CN108821934A - 一种化合物及包含该化合物的有机电致发光装置及其材料 - Google Patents

一种化合物及包含该化合物的有机电致发光装置及其材料 Download PDF

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CN108821934A
CN108821934A CN201810495483.5A CN201810495483A CN108821934A CN 108821934 A CN108821934 A CN 108821934A CN 201810495483 A CN201810495483 A CN 201810495483A CN 108821934 A CN108821934 A CN 108821934A
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CN108821934B (zh
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曹建华
王士波
张建川
董梁
隋岩
唐永顺
华瑞茂
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

本发明公开了一种有机电致发光装置及其材料的制备方法。该材料的结构如式I所示。该式I材料分子具有特殊的螺环结构，能有效阻断分子内的共轭，增加其能阶宽度，同时螺环结构具有较高的分子刚性，具有较高的玻璃化温度、高的热稳定性，使用本发明新颖结构的材料作为空穴层的有机电致发光装置，相较于使用现有技术的空穴层材料的有机电致发光装置具有更高的元件效率。

Description

一种化合物及包含该化合物的有机电致发光装置及其材料
技术领域
本发明属于有机电致发光显示和照明技术领域，涉及一种化合物及包含该化合物的有机电致发光装置及其材料以及制备方法。
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，因此得到了广泛的研究、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，采用传统的真空蒸镀法制备成照明或显示设备，一些产品已进入市场，但材料利用率低，良率低，造成生产成本居高不下。属于第三代技术的OLED溶液制程，是以印刷喷墨设备喷洒溶液状态的RGB发光材料成为像素，RGB三种像素可独立制造。跟传统真空蒸镀法相比，这可减少有机材料的浪费，投资印刷设备的费用也比真空蒸镀设备要低。与白光OLED相比，因为不需要彩色滤光片，可以压低面板生产成本，而使用微共振腔的向上发光结构，能产生高强度的亮度，也是受到瞩目的原因之一。
可喷墨打印等独特的优势被认为是下一代显示发展的方向。磷光发光材料可以同时利用单线态激子和三线态激子，为OLED效率的进一步提高提供了有效的途径。实验证明，采用磷光材料的OLED的外量子效率可以达到23.4％。而实现喷墨打印，需要采用可溶液制备的发光层。一般情况下，制作溶液制备的发光层时，需要将磷光材料掺杂进聚合物主体中，以提高薄膜的质量、抑制磷光三线态激子之间的猝灭以及提高发光层的载流子传输性能。但是大部分聚合物材料分子量分布不均，都是空穴传输材料，导致电子、空穴在发光层中的分布很不平衡，降低了发光效率。因此如何增多发光层中电子的数目，进而提高器件的效率，是一个很重要的问题。
发明内容
为了解决以上技术问题，本发明具体提供了一种式I所示化合物，
其中，
R1、R2、R3、R4各自独立地选自氢原子、氘氢原子、C1-C20烷基、C2-C20烯基、C2-C20炔基、C1-C20烷氧基、C3-C20环烷烃基、C3-C20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含氧芳基、取代的或未取代的C6-C60含硫芳基、取代的或未取代的C6-C60含膦芳基、取代的或未取代的 C6-C60含氮芳基、取代的或未取代的C6-C60含硅芳基、取代的或未取代的C6-C60含硼芳基、取代的或未取代的C2-C60杂环芳基中的任意一种；
X1至X12各自独立地选自碳或氮，且任意相邻两个所述X1至X12不能同时为氮。
所述取代的C6-C60芳基、取代的C6-C60含氧芳基、取代的C6-C60含硫芳基、取代的C6-C60含膦芳基、取代的C6-C60含硅芳基、取代的C6-C60含硼芳基、取代的C6-C60含氮芳基和取代的C2-C60杂环芳基中，取代基优选自氘氢、C1-C20烷基、C2-C20烯基、C2-C20炔基、C1-C20烷氧基、C3-C20环烷烃基和C3-C20环烯烃基中的任意一种或多种。所述C6-C60芳基优选自苯基、萘基、联苯基、蒽基、联蒽基、芘基、并四苯基、菲基、苯并菲基、苯并蒽基、苯并芘基、芴基、螺芴基中的任意一种；
所述C6-C60含氧芳基优选自二苯并[b,d]呋喃-2-基、二苯并[b,d]呋喃-4- 基、苯并呋喃-2-基、苯并呋喃-5-基、苯并呋喃-7-基、9,9-二甲基氧杂蒽-4-基、 9,9-二甲基氧杂蒽-2-基、螺[芴-9,9’-氧杂蒽]-2’-基、螺[芴-9,9’-氧杂蒽]-2-基中的任意一种；
所述C6-C60含硫芳基优选自二苯并[b,d]噻吩-2-基、二苯并[b,d]噻吩-4- 基、4-苯亚砜基苯基、4-苯砜基苯基、苯并噻吩-2-基、苯并噻吩-5-基、苯并噻吩-7-基、9,9-二甲基硫杂蒽-4-基、9,9-二甲基硫杂蒽-2-基、螺[芴-9,9’-硫杂蒽]-2’- 基、螺[芴-9,9’-硫杂蒽]-2-基中的任意一种；
所述C6-C60含膦芳基优选自4-(二苯基氧膦基)苯基、3-(二苯基氧膦基)苯基、二苯并[b]氧膦-5-(4-苯基)-4-基中的任意一种；
所述C6-C60含硅芳基优选自4-(三苯基硅基)苯基、4-(二苯基甲基硅基)苯基、 3-(三苯基硅基)苯基、3-(二苯基甲基硅基)苯基中的任意一种；
所述C6-C60含硼芳基优选自4-(二(2,4,6-三甲基)苯基)-硼烷苯基、二苯并 [b,d]硼烷-5-苯基-4-基、三苯基硼基中的任意一种；
所述C6-C60含氮芳基选自取代的或未取代的C2-C60杂环芳基、取代的或未取代的C6-C60芳基与氮原子组成的群组；
所述取代的或未取代的C2-C60杂环芳基优选为其中包含N、O、S原子中的至少一种的环状结构基团；
具体的，所述C2-C60的杂环芳基可以包含以下II-1～II-17的结构：
其中，Z1、Z2、Z3各自独立地选自氢、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、含有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选自BR’、NR’、PR’、O、S、Se、C＝O、S＝O、SO2、CR’R”、SiR’R”或GeR’R”；
其中R’、R”各自独立地选自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、含有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芳硫基、取代的或未取代的C2-C60杂环芳基中的任意一种或稠合或接合而形成的环。
具体的，所述式I所示化合物优选为以下ONA-1～ONA-99所示化合物：
本发明还公开了含有以上任一所述式I所示化合物的材料。
以上任一所述式I所示化合物可以应用于制备有机发光二极管材料，还可以作为空穴层或发光层材料应用于制备有机电致发光器件。
同时，本发明还提供了含以上任一所述式I所示化合物作为空穴层或发光层的有机电致发光器件。
本发明所提供的有机电致发光器件可以是使用可溶液喷涂制程的发光材料的电致发光OLED器件。
具体的，本发明所提供的有机电致发光器件由下至上依次包含透明基片、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。
其中，构成所述透明基片的材料可以为玻璃或柔性基片。
构成所述阳极层的材料优选为无机材料或有机导电聚合物，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一种或多种。
所述空穴注入层的材料优选为一种或多种以上所述式I所示化合物和/或一种或多种以下所示化合物组成的混合物：
构成所述空穴传输层的材料优选为包含一种或多种以上所述式I所示化合物；
构成所述有机发光层的材料包括主体材料和掺杂材料，其中主体材料包含以下所示化合物中的一种或多种，但不限于以下化合物：
构成所述有机发光层的掺杂材料包含一种或多种以上所述式I所示化合物或包含其它的红色、绿色、蓝色掺杂材料，
所述蓝色掺杂材料为以下所述化合物中的一种或多种，但不限于以下材料：
所述红色掺杂材料为以下所述化合物中的一种或多种，但不限于以下材料：
所述绿色掺杂材料为以下所述化合物中的一种或多种，但不限于以下材料：
所述电子传输层的材料优选包含以下所述化合物中的一种或多种：
构成所述阴极层的材料优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优选为30-50nm，进一步优选为50nm；
所述空穴传输层的厚度优选为10-50nm，进一步优选为40nm；
所述有机发光层的厚度优选为10-100nm，进一步优选为40nm；
所述电子传输层的厚度优选为10-30nm，进一步优选为50nm；
所述阴极层的厚度优选为90-110nm，进一步优选为100nm。
本发明提供的式I所示有机电致发光材料分子具有特殊的螺环结构，能有效阻断分子内的共轭，增加其能阶宽度，同时螺环结构具有较高的分子刚性，具有较高的玻璃化温度、高的热稳定性，使用本发明新颖结构的材料作为空穴层的有机电致发光装置，相较于使用现有技术的空穴层材料的有机电致发光装置具有更高的元件效率。应用于工业工艺时有较佳的热稳定性，还具有易制备与纯化等优点。是作为有机电致发光器件材料的理想选择。更甚者，此材料不仅可作为有机电致发光装置的空穴层材料，还可作为发光层的材料。
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
图1为使用本发明材料的OLED器件结构示意图。
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。
下述实施例中所用缩写定义如下：
THF 四氢呋喃
DMSO 二甲基亚砜
LDA 二异丙基胺基锂
Et3N 三乙胺
Pd2(dba)3 三(二亚苄基丙酮)二钯
Boc2O 二碳酸二叔丁酯
LiTMP 2,2,6,6-四甲基哌啶-1-锂
如图1所示的OLED器件，由下至上依次包含透明基片(1)、阳极(2)、空穴注入层(3)、空穴传输层(4)、有机发光层(5)、电子传输层(6)和阴极层(7)。
实施例1、化合物式ONA-1的制备
第一步：中间体Int.-1的制备
17g的2-氨基联苯用400ml的干燥甲苯溶解，在氮气保护下，加入30g的 2-溴-9,9-二甲基芴和22.5g的叔丁醇钾，再加入1.12g的醋酸钯以及0.1ml的10％三叔丁基磷甲苯溶液，加热回流搅拌反应4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22g的黄色固体，收率61％。
第二步：中间体Int.-2的制备
10g的1-苊烯硼酸SM-2和150ml甲苯混合，加入13g的2-溴碘苯、10.8g 的无水碳酸钠、26.5mg的钯催化剂Pd(PPh3)4，再加入30ml乙醇和30ml水，加热回流搅拌反应10小时，冷却到室温，用乙酸乙酯萃取，有机相干燥，过滤，滤液减压浓缩干，硅胶柱分离纯化，得到11.7g的中间体Int.-2，黄色的固体，产率83％。
第三步：中间体Int.-3的制备
10g的上步中间体Int.-2溶解于150ml干燥的四氢呋喃中，氮气保护下，置于低温槽中，用液氮降温至-78℃，缓慢滴加入14.3ml的2.5M正丁基锂-己烷溶液，控温在-70℃搅拌反应30分钟，8.4g的2-溴芴酮SM-3用25ml的干燥四氢呋喃溶解，在氮气保护下，缓慢滴入上述制备的溶液内，搅拌反应1小时，升到室温搅拌反应30分钟，加入100ml的饱和氯化铵水溶液淬灭反应，用乙酸乙酯萃取三次，有机相用无水Na2SO4干燥，过滤，滤液减压浓缩干，得18.0g 的黄色油状物。
得到的黄色油状物用120ml冰醋酸溶解，加入1ml的浓盐酸，加热回流搅拌反应2小时，冷却到室温，过滤，滤饼用乙醇洗，再用硅胶柱分离纯化，得到13.2g的Int.-3，白色固体，收率86.4％。
第四步：化合物ONA-1的制备
5g的上步中间体Int.-3和3.7g的中间体Int.-1混合，加入50ml的二甲苯，加入1.2g的叔丁醇钠和5mg的Pd2(dba)3，在氮气保护下加入0.02ml的10％三叔丁基磷己烷溶液，升温至110℃搅拌反应8小时，冷却到室温，加入50ml 水搅拌30分钟，分出上层有机相，水洗，干燥后减压浓缩干，用甲苯重结晶得到5.7g的产物ONA-1，黄色固体，产率74％。
实验数据：
(1)1HNMR(δ、CDCl3)：7.952～7.932(m,2H),7.829～7.685(m,6H), 7.533～7.512(m,2H),7.442～7.389(m,3H),7.358～7.127(m,15H),7.115～7.074(m, 3H),7.016～6.983(m,2H),1.416(s,6H)；
(2)ESI-MS：C58H39N，标准分子量749.3083，测试结果750.3072[M+H]；
实施例2、化合物式ONA-38的制备
第一步：中间体Int.-4的制备
8.5g的4-氨基联苯用200ml的干燥甲苯溶解，在氮气保护下，加入15.0g 的2-溴-9,9-二甲基芴和11.2g的叔丁醇钾，再加入0.56g的醋酸钯以及0.05ml 的10％三叔丁基磷甲苯溶液，加热回流搅拌反应4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14.7g的黄色固体，收率74％。
第二步：中间体Int.-5的制备
10g的中间体Int.-2溶解于150ml干燥的四氢呋喃中，氮气保护下，置于低温槽中，用液氮降温至-78℃，缓慢滴加入14.3ml的2.5M正丁基锂-己烷溶液，控温在-70℃搅拌反应30分钟，8.4g的4-溴芴酮SM-5用25ml的干燥四氢呋喃溶解，在氮气保护下，缓慢滴入上述制备的溶液内，搅拌反应1小时，升到室温搅拌反应30分钟，加入100ml的饱和氯化铵水溶液淬灭反应，用乙酸乙酯萃取三次，有机相用无水Na2SO4干燥，过滤，滤液减压浓缩干，得17.6g的黄色油状物。
得到的黄色油状物用120ml冰醋酸溶解，加入1ml的浓盐酸，加热回流搅拌反应4小时，冷却到室温，过滤，滤饼用乙醇洗，再用硅胶柱分离纯化，得到12.0g的Int.-5，白色固体，收率78％。
第三步：化合物ONA-38的制备
5g的上步中间体Int.-4和6.8g的中间体Int.-5混合，加入50ml的二甲苯，加入1.6g的叔丁醇钠和6mg的Pd2(dba)3，在氮气保护下加入0.02ml的10％三叔丁基磷己烷溶液，升温至110℃搅拌反应8小时，冷却到室温，加入50ml 水搅拌30分钟，分出上层有机相，水洗，干燥后减压浓缩干，用甲苯重结晶得到7.0g的产物ONA-38，黄色固体，产率68％。
实验数据：
(1)1HNMR(δ、CDCl3)：7.703～7.533(m,8H),7.511～7.445(m,2H), 7.416～7.324(m,10H),7.247～7.073(m,13H),1.414(s,6H)；
(2)ESI-MS：C58H39N，标准分子量749.3083，测试结果750.3073[M+H]；
实施例3、化合物式ONA-2～ONA-36的制备
参考实施例1的制备方法可制备化合物式ONA-2～ONA-36。
实施例4、化合物式ONA-37、ONA-39～ONA-58的制备
参考实施例2的制备方法可制备化合物式ONA-37、ONA-39～ONA-58。
实施例5、化合物式ONA-65的制备
第一步：中间体Int.-6的制备
10g的4-碘二苯并[b,d]呋喃用200ml的干燥甲苯溶解，在氮气保护下，加入6.3g的苯胺和4.9g的叔丁醇钠，再加入0.38g的醋酸钯以及0.02ml的10％三叔丁基磷甲苯溶液，加热回流搅拌反应2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7.7g的黄色固体，收率88％。
第二步：中间体Int.-7的制备
10g的中间体Int.-2溶解于150ml干燥的四氢呋喃中，氮气保护下，置于低温槽中，用液氮降温至-78℃，缓慢滴加入14.3ml的2.5M正丁基锂-己烷溶液，控温在-70℃搅拌反应30分钟，11.0g的2,7-二溴芴酮SM-7用50ml的干燥四氢呋喃溶解，在氮气保护下，缓慢滴入上述制备的溶液内，搅拌反应1小时，升到室温搅拌反应30分钟，加入100ml的饱和氯化铵水溶液淬灭反应，用乙酸乙酯萃取三次，有机相用无水Na2SO4干燥，过滤，滤液减压浓缩干，得24.2g 的黄色油状物。
得到的黄色油状物用120ml冰醋酸溶解，加入2ml的浓盐酸，加热回流搅拌反应4小时，冷却到室温，过滤，滤饼用乙醇洗，再用硅胶柱分离纯化，得到12.3g的Int.-5，白色固体，收率69％。
第三步：化合物ONA-65的制备
5g的上步中间体Int.-7和5.9g的中间体Int.-6混合，加入50ml的二甲苯，加入2.2g的叔丁醇钠和8.5mg的Pd2(dba)3，在氮气保护下加入0.03ml的10％三叔丁基磷己烷溶液，升温至110℃搅拌反应8小时，冷却到室温，加入50ml 水搅拌30分钟，分出上层有机相，水洗，干燥后减压浓缩干，用甲苯重结晶得到4.6g的产物ONA-65，黄色固体，产率56％。
实验数据：
(1)1HNMR(δ、CDCl3)：7.009～7.030(m,2H),7.106～7.185(m,4H), 7.302～7.342(m,4H),7.370～7.431(m,8H),7.464～7.505(m,4H),7.512～7.575(m, 8H),7.660～7.679(d,2H),7.704～7.780(m,6H),7.792～7.811(m,2H)；
(2)ESI-MS：C67H40N2O2，标准分子量904.309，测试结果905.3076[M+H]；
实施例6、化合物式ONA-59～ONA-64、ONA-66～ONA-73的制备
参考实施例5的制备方法可制备化合物式ONA-59～ONA-64、 ONA-66～ONA-73。
实施例7、化合物式ONA-92的制备
10g的中间体Int.-3与100ml的甲苯混合，在氮气保护下，加入6.3g的2- 苯并菲硼酸SM-8和4.5g的碳酸钠，再加入12.3mg的Pd(PPh3)4以及20ml 的乙醇和20ml的水的混合溶液，加热回流搅拌反应8小时，冷却到室温，分出有机相，水相用乙酸乙酯萃取，收集有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得11.4g的白色固体，收率87％。
实验数据：
(1)1HNMR(δ、CDCl3)：7.104～7.132(m,3H),7.140～7.158(m,2H), 7.172～7.433(m,12H),7.474～7.495(m,2H),7.505～7.518(m,2H),7.706～7.719(d, 2H),7.914～7.923(m,3H),8.102～8.110(m,1H),8.552(s,1H)；
(2)ESI-MS：C49H28，标准分子量616.2191，测试结果616.2184[M+]；
实施例8、化合物式ONA-74～ONA-91、ONA-93～ONA-99的制备
参考实施例5的制备方法可制备化合物式ONA-74～ONA-91、 ONA-93～ONA-99。
实施例9、OLED器件的制备(OLED-1～OLED-5)
1)将涂布了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1×10-5～9×10-4Pa，在ITO玻璃基片上真空蒸镀一层TDATA，作为器件的空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为50nm；
3)在空穴注入层上继续真空蒸镀本发明的化合物(式I)作为器件的空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
4)在空穴传输层上继续真空蒸镀一层mCBP作为主体材料和Ir(hpiq)2(acac) 为掺杂材料作为器件的发光层，mCBP:Ir(hpiq)2(acac)＝90:10，作为器件的有机发光层，蒸镀速率为0.1nm/s，所得有机发光层的膜厚为40nm；
5)在有机发光层上真空蒸镀一层Liq和Slichem-EL-068作为器件的电子传输层，Liq:Slichem-EL-068＝95:5，蒸镀速率为0.1nm/s，蒸镀膜厚为50nm；
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，见附图1。
按照与上相同的步骤，将步骤3)中的化合物(式I)选为化合物ONA-1，得到本发明提供的OLED-1；
按照与上相同的步骤，将步骤3)中的化合物(式I)选为化合物ONA-16，得到本发明提供的OLED-2；
按照与上相同的步骤，将步骤3)中的化合物(式I)选为化合物ONA-38，得到本发明提供的OLED-3；
按照与上相同的步骤，将步骤3)中的化合物(式I)选为化合物ONA-59，得到本发明提供的OLED-4；
按照与上相同的步骤，将步骤3)中的化合物(式I)改为化合物NPB，得到本发明提供的OLED-5作为对照器件，化合物NPB的结构如下：
所得器件OLED-1至OLED-5的性能检测结果如表1所示。
表1、OLED-1至OLED-5的性能检测结果
由上可知，本专利发明的有机材料作为空穴传输层的材料制备成的器件起亮电压低，亮度保持在2000cd/m2条件下，器件的效率均超过的15cd/A，而且在器件未封装完好的条件下，其半衰期都达到了300小时。
实施例10、OLED器件的制备(OLED-6～OLED-9)
1)将涂布了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～ 9×10-4Pa，在ITO玻璃基片上真空蒸镀一层TDATA，作为器件的空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为50nm；
3)在空穴注入层上继续真空蒸镀NPB作为器件的空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
4)在空穴传输层上继续真空蒸镀一层本发明的化合物式(I)作为主体材料和BD18为掺杂材料作为器件的发光层，化合物式(I):BD18＝92:8，作为器件的有机发光层，蒸镀速率为0.1nm/s，所得有机发光层的膜厚为40nm；
5)在有机发光层上真空蒸镀一层Liq和Slichem-EL-068作为器件的电子传输层，Liq:Slichem-EL-068＝95:5，蒸镀速率为0.1nm/s，蒸镀膜厚为50nm；
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，见附图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ONA-81，得到本发明提供的OLED-6。
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ONA-92，得到本发明提供的OLED-7。
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ONA-94，得到本发明提供的OLED-8。
按照与上相同的步骤，将步骤4)中的化合物(式I)改为化合物ADN，得到本发明提供的OLED-9作为对照器件。
所得器件OLED-6至OLED-9的性能检测结果如表2所示。
表2、OLED-6至OLED-9的性能检测结果
由上可知，本专利发明的有机材料作为发光层的材料制备成的器件起亮电压低，亮度保持在2000cd/m2条件下，器件的效率均超过的16cd/A，而且在器件未封装完好的条件下，其半衰期都达到了100小时。
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 (14)

1.式I所示化合物，
其中，
R1、R2、R3、R4各自独立地选自氢原子、氘氢原子、C1-C20烷基、C2-C20烯基、C2-C20炔基、C1-C20烷氧基、C3-C20环烷烃基、C3-C20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含氧芳基、取代的或未取代的C6-C60含硫芳基、取代的或未取代的C6-C60含膦芳基、取代的或未取代的C6-C60含氮芳基、取代的或未取代的C6-C60含硅芳基、取代的或未取代的C6-C60含硼芳基、取代的或未取代的C2-C60杂环芳基中的任意一种；
X1至X12各自独立地选自碳或氮，且任意相邻两个所述X1至X12不能同时为氮。
2.根据权利要求1所述的化合物，其特征在于：所述取代的C6-C60芳基、取代的C6-C60含氧芳基、取代的C6-C60含硫芳基、取代的C6-C60含膦芳基、取代的C6-C60含硅芳基、取代的C6-C60含硼芳基、取代的C6-C60含氮芳基和取代的C2-C60杂环芳基中，取代基选自氘氢、C1-C20烷基、C2-C20烯基、C2-C20炔基、C1-C20烷氧基、C3-C20环烷烃基和C3-C20环烯烃基中的任意一种或多种。
3.根据权利要求1所述的化合物，其特征在于：所述C6-C60芳基选自苯基、萘基、联苯基、蒽基、联蒽基、芘基、并四苯基、菲基、苯并菲基、苯并蒽基、苯并芘基、芴基、螺芴基中的任意一种；
所述C6-C60含氧芳基选自二苯并[b,d]呋喃-2-基、二苯并[b,d]呋喃-4-基、苯并呋喃-2-基、苯并呋喃-5-基、苯并呋喃-7-基、9,9-二甲基氧杂蒽-4-基、9,9-二甲基氧杂蒽-2-基、螺[芴-9,9’-氧杂蒽]-2’-基、螺[芴-9,9’-氧杂蒽]-2-基中的任意一种；
所述C6-C60含硫芳基选自二苯并[b,d]噻吩-2-基、二苯并[b,d]噻吩-4-基、4-苯亚砜基苯基、4-苯砜基苯基、苯并噻吩-2-基、苯并噻吩-5-基、苯并噻吩-7-基、9,9-二甲基硫杂蒽-4-基、9,9-二甲基硫杂蒽-2-基、螺[芴-9,9’-硫杂蒽]-2’-基、螺[芴-9,9’-硫杂蒽]-2-基中的任意一种；
所述C6-C60含膦芳基选自4-(二苯基氧膦基)苯基、3-(二苯基氧膦基)苯基、二苯并[b]氧膦-5-(4-苯基)-4-基中的任意一种；
所述C6-C60含硅芳基选自4-(三苯基硅基)苯基、4-(二苯基甲基硅基)苯基、3-(三苯基硅基)苯基、3-(二苯基甲基硅基)苯基中的任意一种；
所述C6-C60含硼芳基选自4-(二(2,4,6-三甲基)苯基)-硼烷苯基、二苯并[b,d]硼烷-5-苯基-4-基、三苯基硼基中的任意一种；
所述C6-C60含氮芳基选自由取代的或未取代的C2-C60杂环芳基、取代的或未取代的C6-C60芳基与氮原子组成的群组；
所述取代的或未取代的C2-C60杂环芳基为其中包含N、O、S原子中的至少一种的环状结构基团。
4.根据权利要求1所述的化合物，其特征在于：所述C2-C60的杂环芳基包含以下II-1～II-17的结构：
其中，Z1、Z2、Z3各自独立地选自氢、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、含有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选自BR’、NR’、PR’、O、S、Se、C＝O、S＝O、SO2、CR’R”、SiR’R”或GeR’R”；
其中R’、R”各自独立地选自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、含有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芳硫基、取代的或未取代的C2-C60杂环芳基中的任意一种或稠合或接合而形成的环。
5.根据权利要求1所述的化合物，其特征在于：所述式I所示化合物为以下ONA-1～ONA-99所示化合物：
6.含有权利要求1-5中任一所述式I所示化合物的材料。
7.权利要求1-5中任一所述式I所示化合物在制备有机发光二极管材料中的应用。
8.权利要求1-5中任一所述式I所示化合物作为空穴层或发光层材料在制备有机电致发光器件中的应用。
9.含有权利要求1-5中任一所述式I所示化合物作为空穴层或发光层的有机电致发光器件。
10.根据权利要求9所述的器件，其特征在于：所述有机电致发光器件由下至上依次包含透明基片、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。
11.根据权利要求10所述的器件，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，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一种或多种。
12.根据权利要求10所述的器件，其特征在于：所述空穴注入层的材料为一种或多种权利要求1-5中任一所述式I所示化合物和/或一种或多种以下所示化合物组成的混合物：
构成所述空穴传输层的材料包含一种或多种权利要求1-5中任一所述式I所示化合物；
构成所述有机发光层的材料包括主体材料和掺杂材料，所述主体材料包含以下所示化合物中的一种或多种：
构成所述有机发光层的掺杂材料包含一种或多种权利要求1-5中任一所述式I所示化合物或包含红色、绿色、蓝色掺杂材料，
所述蓝色掺杂材料为以下所述化合物中的一种或多种：
所述红色掺杂材料为以下所述化合物中的一种或多种：
所述绿色掺杂材料为以下所述化合物中的一种或多种：
所述电子传输层的材料包含以下所述化合物中的一种或多种：
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。
13.根据权利要求10-12中任一所述的器件，其特征在于：
所述空穴注入层的厚度为30-50nm；
所述空穴传输层的厚度为10-50nm；
所述有机发光层的厚度为10-100nm；
所述电子传输层的厚度为10-30nm；
所述阴极层的厚度为90-110nm。
14.根据权利要求10-12中任一所述的器件，其特征在于：
所述空穴注入层的厚度为50nm；
所述空穴传输层的厚度为40nm；
所述有机发光层的厚度为40nm；
所述电子传输层的厚度为50nm；
所述阴极层的厚度为100nm。
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