CN112125854B - 一种有机电致发光材料及使用该种材料的有机电致发光器件 - Google Patents
一种有机电致发光材料及使用该种材料的有机电致发光器件 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及有机电致发光材料技术领域,具体涉及一种有机电致发光材料及使用该种材料的有机电致发光器件。
背景技术
有机电致发光器件(Organic Light-emitting Devices,OLED)是利用如下原理的自发性发光器件:当施加电场时,荧光物质通过正极注入的空穴和负极注入的电子的重新结合而发光。这种自发光器件,具有电压低、亮度高、视角宽、响应快、温度适应性好等特性,并且超薄,能制作在柔性面板上等优点,广泛应用于手机、平板电脑、电视和照明等领域。
对于有机电致发光器件提高性能的研究包括:降低器件的驱动电压,提高器件的发光效率,提高器件的使用寿命等。为了实现有机电致发光器件性能的不断提升,不但需要有机电致发光器件的结构和制作工艺的创新,更需要有机电致光电功能材料的不断研究和创新,创制出更高性能的有机电致功能材料。
就当前有机电致发光产业的实际需求而言,目前有机电致发光材料的发展还远远不够,落后仅电子有机半导体二极管器件为在两个金属、无机物或有机化合物的电极之间通过旋涂或沉积一层或多层有机材料而制备的器件。
连接到仅电子有机半导体二极管器件的电压到达开启电压后,由阴极产生的电子经电子传输层传输到阳极,相反地,空穴不能从阳极注入。仅电子有机半导体二极管器件中的电子传输材料可应用到其它半导体器件如有机电致发光器件。
有机电致发光器件市场庞大,因而稳定、高效的有机电子传输材料及空穴阻挡材料对有机电致发光器件的应用和推广具有重要作用,同时也是有机电致发光大面积面板显示的应用推广的迫切需求。
发明内容
发明目的:针对上述技术问题,本发明提供了一种有机电致发光材料及使用该种材料的有机电致发光器件,该种有机电致发光材料既可作为电子传输材料使用,又可以作为空穴阻挡材料使用。
为了达到上述发明目的,本发明所采用的技术方案如下:
一种机电致发光材料,其结构式如下所示:
其中,L1和L2独立地选自取代或未取代的C6-C14的芳香基、取代或未取代的C5-C18的杂芳香基;
X、Y、Z独立地选自N或C;
m、n独立地选自0或1;
R1、R2、R3、R4独立地选自取代或未取代的C1-C3的烷基、取代或未取代的C6-C14的芳香族基团、取代或未取代的C5-C18的杂芳香族基团;
R5选自取代或未取代的C6-C24的芳香基,取代或未取代的C5-C18的杂芳香基;
R6选自氢、氰基或三氟甲基。
进一步地,L1、L2独立地选自苯基、联苯基、萘基、蒽基、氧芴基、硫芴基、二甲基芴基或N-苯基咔唑基。
进一步地,R5选自苯基、联苯基、三联苯基、氧芴基、二甲基芴基、邻二苯基苯或N-苯基咔唑基中的任意一种。
进一步地,上述有机电致发光材料为下列结构式化合物中的任意一种:
上述机电致发光材料的制备方法,包括如下步骤:
步骤1:
将结构通式为的化合物A、结构通式为的化合物B、钯催化剂、碳酸钾加入到甲苯、乙醇、水按一定体积比组成的混合溶液中,加热至回流并搅拌反应8-12h,反应完成后冷却至室温,萃取分液,减压浓缩后柱层析纯化得到中间体C;
步骤2:
步骤3:
将中间体E、结构通式为的化合物F、钯催化剂、碳酸钾、加入到甲苯、乙醇、水按一定体积比组成的混合溶液中,加热至回流并搅拌反应8-12h,反应完成后冷却至室温,萃取分液,减压浓缩后柱层析纯化得到所述机电致发光材料。
进一步地,步骤1、步骤2和步骤3中的钯催化剂均为四(三苯基膦)钯。
进一步地,步骤3中甲苯、乙醇、水的体积比为7:3:2。
上述机电致发光材料在制备有机电致发光器件或有机半导体二极管器件中的应用。
一种有机电致发光器件,包括第一电极、第二电极和置于所述两电极之间的一个或多个有机化合物层,至少一个有机化合物层包含至少一种上述机电致发光材料。
本发明的有益效果:
本发明设计的有机电致发光材料,由于其具有较高的HOMO值和较低的LUMO值,使其适用于作为电子传输材料及空穴阻挡材料使用,该类材料的使用能够在不降低电子传输速率的前提下,将空穴有效的阻挡在发光层,避免空穴进入电子传输层与电子进行复合产生激子,进而大幅度提高有机电致发光器件的发光效率及寿命。
如下结构式III,
该结构具有较大的共轭体系及丰富的电子云密度,具有非常良好的热稳定性能及载流子传输性能,加之其本发明材料的低LUMO值的特性,使该类材料可作为性能优良的电子传输材料使用;并且由于本发明材料的高HOMO值特性,使该类材料同时可以作为空穴阻挡材料来进行使用。
氰基作为良好的吸电子基团,该基团的引入,能够在不影响材料分子的热稳定性的情况下,有效提高材料分子的HOMO能级值,降低材料分子的LUMO能级值,使其同时具备良好的空穴阻挡能力及电子传输能力。
经器件验证,本发明的有机电致发光材料能使器件的驱动电压大大降低,大幅度减少了电能的消耗、显著提高了发光效率,另外通过低驱动电压,有机电致发光器件的寿命有效提高。
附图说明
图1为本发明应用例10的发光亮度随发光时间变化的关系图,由图1可以得出本发明应用例10的T97寿命为376h;
图2为本发明应用例10的发光效率随电流密度变化的关系图,由图2可以得出当电流密度为10mA/cm2,本发明应用例10的发光效率为9.1Cd/A;
图3为本发明应用例10的发光亮度随电压变化的关系图,由图3可以得出本发明应用例10的启动电压为2.9V。
具体实施方式
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
1的合成方法如下:
1)中间体C的合成:
将化合物A(1eq,314.76g/mol,00.0031mol,10.0g)、化合物B(1.1eq,4.19g,122.05g/mol,0.035mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.049mol,6.84g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体C(6.7g,收率69.4%),MS(EI):312(M+)。
2)中间体E的合成:
将中间体C(1eq,312.89g/mol,0.019mol,6.0g)、化合物D(1.1eq,430.21g/mol,
0.021mol,9.09g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.03mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(8.36g,收率71.7%),MS(EI):619(M+)。
3)化合物1的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.012mol)、化合物F(1.1eq,147.05g/mol,1.92g,0.030mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.019mol,2.64g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物1(5.09g,收率68.4%),MS(EI):642(M+)。
实施例2:
2的合成方法如下:
1)中间体C的合成:
将化合物A(1eq,313.77g/mol,0.031mol,10.0g)、化合物B(1.1eq,4.14g,122.05g/mol,0.034mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.049mol,6.85g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体C(9.73g,收率70.9%),MS(EI):311(M+)。
2)中间体E的合成:
将中间体C(1eq,311.89g/mol,0.029mol,9.0g)、化合物D(1.1eq,430.21g/mol,0.031mol,13.57g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.046mol,6.41g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(17.97g,收率71.7%),MS(EI):618(M+)。
3)化合物2的合成:
将中间体E(1eq,618.17g/mol,17.0g,0.027mol)、化合物F(1.1eq,147.05g/mol,4.36g,0.029mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.043mol,5.96g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物2(17.32g,收率69.4%),MS(EI):641(M+)。
实施例3:
步骤1-2与实施例1基本相同,其余步骤如下:
3)化合物3的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.013mol)、化合物F(1.1eq,147.05g/mol,2.07g,0.014mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.021mol,2.89g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物3(5.60g,收率67.1%),MS(EI):642(M+)。
实施例4:
步骤1-2与实施例2基本相同,其余步骤如下:
3)化合物4的合成:
将中间体E(1eq,618.17g/mol,10.0g,0.016mol)、化合物F(1.1eq,147.05g/mol,2.59g,0.017mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.025mol,3.53g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物2(7.03g,收率68.6%),MS(EI):641(M+)。
实施例5:
步骤1-2与实施例1基本相同,其余步骤如下:
3)化合物5的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.012mol)、化合物F(1.1eq,223.08g/mol,3.16g,0.014mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.019mol,2.65g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物5(5.97g,收率69.4%),MS(EI):718(M+)。
实施例6:
步骤1-2与实施例2基本相同,其余步骤如下:
3)化合物6的合成:
将中间体E(1eq,618.17g/mol,13.0g,0.021mol)、化合物F(1.1leq,223.08g/mol,5.16g,0.023mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.033mol,4.63g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物6(9.84g,收率65.4%),MS(EI):717(M+)。
实施例7:
步骤1-2与实施例1基本相同,其余步骤如下:
3)化合物7的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.013mol)、化合物F(1.1eq,223.08g/mol,3.12g,0.014mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.021mol,2.87g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物7(6.42g,收率68.8%),MS(EI):718(M+)。
实施例8:
步骤1-2与实施例2基本相同,其余步骤如下:
3)化合物8的合成:
将中间体E(1eq,618.17g/mol,10.0g,0.016mol)、化合物F(1.1eq,223.08g/mol,3.79g,0.017mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.025mol,3.53g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物8(7.53g,收率65.7%),MS(EI):717(M+)。
实施例9:
步骤1与实施例1基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,312.89g/mol,0.019mol,6.0g)、化合物D(1.1eq,430.21g/mol,0.021mol,9.09g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.03mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(8.38g,收率71.2%),MS(EI):619(M+)。
3)化合物9的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.012mol)、化合物F(1.1eq,147.05g/mol,1.92g,0.030mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.019mol,2.64g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物9(5.12g,收率66.4%),MS(EI):642(M+)。
实施例10:
步骤1与实施例2基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,311.89g/mol,0.029mol,9.0g)、化合物D(1.1eq,430.21g/mol,0.031mol,13.57g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.046mol,6.41g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(12.85g,收率71.5%),MS(EI):618(M+)。
3)化合物10的合成:
将中间体E(1eq,618.17g/mol,12.0g,0.019mol)、化合物F(1.1eq,147.05g/mol,3.11g,0.021mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.031mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物10(8.43g,收率69.1%),MS(EI):641(M+)。
实施例11:
步骤1与实施例1基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,312.89g/mol,0.019mol,6.0g)、化合物D(1.1eq,430.35g/mol,0.021mol,9.09g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.03mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(8.41g,收率71.4%),MS(EI):620(M+)。
3)化合物11的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.012mol)、化合物F(1.1eq,147.05g/mol,1.92g,0.030mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.019mol,2.64g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物11(4.96g,收率64.4%),MS(EI):642(M+)。
实施例12:
步骤1与实施例2基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,311.89g/mol,0.029mol,9.0g)、化合物D(1.1eq,430.21g/mol,0.031mol,13.57g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.046mol,6.41g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(12.81g,收率71.3%),MS(EI):618(M+)。
3)化合物12的合成:
将中间体E(1eq,618.17g/mol,12.0g,0.019mol)、化合物F(1.1eq,147.05g/mol,3.11g,0.021mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.031mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物12(8.45g,收率69.3%),MS(EI):641(M+)。
实施例13:
步骤1与实施例1基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,312.89g/mol,0.019mol,6.0g)、化合物D(1.1eq,430.21g/mol,0.021mol,9.09g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.03mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(8.41g,收率71.4%),MS(EI):619(M+)。
3)化合物13的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.013mol)、化合物F(1.1eq,223.08g/mol,3.16g,0.014mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.021mol,2.87g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物13(6.36g,收率68.2%),MS(EI):718(M+)。
实施例14:
步骤1与实施例2基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,311.89g/mol,0.029mol,9.0g)、化合物D(1.1eq,430.21g/mol,0.031mol,13.57g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.046mol,6.41g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(12.78g,收率71.1%),MS(EI):618(M+)。
3)化合物14的合成:
将中间体E(1eq,618.17g/mol,12.0g,0.019mol)、化合物F(1.1eq,223.08g/mol,4.66g,0.021mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.031mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物14(8.92g,收率65.5%),MS(EI):717(M+)。
实施例15:
步骤1与实施例1基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,312.89g/mol,0.019mol,6.0g)、化合物D(1.1eq,430.21g/mol,0.021mol,9.09g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.03mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(8.43g,收率71.6%),MS(EI):619(M+)。
3)化合物15的合成:
将中间体E(1eq,619.16g/mol,8.0g,0.013mol)、化合物F(1.1eq,223.08g/mol,3.16g,0.014mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.021mol,2.87g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物15(6.26g,收率67.1%),MS(EI):718(M+)。
实施例16:
步骤1与实施例2基本相同,其余步骤如下:
2)中间体E的合成:
将中间体C(1eq,311.89g/mol,0.029mol,9.0g)、化合物D(1.1eq,430.21g/mol,0.031mol,13.57g)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.046mol,6.41g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到中间体E(12.74g,收率70.9%),MS(EI):618(M+)。
3)化合物16的合成:
将中间体E(1eq,618.17g/mol,12.0g,0.019mol)、化合物F(1.1eq,223.08g/mol,4.68g,0.021mol)、四(三苯基膦)钯(0.03eq,1155.58g/mol,0.001mol、1.07g)和碳酸钾(1.6eq,138.21g/mol,0.031mol,4.19g)置于300ml的圆底烧瓶中,向其中加入甲苯(70ml)、乙醇(30ml)和水(20ml),加热混合物至回流并搅拌12h,反应完成后,使反应器冷却至室温,用乙酸乙酯萃取反应混合物,减压浓缩有机层,通过柱层析纯化得到化合物16(9.22g,收率67.7%),MS(EI):717(M+)。
以下将通过实施例和对照例对本发明进行详细的说明。下属实施例于对照例只是为了举例说明本发明,本发明的范围并不限于下述实施例和对照例。
《有机电致发光器件的制造》
应用例1:
将本发明作为电子传输层材料使用,其器件制备及性能效果去下:
其采用ITO作为反射层阳极基板材料,并以N2等离子或UV-Ozone对其进行表面处理。在阳极基板上方,向空穴注入层(HIL)沉积HAT-CN10纳米厚度的HAT-CN,在其上方选使用NPD以120纳米厚度形成空穴传输层(HTL),在上述空穴传输层(HTL)上,真空蒸镀形成blue EML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光主体材料,选择BD-1为dopant材料,掺杂5%的BD-1形成厚度为25纳米的发光层,在上述发光层上,选择本发明的有机电致发光材料1,并按照化合物1:LiQ=1:1的比例进行掺杂,蒸镀35纳米厚度形成电子传输层(ETL),在电子传输层上以2纳米厚度的LiQ进行蒸镀,形成电子注入层(EIL)。此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。
此外,在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封,以保护有机电致发光器件不被大气中的氧气或水分所影响至此制备获得有机电致发光器件。
应用例2-16
与应用例1的区别在于,分别用有机电致发光材料2-16替换有机电致发光材料1,其余与应用例1相同,据此制作出应用例2-16的有机电致发光器件。
对照例1、2
与应用例1的区别在于,分别使用PBD和p-EtAZ代替本发明应用例1中的有机电致发光材料1作为ETL,其余与应用例1相同,据此制作出对照例1、2的有机电致发光器件。
上述应用例所制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm2的条件下测定的,结果如表1所示。
表1不同实验组器件性能测试结果:
由如上表1的实验对比数据可知,采用本发明的有机电致发光器件的应用例1-16,与对照例1,2相比,电压大幅度降低,发光效率显著提高,且色坐标蓝移,可以大大提高OLED器件的蓝光色彩饱和度。由此可见,本发明的化合物能使器件的驱动电压大大降低,大幅度减少了电能的消耗、显著提高了发光效率。另外通过低驱动电压,高的色彩饱和度,有机电致发光器件的寿命有效提高,色彩更加鲜艳。
《有机电致发光器件的制造》
应用例17:
将本发明作为空穴阻挡层材料使用,其器件制备及性能效果去下:
其采用ITO作为反射层阳极基板材料,并以N2等离子或UV-Ozone对其进行表面处理。在阳极基板上方,向空穴注入层(HIL)沉积HAT-CN10纳米厚度的HAT-CN,在其上方选使用NPD以120纳米厚度形成空穴传输层(HTL),在上述空穴传输层(HTL)上,真空蒸镀形成blue EML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光主体材料,选择BD-1为dopant材料,掺杂5%的BD-1形成厚度为25纳米的发光层,在上述发光层上,选择本发明的有机电致发光材料1进行蒸镀,以形成10nm厚度的空穴阻挡层(HBL),在上述空穴阻挡层上,选择本发明的有机电致发光材料1,并按照化合物1:LiQ=1:1的比例进行掺杂,蒸镀35纳米厚度形成电子传输层(ETL),在电子传输层上以2纳米厚度的LiQ进行蒸镀,形成电子注入层(EIL)。此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。
此外,在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封,以保护有机电致发光器件不被大气中的氧气或水分所影响至此制备获得有机电致发光器件。
应用例18-33
与应用例17的区别在于,分别用有机电致发光材料2-16替换有机电致发光材料1,其余与应用例17相同,据此制作出应用例18-32的有机电致发光器件。
对照例3、4
与应用例17的区别在于,分别使用TPBi和BCP代替本发明应用例1中的有机电致发光材料1作为HBL,其余与应用例17相同,据此制作出对照例3、4的有机电致发光器件。
上述应用例所制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm2的条件下测定的,结果如表2所示。
表2不同实验组器件性能测试结果:
由如上表2的实验对比数据可知,采用本发明的有机电致发光器件的应用例17-32,与对照例3,4相比,电压大幅度降低,发光效率显著提高。由此可见,本发明的化合物能使器件的驱动电压大大降低,大幅度减少了电能的消耗、显著提高了发光效率。另外通过低驱动电压,有机电致发光器件的寿命有效提高,色彩更加鲜艳。
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