CN106967060B - 系列咔唑衍生物及应用 - Google Patents

系列咔唑衍生物及应用 Download PDF

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CN106967060B
CN106967060B CN201710193446.4A CN201710193446A CN106967060B CN 106967060 B CN106967060 B CN 106967060B CN 201710193446 A CN201710193446 A CN 201710193446A CN 106967060 B CN106967060 B CN 106967060B
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organic electroluminescent
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CN106967060A (zh
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曹建华
王士波
华瑞茂
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了一系列咔唑衍生物的制备方法与在有机发光二极管中的应用。该材料的结构如式I所示。利用该材料制备的有机电致发光器件可显著提高器件的功率效率和外量子效率，延长橙黄光或红光器件的寿命，并且材料合成以及提纯的方法简单适于大规模生产等特点，是作为有机电致发光器件发光材料的理想选择。该有机电致发光二极管材料作为载流子传输材料或者单独作为发光材料或者作为发光层中的主体材料的应用也在保护范围内。
Figure DDA0001256785880000011

Description

系列咔唑衍生物及应用
技术领域
本发明属于有机电致发光显示技术领域，涉及一系列荧光材料的制备方法与在有机电致发光二极管的应用，具体涉及一种系列咔唑衍生物及有机电致发光器件。
背景技术
有机电致发光(简称OLED)及相关的研究早在1963年pope等人首先发现了有机化合物单晶蒽的电致发光现象。1987年美国的柯达公司用蒸镀有机小分子的方法制成了一种非晶膜型器件，将驱动电压降到了20V以内。这类器件由于具有超轻薄、全固化、自发光、亮度高、视角宽、响应速度快、驱动电压低、功耗小、色彩鲜艳、对比度高、工艺过程简单、温度特性好、可实现柔软显示等优点，可广泛应用于平板显示器和面光源，因此得到了广泛地研究、开发和使用。
经过二十几年的发展，有机EL材料已经全面实现了红、蓝、绿色发光，应用领域也从小分子扩展到了高分子以及金属络合物等领域。最近几年有机电发光显示技术己趋于成熟，一些产品已进入市场，但在产业化时程中，仍有许多问题亟待解决，特别是用于制作器件的各种有机材料，其载流子注入、传输性能，材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决。尤其是发光器件在发光效率和使用寿命还达不到实用化要求，这大限制了OLED技术的发展。而利用三线态发光的金属配合物磷光材料具有高的发光效率，其绿光和红光材料已经达到使用要求，但是金属配合物特殊的电子结构特征，导致其蓝光材料无法达到使用要求。
介于荧光和磷光之间的热激活延迟荧光材料的出现，大大提高了荧光材料的发光效率，几乎达到磷光材料的发光效率，弥补了磷光蓝光材料的不足，同时避免了使用贵重的稀有金属，大大降低了材料成本。但是已经报道的热激活延迟荧光材料由于在固体状态下存在聚集荧光淬灭效应，只能采用掺杂的方式制备OLED器件。因此，开发出具有在固态下聚集诱导发光的热致激活延迟荧光材料是解决上述问题的一个途径。
发明内容
本发明的目的是提供一种高效的荧光材料与在有机电致发光二极管中的应用。
本发明提供的有机电致发光材料，其结构通式如式I所示，
Figure BDA0001256785860000021
其中：
R1、R4、R5、R8、R9、R11、R14、R15、R18分别独立地选自氢、C1-C10烷基、C2-C10烯基、C2-C10炔基、C1-C10烷氧基、C3-C10环烷烃基、C3-C10环烯烃基、取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫基、取代的或未取代的C6-C60芳膦基、取代的或未取代的C6-C60芳硅基、取代的或未取代的C6-C60芳硼基、取代的或未取代的C2-C60杂环芳基中的任意一种，所述取代的取代基选自氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C10烷基、C2-C10烯基、C2-C10炔基、C1-C10烷氧基、C3-C10环烷烃基、C3-C10环烯烃基中的一种或多种；
R2、R3、R6、R7、R12、R13、R16、R17分别独立地选自氢、取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳胺基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫基、取代的或未取代的C6-C60芳膦基、取代的或未取代的C6-C60芳硅基、取代的或未取代的C6-C60芳硼基、取代的或未取代的C2-C60杂环芳基中的任意一种，所述取代的取代基选自氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C10烷基、C2-C10烯基、C2-C10炔基、C1-C10烷氧基、C3-C10环烷烃基、C3-C10环烯烃基中的一种或多种；
R10表示环状结构。
所述取代的或未取代的C2-C60杂环芳基，其中包含N、O、S原子中的至少一种的环状结构；
具体的所述C2-C60的杂环芳基包含以下II-1～II-15的结构：
Figure BDA0001256785860000031
所述式II-1～II-15中，Z1、Z2、Z3独立的选自氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、C2-C60炔基、C1-C60烷氧基、C3-C60环烷烃基、C3-C60环烯烃基、C6-C60芳基、至少含有一个-F、-CN或C1-C10烷基的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫醚基、取代的或未取代的C2-C60杂环芳基中的任意一种；
x1为1～4的整数；x2为1～3的整数；x3为1～2的整数；x4为1～6的整数；x5为1～5的整数；
T1为氧或硫原子；
具体的，所述式I所示化合物为如下表结构式中的任意一种，但不限于以下所列结构：
Figure BDA0001256785860000041
Figure BDA0001256785860000051
Figure BDA0001256785860000061
Figure BDA0001256785860000071
Figure BDA0001256785860000081
本发明还提供一种式I材料的电致发光OLED器件；
具体的，所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极层组成；
其中，构成所述透明基片的材料为玻璃或柔性基片；
构成所述阳极层的材料为无机材料或有机导电聚合物；其中，所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜；所述有机导电聚合物选自聚噻吩、聚乙烯基苯磺酸钠和聚苯胺中的至少一种；
构成所述空穴注入层的材料含有以下化合物中的一种或多种，但不限于以下化合物：
Figure BDA0001256785860000082
构成所述空穴传输层的材料含有以下化合物中的一种或多种，但不限于以下化合物：
Figure BDA0001256785860000083
构成所述有机发光层的材料包括本发明的化合物式(I)和/或以下化合物中的一种或多种，但不限于以下化合物：
Figure BDA0001256785860000091
构成所述电子传输层的材料为金属的配合物，结构如下，但不限于以下材料：
Figure BDA0001256785860000092
构成所述阴极层的材料选自下述元素中的任意一种或任意两种组成的合金或下述元素的氟化物：锂、镁、银、钙、锶、铝、铟、铜、金和银。
其中，所述空穴注入层的厚度为30-50nm，具体为30nm；
所述空穴传输层的厚度为5-15nm，具体为10nm；
所述有机发光层的厚度为10-100nm，具体为40nm；
所述电子传输层的厚度为10-30nm，具体为50nm；
所述阴极层的厚度为90-110nm，具体为60nm。
本发明提供的式I所示有机电致发光材料，具有较高的玻璃化温度、高的热稳定性和优良的成膜性能。其合成工艺简单，提纯的方法简单适于大规模生产等特点，并可通过连接不同的基团调节产物的能级、发光性能、热稳定性等，是作为有机电致发光器件发光层材料的理想选择。本发明使用上述材料的OLED器件，其色纯度高、稳定性好，从而使器件的发光效率和寿命都能达到实用化的要求。
具体实施方式
下面结合具体实施例对本发明的特征和技术内容作进一步阐述，但本发明并不限于以下实施例。请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明，并非用来对本发明加以限制。所述原材料如无特别说明均能从公开商业途径而得。
下述实施例对OLED材料及器件进行性能测试的测试仪器及方法如下：
OLED器件性能检测条件：
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；
电流密度和起亮电压：使用数字源表Keithley 2420测试；
功率效率：使用NEWPORT 1931-C测试。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案和其它有益效果显而易见。
附图中：
图1为本发明系列咔唑衍生物的制备方法流程图；
图2为本发明使用化合物式(1)制作的OLED器件结构示意图；
图3为本发明化合物式(A21)的紫外吸收光谱图；
图4为本发明化合物式(A21)的荧光光谱图；
图5为本发明化合物式(A30)的紫外吸收光谱图；
图6为本发明化合物式(A30)的荧光光谱图。
具体实施方式
以下通过具体的实施例对本发明作进一步的阐述，但本发明并不限于此特定例子。
实施例1、化合物A11的制备
第一步：中间体苯并噻二唑的制备
10.0g(92.5mmol)的邻苯二氨和300ml的二氯甲烷混合，加入37.4g(370mmol)的三乙胺，搅拌溶解，缓慢滴加入13.6ml(184.9mmol)的氯化亚砜，升温回流反应5小时，冷却到室温，减压浓缩干，加入700ml的水，滴加入浓盐酸调PH为酸性，过滤，滤饼再用乙醇重结晶，得11g黄色固体，收率88％。
第二步：中间体4,7-二溴苯并噻二唑的制备
将10g(73.4mmol)上步中间体和100ml的48％氢溴酸混合，室温下滴加入35g(22.3mmol)的溴素，升温回流反应6小时，冷却到室温，加入100ml的饱和亚硫酸氢钠水溶液，过滤，滤饼再用水洗，乙醇重结晶，得20.7g黄色固体，收率96％。
第三步：化合物A2的制备
将5g(17.0mmol)的4,7-二溴苯并噻二唑和2.8g(16.8mmol)的3-(N,N-二苯基)胺基咔唑混合，加入324mg(1.7mmol)的碘化亚铜和9.4g(68mmol)的碳酸钾，加入100ml的二甲苯，加入399mg(3.4mmol)的L-脯氨酸，搅拌升温回流反应12小时，冷却到室温，过滤，滤饼用甲苯洗，滤液减压浓缩干，加入100ml的无水乙醇加热至沸，趁热过滤，得8.4g黄色固体，收率62％。MS(MALDI-TOF)：m/z 801.273[M+1]+。1H-NMR(δ，CDCl3)：7.055～7.358(28H,m)，7.563～7.584(2H,m)，7.624～7.638(2H,m)，7.644～7.662(2H,m)，8.324～8.341(2H,m)。
第四步：中间体3,6-二(3-二苯胺基)咔唑)苯-1,2-二氨的制备
将5g(6.2mmol)的化合物A2和725mg(18.7mmol)的硼氢化钠混合，加入100ml的四氢呋喃和10ml水，搅拌升温回流反应12小时，冷却到室温，减压浓缩干，加入100ml水，过滤，得4.6g黄色固体，收率95％。
第五步：化合物A11的制备
将4g(5.1mmol)上述制备的二氨基中间体和750mg(5.1mmol)的40％乙二醛水溶液混合，加入50ml的四氢呋喃，搅拌升温至回流，加入0.1ml的浓盐酸，回流反应4小时，冷却到室温，减压浓缩干，加入50ml水，过滤，得2.8g黄色固体，收率68％。MS(MALDI-TOF)：m/z794.323[M]+。1H-NMR(δ，CDCl3)：7.054～7.353(28H,m)，7.561～7.582(2H,m)，7.623～7.637(2H,m)，7.643～7.661(2H,m)，8.322～8.339(2H,m)，8.852(2H,s)。
实施例2、化合物A21的制备
第一步：化合物A3的制备
合成操作参照实施例1的第三步，将实施例1第三步的3-(N,N-二苯基)胺基咔唑替换为3-咔唑基咔唑，得到黄色的固体，收率55％。MS(MALDI-TOF)：m/z 797.244[M+1]+。1H-NMR(δ，CDCl3)：7.153～7.448(16H,m)，7.562～7.585(4H,m)，7.664～7.692(6H,m)，7.847～7.865(2H,m)，8.124～8.146(4H,m)。
第二步：中间体3,6-二(9H-[3,9’-二咔唑]-9-基)苯-1,2-二氨
合成操作参照实施例1的第四步，将实施例1第四步的A2替换为A3，得到黄色的固体，收率95％。
第三步：化合物A21的制备
将5g(6.5mmol)上述制备的二氨基中间体和1.3g(6.2mmol)的菲醌混合，加入50ml的冰醋酸，搅拌升温回流反应6小时，冷却到60℃，过滤，滤饼用醋酸洗，水洗，乙醇洗，得5g黄色固体，收率81.7％。
MS(MALDI-TOF)：m/z 941.322[M+1]+。1H-NMR(δ，CDCl3)：7.155～7.252(12H,m)，7.465～7.626(14H,m)，7.846～7.869(4H,m)，7.882～7.905(4H,m)，8.123～8.145(4H,m)，9.121～9.133(2H,m)。
实施例3、化合物式A40的制备
第一步：中间体1-(4-(1-苯基-1H-苯并[d]咪唑-2-基)苯基)吲哚-2,3-二酮的制备
10g(0.068mol)的靛红和100ml的N,N-二甲基甲酰胺混合，加入18.8g(0.136mol)的碳酸钾和1.3g(6.8mmol)的碘化亚铜，再加入2g(17mmol)的L-脯氨酸、29.6g(0.075mol)的2-(4-碘苯基)-1-苯基-1H-苯并[d]咪唑，在氮气保护下，搅拌升温至150℃反应12小时，冷却到室温，过滤，将滤液倒入500ml的冰水中，过滤，滤饼用水洗，乙醇洗，得16g褐色固体，收率58％。
第二步：化合物A40的制备
将10.5g(24mmol)的3,6-二咔唑基-1,2-二氨基苯中间体和10g(24mmol)的上步中间体混合，加入150ml的醋酸，搅拌升温回流反应8小时，冷却到室温，过滤，滤饼用水洗，乙醇洗，得11g黄色固体，收率56％。MS(MALDI-TOF)：m/z 818.294[M+1]+。1H-NMR(δ，CDCl3)：7.253～7.528(21H,m)，7.535～7.641(8H,m)，7.816～7.824(2H,m)，8.246～8.259(3H,m)，8.646～7.655(1H,m)。
实施例4、化合物A52的制备
将10g(22.8mmol)的3,6-二咔唑基-1,2-二氨基苯中间体和2.3g(7.6mmol)的八水合环己六酮混合，加入200ml的冰醋酸，加入0.5g的对甲基苯磺酸，搅拌升温回流反应12小时，冷却到室温，过滤，滤饼用水洗，乙醇洗，得8.3g褐色固体，收率82％。MS(MALDI-TOF)：m/z 1374.460[M]+。1H-NMR(δ，DMSO-d6)：7.155～7.468(36H,m)，7.822～7.840(6H,m)，7.865～7.884(6H,m)，8.122～8.139(6H,m)。
实施例5、化合物A77的制备
第一步：中间体4,4’-二咔唑基苯偶酰的制备
4g(10.8mmol)的4,4’-二溴苯偶酰分散在80ml硝基苯中，加入4g(24mmol)的咔唑、419mg(2.2mmol)的碘化亚铜、4.5g(32mmol)的碳酸钾和1.1g的18-冠-6，在氮气保护下升温回流反应8小时，冷却到室温，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得4.6g黄色固体，收率78％。
第二步：化合物A72的制备
将3.5g(7.4mmol)的3,6-二咔唑基-1,2-二氨基苯中间体和4g(7.4mmol)的上步中间体混合，加入80ml的冰醋酸，搅拌升温回流反应12小时，冷却到室温，过滤，滤饼用水洗，乙醇洗，得6.4g黄色固体，收率92％。MS(MALDI-TOF)：m/z 943.352[M+1]+。1H-NMR(δ，CDCl3)：7.155～7.293(12H,m)，7.324～7.396(10H,m)，7.724～7.792(12H,m)，7.816～7.827(4H,m)，8.116～8.131(4H,m)。
第三步：化合物A77的制备
将6.0g(6.36mmol)的化合物A72溶解在600ml的无水二氯甲烷中，在氮气保护下，加入10.3g(63.6mmol)的无水三氯化铁，室温搅拌反应6小时，减压浓缩干，加入100ml的无水甲醇，升温至沸腾，趁热过滤，得到灰色的固体，再用硅胶柱分离纯化，得到3.3g黄色固体，收率55％。MS(MALDI-TOF)：m/z 941.343[M+1]+。1H-NMR(δ，CDCl3)：7.156～7.294(12H,m)，7.325～7.397(10H,m)，7.627～7.642(6H,m)，7.662～7.679(6H,m)，7.806～7.810(4H,m)，8.546(2H,s)。
实施例6、化合物A82的制备
第一步：中间体4-(4,7-二(9H-咔唑-9-基)-1H-苯并[d]咪唑-2-基)-N,N-二苯基胺的制备
将4.4g(10mmol)的3,6-二咔唑基-1,2-二氨基苯中间体和2.8g(10mmol)的4-二苯胺基苯甲醛混合，加入50ml的N,N-二甲基甲酰胺，搅拌升温至150℃反应8小时，冷却到室温，将反应液倒入冰水中，过滤，滤饼用水洗，乙醇洗，得6g黄色固体，收率88％
第二步：化合物A82的制备
将5g(7.2mmol)的上步中间体和1.77g(8.6mmol)碘代苯混合，加入80ml的N,N-二甲基甲酰胺，再加入138mg(0.72mmol)的碘化亚铜、344mg(8.6mmol)的氢氧化钠，搅拌升温回流反应2小时，冷却到室温，将反应液倒入冰水中，过滤，滤饼用水洗，乙醇洗，得4.8g黄色固体，收率87％。MS(MALDI-TOF)：m/z 768.312[M+1]+。1H-NMR(δ，CDCl3)：7.032～7.163(14H,m)，7.206～7.468(15H,m)，7.736～7.776(4H,m)，7.884～7.904(2H,m)，8.279～8.297(2H,m)。
实施例7、制备器件OLED-1～OLED-3
1)将溅射了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10-5～9×10-3Pa，在上述阳极层膜上蒸镀化合物HATCN作为空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
3)在上述空穴注入层上继续蒸镀NPB为空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为10nm；
4)在空穴传输层上继续蒸镀DPEPO为主体材料和本发明的化合物(式I)为掺杂材料，DPEPO:式I化合物＝90:10，作为器件的有机发光层，蒸镀速率为0.1nm/s，蒸镀所得有机发光层的膜厚为20nm；
5)在有机发光层上继续蒸镀一层Liq作为器件的电子传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
6)在电子传输层之上依次蒸镀镁/银合金层作为器件的阴极层，其中镁/银合金层的蒸镀速率为2.0～3.0nm/s，蒸镀膜厚为100nm，镁和银的质量比为1：9，得到本发明提供的OLED器件。
按照与上相同的步骤，将步骤4)中的化合物(式I)选为化合物A21，得到本发明提供的OLED-1；
按照与上相同的步骤，将步骤4)中的化合物(式I)选为化合物A82，得到本发明提供的OLED-2；
按照与上相同的步骤，将步骤4)中的化合物(式I)替换为DMAC-DPS，得到对比器件OLED-3；
Figure BDA0001256785860000151
所得器件OLED-1至OLED-3的性能检测结果如表1所示。
表1、OLED-1至OLED-3的性能检测结果
Figure BDA0001256785860000152
由上可知，本专利发明的有机材料制备成的器件起亮电压低，在亮度相同的条件下，器件的外量子效率明显比对比器件OLED-3中以DMAC-DPS作为掺杂材料的高，而且器件的寿命要长很多。
实施例8、制备器件OLED-4～OLED-6
1)将溅射了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10-5～9×10-3Pa，在上述阳极层膜上蒸镀化合物HATCN作为空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
3)在上述空穴注入层上继续蒸镀NPB为空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为10nm；
4)在空穴传输层上继续蒸镀本发明的化合物(式I)为主体材料，Ir(CHPIQ)2acac为掺杂材料，式I化合物:Ir(CHPIQ)2acac＝90:10，作为器件的有机发光层，蒸镀速率为0.1nm/s，蒸镀所得有机发光层的膜厚为20nm；
5)在有机发光层上继续蒸镀一层Liq作为器件的电子传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
6)在电子传输层之上依次蒸镀镁/银合金层作为器件的阴极层，其中镁/银合金层的蒸镀速率为2.0～3.0nm/s，蒸镀膜厚为100nm，镁和银的质量比为1：9，得到本发明提供的OLED器件。
按照与上相同的步骤，将步骤4)中的化合物(式I)选为化合物A30，得到本发明提供的OLED-4；
按照与上相同的步骤，将步骤4)中的化合物(式I)选为化合物A57，得到本发明提供的OLED-5；
按照与上相同的步骤，将步骤4)中的化合物(式I)替换为PPQ-BCZ，得到对比器件OLED-6；
Figure BDA0001256785860000161
所得器件OLED-4至OLED-6的性能检测结果如表2所示。
表2、OLED-4至OLED-6的性能检测结果
Figure BDA0001256785860000162
由上可知，本专利发明的有机材料制备成的器件起亮电压低，在亮度相同的条件下，器件的外量子效率明显比对比器件OLED-6中以PPQ-BCZ作为主体材料的高，而且器件的寿命要长很多。
尽管结合优选实施例对本发明进行了说明，但本发明并不局限于上述实施例和附图，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。

Claims (9)

1.一种化合物，其选自以下的化合物组成的组：
Figure FDA0002505059180000011
Figure FDA0002505059180000021
Figure FDA0002505059180000031
2.权利要求1所述化合物在制备有机发光二极管材料中的应用。
3.权利要求1所述化合物作为发光层材料在制备有机电致发光器件中的应用。
4.含有权利要求1所述化合物作为发光层的有机电致发光器件。
5.根据权利要求4所述的有机电致发光器件，其特征在于：所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极层组成。
6.根据权利要求5所述的有机电致发光器件，其特征在于：构成所述透明基片的材料为玻璃或柔性基片；构成所述阳极层的材料为无机材料或有机导电聚合物；其中，所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜；所述有机导电聚合物选自聚噻吩、聚乙烯基苯磺酸钠和聚苯胺中的至少一种。
7.根据权利要求6所述的器件，其特征在于：所述空穴注入层含有以下化合物中的一种或多种：
Figure FDA0002505059180000041
所述空穴传输层含有以下化合物中的一种或多种：
Figure FDA0002505059180000042
构成所述有机发光层的材料还包含以下材料中的一种或多种：
Figure FDA0002505059180000043
Figure FDA0002505059180000051
构成所述电子传输层的材料为Liq、Gaq3、TPBI或Slichem-EL-068，结构如下：
Figure FDA0002505059180000052
构成所述阴极层的材料选自下述元素中的任意一种或任意两种组成的合金或下述元素的氟化物：锂、镁、银、钙、锶、铝、铟、铜、金和银。
8.根据权利要求6或7所述的器件，其特征在于：
其中，所述空穴注入层的厚度为30-50nm；
所述空穴传输层的厚度为5-15nm；
所述有机发光层的厚度为10-100nm；
所述电子传输层的厚度为10-50nm；
所述阴极层的厚度为90-110nm。
9.根据权利要求6或7所述的器件，其特征在于：
其中，所述空穴注入层的厚度为40nm；
所述空穴传输层的厚度为10nm；
所述有机发光层的厚度为20nm；
所述电子传输层的厚度为40nm；
所述阴极层的厚度为100nm。
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