J＝6Hz,2H),7.05(d,J＝8.0Hz,1H),6.86(dd,J＝8.0Hz,J＝1.4Hz,1H)；TLC Rf 0.32(ethyl acetate/hexanes,3/1)；HRMS calcdfor C54H32N4:736.2627,found:736.2633。
以化学式4所示的化合物为例示，其光谱测量结果如下：Tm 338℃(DSC)；M.W.:690.81；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),7.63-7.49(m,10H),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),7.02(t,J＝4.8,2H)；TLC Rf0.30(ethyl acetate/hexanes,4/1)；HR-MS(ESI)Anal.Calcd for C48H30N6:600.2532,found:690.2535。
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(PLλmax)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二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，其玻璃转换温度介于154℃至194℃之间，且该热裂解温度介于426℃至443℃之间；这表示本发明较佳实施例所提供的二苯并咪唑稠合的顺式二苯乙烯/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(n＝1) T<sub>g</sub>(℃) T<sub>d</sub>(℃) λ<sub>max</sub>(nm) PLλ<sub>max</sub>(nm)
实施例1(CN BS CN) 194 435 365 430
实施例2(PyBSPy) 175 443 376 413
实施例3(PmBSPm) 154 426 365 427
实施例4(Pm’BSPm’) 176 430 383 425
吸收光谱峰值(λmax)以及光致发光光谱峰值(PLλmax)的测量方式及测量条件如下。吸收光谱(10M in CH2Cl2)以SP-8001光电二极管矩阵检测器(Diode Array spectrometer)进行测量，溶剂为光谱测量用等级(spectrophotometric grade)。发散光谱(Emissionspectra，10M)以FP-6500荧光光谱仪(luminescence spectrometer)测量。循环伏安法(Cyclic Voltammetry，CV)则是以CH1604A电化学分析仪(Ch Instruments CH1604Apotentiostat)进行测量，将底物(1.0mM)溶于含有0.1M四丁基高氯酸铵(Bu4N+ClO4 -)或四丁基磷酸氢铵(Bu4N+PF6 -)的无水除气后的溶剂中，作为支撑电极。以白金导线作为相对电极(counter electrode)，而以玻璃碳电极(glassy carbon electrode)作为工作电极，并以Ag/AgCl作为参考电极。
稳定态光物理测量(steady-state photophysical measurement)则以以下方式及条件进行。吸收光谱以HP-8453光电二极管矩阵检测器(Diode Array spectrometer)进行测量，溶剂为光谱测量用等级(spectrophotometric grade)的二氯甲烷。发散光谱(Emission spectra，10M)以Aminco-Bowman Series 2荧光光谱仪(luminescencespectrometer)测量。于二氯甲烷下测量的发散光谱(10M)，将其最大发散强度标准化至相同(最大值为1)。荧光量子产率(Fluorescence quantum yield，Φf，％)的测量则将于二氯甲烷下(in 10M)测量的发散荧光光谱面积积分，并与在相同条件下测量香豆素-1(Coumarin-1，Φf＝0.90，CH2Cl2)或香豆素-6(Coumarin-6，Φf＝0.78,EtOH)的数值进行比较。荧光量子产率以下公式(1)进行计算：
Φsample f＝(Asample/Astandard)×(astandard/asample)×(nsample/nstandard)2×Φstandard f 公式(1)
其中A代表待测物、香豆素-1或香豆素-6的荧光发散光谱面积。N为待测物、香豆素-1或香豆素-6的溶剂折射率。二氯甲烷的折射率n为1.42，乙醇的折射率n为1.36。
更进一步来说，利用循环伏安法(Cyclic Voltammetry，CV)可获得各实施例的二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物的氧化电位(oxidationpotential，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4的二苯并咪唑稠合的顺式二苯乙烯/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 orbitalenergy level，EHOMO)与最低未占有分子轨道能阶(lowest unoccupied molecularorbital energy level，ELUMO)。其中，所获得的实施例1至实施例4的EHOMO与ELUMO整理于下列表2的中。由表2可知，实施例1至实施例4的二苯并咪唑稠合的顺式二苯乙烯/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5.65eV与5.78eV之间，且最低未占有分子轨道能阶(ELUMO)介于2.56eV与2.67eV之间。这些化合物的氧化电位介于0.85V至0.95V之间，且这些化合物的还原电位介于-2.01V至-2.24V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(CN BS CN) 0.85 -2.24 3.03 5.65 2.66
实施例2(PyBSPy) 0.95 -2.15 3.12 5.73 2.61
实施例3(PmBSPm) 0.89 -2.01 3.13 5.69 2.56
实施例4(Pm’BSPm’) 0.93 -2.08 3.11 5.78 2.67
循环伏安法(Cyclic Voltammetry，CV)则以下列方法及条件进行。以CH1604A电化学分析仪(Ch Instruments CH1604A potentiostat)进行测量，将底物(1.0mM)溶于含有0.1M四丁基高氯酸铵(n-Bu4NClO4)的无水除气后的溶剂中，作为支撑电极。以白金导线作为相对电极(counter electrode)，而以玻璃碳电极(glassy carbon electrode)作为工作电极，并以Ag/AgCl作为参考电极。
示差扫描热量(differential scanning calorimetry，DSC)分析则以下列方法及条件进行。以SEIKO SSC 5200DSC Computer/Thermal Analyzer分析仪进行示差扫描热量分析。样品先加热(20C/min)至熔解，并以液态氮进行淬息(quench)。玻璃转换温度(Tg)则加热(10C/min)冷却后的样本的方式进行记录。
热重分析(thermogravimetric analysis，TGA)则以下列方法及条件进行。以SEIKO TG/DTA200instrument测量仪进行测量，熔点则以Hargo MP-2D instrument测量仪进行测量后记录。
为了证实上述呈现的二苯并咪唑稠合的顺式二苯乙烯/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(MaximumLuminance，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
于上述表3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)是作为电洞注入层(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)，其化学式如下化学式(V)所示。
[化学式2”]
[化学式(V)]
上述各组组件依以下方式及条件进行制造。所使用的材料均为商业上可购得或以前述各实施例的方式可制得，并使用前在高真空下进行梯度升华(gradientsublimation)。基板为氧化铟锡玻璃(indium tin oxide(ITO)coated glass)，片电阻值为约30欧姆/单位面积(Ω/□)。图案化后的氧化铟锡基板依序以于洗涤剂(detergentsolution)、二次蒸馏水(doubly distilled water)、以及乙醇中进行超音波震荡5分钟，接着以氮气吹干。氧化铟锡基板于加载真空腔前以氧电浆(oxygen plasma)处理5分钟。有机层则于腔室(ULVAC，TU-12RE)中以0.1-0.3nm/s的速率进行热沉积(depositedthermally)，压力为5×10-6Torr。以α-NPB为电洞传输层(hole transporting layer，HTL)，厚度为40纳米(nm)。发光材料层(light-emitting layer，LEL)厚度为40纳米(nm)。以Alq3、TPBI或前述各实施例的材料作为电子传输层(electron-transporting layer，ETL)及电洞阻挡层(hole-blocking layer，HBL)，厚度为40纳米。电子注入层为LiF，厚度为1nm。以150nm的铝作为阴极。各组的电流-电压-光强度(Current-voltage-light intensity，I-V-L)及光谱测量，则以PRECISE GAUGE EL-1003测量仪进行测量并记录。
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之中。
表4
组件组别 λ<sub>max</sub> nm) V<sub>on</sub>(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1 516 2.5 17.6 47.3/48.5 104,200
实验组2 516 2.3 17.7 44.5/52.7 117,075
实验组3 516 2.2 12.8 38.7/46.9 93,800
实验组4 516 2.1 19.4 42.2/50.5 120,106
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5 516 4.7 12.9 33.8/19.8 76,930
实验组6 516 4.7 13.6 36.2/20.1 54,900
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1-4)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1(CN BS CN)以及实验组3(PmBSPm)有更佳的效果，其外部量子效率(ηext)介于12.8-17.6％，电流效率(ηc)介于38.7-47.3cd/A，功率效率(ηp)介于46.9-48.5lm/w，而最大亮度(Lmax)介于93,800-104,200cd/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3及实验组4)，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6，PmBSPm)，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5及6的绿色磷光有机发光二极管的半衰寿命(LT50)分别为11,620以及12,630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二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物，是由顺式二苯乙烯是化合物(cis-Stilbene based compound)以及芴是化合物(fluorene based compound)所构成的顺式二苯乙烯/芴螺旋体衍生物，具有介于154℃至194℃之间的玻璃转换温度、介于426℃至443℃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，以本发明的二苯并咪唑稠合的顺式二苯乙烯/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 TransportLayer，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以及咪唑段。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；所述的咪唑段是连接所述的顺式二苯基乙烯段。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(organicphotodetector)、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)。
此外，本发明亦提供另一较佳实施例，为一种合成方法，用以合成以化学式B所示的化合物。所述合成方法包括以下步骤：将化学式B-1所示的化合物与化学式B-2所示的化合物进行反应，以形成如化学式B所示的化合物。
以下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二苯并咪唑稠合的顺式二苯乙烯/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多种特性。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二苯并咪唑稠合的顺式二苯乙烯/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：
合成式I
取100毫升双颈圆底瓶，内放搅拌子，上接回流管并开启回流装置，真空干燥后，充入氮气，分别加入化合物4e 1594毫克(3毫摩尔)与化合物2 815.1毫克(4.5毫摩尔)与乙酸铵(NH4OAc)3004.9毫克(39毫摩尔)于反应瓶中，并打入15毫升的乙酸(Acetic acid)，以磁石搅拌混合均匀，将反应瓶置入70℃油锅中，使其反应30小时后，以TLC确定无起始物存在，升上反应瓶待其回温，将回流管卸下且以正己烷拭去残余的硅油。使用二氯甲烷(3×20毫升)与水萃取，所得到的萃取液加入硫酸镁干燥，过滤，回旋浓缩将溶剂抽干，粗产物以管柱层析纯化(乙酸乙酯/正己烷，1/8)，所得产物再利用二氯甲烷与正己烷以再结晶方式进行纯化，可得到固体1655毫克的如化学式B所示的产物，产率为80％。
综上所述，本发明的以二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生的双极型化合物及包含所述化合物的光电器件。所述化合物具有氰基芳基(cyanoaryl)及氰基杂芳基(cyano-heteroaryl)的取代基，且为二苯并咪唑稠合的顺式二苯乙烯/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。所述化合物并具有介于154℃至194℃之间的玻璃转换温度、介于426℃至443℃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，以本发明的二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生化合物作为电子传输层(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，此二苯并咪唑稠合的顺式二苯乙烯/芴螺旋体衍生物亦可应用于有机发光二极管之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 (5)

1.一种化合物，其特征在于，所述化合物的化学结构由以下化学式2、化学式3、化学式4或化学式5表示：
其中R是氢原子，n是1或2。
2.一种光电器件，其特征在于，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。
3.根据权利要求2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。
4.一种合成方法，用以合成以化学式B所示的化合物，所述合成方法包括：
将化学式B-1所示的化合物与化学式B-2所示的化合物进行反应，以形成如化学式B所示的化合物；
5.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。
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