CN111675701A - 一种基于三苯胺结构的有机电致发光化合物及有机电致发光器件 - Google Patents
一种基于三苯胺结构的有机电致发光化合物及有机电致发光器件 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及有机电致发光技术领域,具体涉及一种基于三苯胺结构的有机电致发光化合物及有机电致发光器件。
背景技术
有机电致发光器件(Organic Light Emitting Display,简称OLED)作为新型的平板显示器,与液晶显示器(Liquid Crystal Display,简称LCD)相比,具有薄、轻、宽视角、主动发光、发光颜色连续可调、成本低、响应速度快、能耗小、驱动电压低、工作温度范围宽、生产工艺简单、发光效率高及可柔性显示等优点,得到了产业界和科学界的极大关注。
有机电致发光器件的发光原理是在阴阳两极施加电场时,阳极侧的空穴和阴极侧的电子会向发光层移动,在发光层结合形成激子,激子处于激发态向外释放能量,从激发态释放能量变为基态释放能量的过程对外发光。自1987年美国柯达公司报道有机分子电致发光和1990年英国剑桥大学报道聚合物电致发光以来,世界各国纷纷开展研究与开发。该类材料具有结构简单、成品率高、成本低、主动发光、响应速度快、分率高等优点,且具有驱动电压低、全固态、非真空、抗荡、耐低温(-40℃)等性能。近年来,OLED材料在智能手机领域得到了广泛应用,被认为是未来最有可能替代液晶显示器的一种新技术,引起极大关注。
目前国内外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。
为了实现有机电致发光器件的优异发光性能,构成有机材料层的材料,如空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层以及诸如主体和/或掺杂剂的发光材料应该是稳定的,并具有良好效率。然而,用于有机电致发光器件的有机材料层材料的开发至今仍远不能令人满意,因而仍需要不断开发新材料。
发明内容
发明目的:针对上述技术问题,本发明提供了一种基于三苯胺结构的有机电致发光化合物及有机电致发光器件。
为了达到上述发明目的,本发明所采用的技术方案如下:
一种基于三苯胺结构的有机电致发光化合物,其结构式如下所示:
Ar1、Ar2相同或不同,各自独立的为C6-C30的芳香基、C5-C30的杂芳香基,所述C6-C30的芳香基、C5-C30的杂芳香基中的至少一个氢可以被C1-C4的烷基、C1-C4的氘代烷基、苯基、氰基取代或非取代;
L为C6-C30的亚芳香基,且L不为亚苯基;
m、n各自独立的为1或2。
进一步地,Ar1、Ar2相同或不同,各自独立的为苯基、联苯基、吡啶基、嘧啶基、三嗪基、蒽基、萘基、菲基、氧芴基、硫芴基、咔唑基、N苯基咔唑基、芴基、9,9-二甲基芴基、9,9-二苯基芴基、9-甲基-9-苯基芴基、9,9'-螺二芴基;
所述苯基、联苯基、吡啶基、嘧啶基、三嗪基、蒽基、萘基、菲基、氧芴基、硫芴基、咔唑基、N-苯基咔唑基、芴基、9,9-二甲基芴基、9,9-二苯基芴基、9-甲基-9-苯基芴基、9,9'-螺二芴基为未取代或其中的至少一个氢被氘、C1-C4的烷基、C1-C4的氘代烷基、苯基、氰基取代。
进一步地,当Ar1、Ar2同时为苯基时,m、n不同时为1。
进一步地,L为亚萘基或亚蒽基。
进一步地,所述有机电致发光化合物的结构式为如下所示的任意一种:
进一步地,其结构式为如下所示的任意一种:
进一步地,所述有机电致发光化合物为下列化合物中的任意一种:
上述有机电致发光化合物在制备有机电致发光器件中的应用。
一种有机电致发光器件,包括相对设置的阳极和阴极,以及设于所述阳极和所述阴极之间的功能层;所述功能层含有上述的有机电致发光化合物。
进一步地,所述功能层包括:空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层,所述空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层中的至少一层含有上述的有机电致发光化合物。
进一步地,所述空穴传输层、电子阻挡层、发光层中的至少一层含有上述的有机电致发光化合物。
一种OLED显示设备,含有上述有机电致发光器件。
本发明所述室温均为25±5℃。
本发明的有益效果:
本发明设计的有机电致发光化合物,由于在分子中引入了萘基与蒽基的共轭结构,增加了材料分子的空穴迁移率,进而有效降低了发光器件的电压。同时萘基与蒽基的引入增加了材料分子的扭矩、空间位阻及热稳定性,扭矩及空间位阻的增大有效提高了材料分子的三线态能级(T1),有效避免了能量从发光层到电子阻挡层的反向传递,进而大幅度提高了器件的效率及寿命。热稳定性的提高,进一步提高了器件的寿命。
附图说明
图1为本发明提供的有机电致发光器件的结构示意图;
图中标号分别代表:
1-阳极、2-空穴注入层、3-空穴传输层、4-电子阻挡层、5-发光层、6-空穴阻挡层、7-电子传输层、8-电子注入层、9-阴极。
图2为本发明有机电致发光化合物1的DSC图,由图2可知,本发明有机电致发光化合物1的玻璃化温度Tg值为153.02℃;
图3为本发明有机电致发光化合物1的TGA图,由图3可知,本发明有机电致发光化合物1热失重温度Td值为379.50℃;
图4为应用例1和对照例1所制备的有机电致发光器件的发光寿命曲线,由图4可知,应用例1和对照例所制备的有机电致发光器件的发光寿命T97%分别为344h、301h。
图5为本发明有机电致发光化合物1的HNMR图。
具体实施方式
以下进一步说明和描述了各个方面的实施例。应当理解,本文的描述并非旨在将权利要求书限制于所描述的特定方面。相反,旨在覆盖可包括在由所附权利要求书限定的本公开的精神和范围内的替代、修改和等同物。
如本文所用,“Ca至Cb”烃基被限定为具有碳数为“a”(包含在内)至“b”(包含在内)的烃基。如本文所用,“a和/或b”表示“a”或“b”或“a和b”。
如本文所用,在“取代的”或“未取代的”中,术语“取代的”是指该基团中的至少一个氢与氘、烃基、烃衍生物基、卤素或氰基(-CN)重新配位。术语“未取代的”是指该基团中的至少一个氢不与氘、烃基、烃衍生物基、卤素或氰基(-CN)重新配位。烃基或烃衍生物基团的实例可包括C1至C30烷基、C2至C30烯基、C2至C30炔基、C6至C30芳基、C5至C30杂芳基、C1至C30烷氨基、C6至C30芳氨基、C6至C30杂芳氨基、C6至C30芳基杂芳氨基等,但不限于此。
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:
有机电致发光化合物1的制备方法如下:
S1:
氮气保护下,将化合物1-a(10g,384.47g/mol,26.01mmol),化合物1-b(1eq,8.41g,323.18g/mol,26.01mmol)、叔丁醇钠(1.1eq,2.75g,96.1g/mol,28.61mmol)、三(二亚苄基丙酮)二钯(0.05eq,1.19g,915g/mol,1.3mmol)、三叔丁基膦(0.05eq,0.26g,202.32g/mol,1.3mmol)、100ml甲苯加入反应瓶中,加料完毕后升温至回流反应8h,反应完毕后自然冷却至室温,加入100mL水,搅拌30min,经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物1-c(8.66g,收率53.1%),ESI-MS(m/z)(M+):理论值626.74,实测值626.88。
S2:
氮气保护下,将化合物1-c(5g,626.74g/mol,7.98mmol),化合物1-d(1eq,1.86g,233.10g/mol,7.98mmol)、叔丁醇钠(1.1eq,0.84g,96.1g/mol,8.78mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.37g,915g/mol,0.4mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.4mmol)、50ml甲苯加入反应瓶中,加料完毕后升温至回流反应8h,反应完毕后自然冷却至室温,加入50mL水,搅拌30min,经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到有机电致发光化合物1(3.15g,收率50.6%),ESI-MS(m/z)(M+):理论值778.94,实测值778.54,元素分析结果(分子式C58H38N2O):理论值C,89.43;H,4.92;N,3.60;O,2.05;实测值C,89.44;H,4.92;N,3.60;O,2.05。
实施例2:
有机电致发光化合物2的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b替换为化合物2-b,收率53.5%,ESI-MS(m/z)(M+):理论值778.94,实测值778.82,元素分析结果(分子式C58H38N2O):理论值C,89.43;H,4.92;N,3.60;O,2.05;实测值C,89.43;H,4.92;N,3.60;O,2.04。
实施例3:
有机电致发光化合物3的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-d替换为化合物3-d,收率46.9%,ESI-MS(m/z)(M+):理论值855.03,实测值856.24,元素分析结果(分子式C64H42N2O):理论值C,89.90;H,4.95;N,3.28;O,1.87;实测值C,C,89.90;H,4.95;N,3.28;O,1.87。
实施例4:
有机电致发光化合物6的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b、1-d分别替换为化合物4-b、4-d,收率48.8%,ESI-MS(m/z)(M+):理论值856.02,实测值857.16,元素分析结果(分子式C62H41N5):理论值C,86.99;H,4.83;N,8.18;实测值C,C,86.99;H,4.82;N,8.18。
实施例5:
有机电致发光化合物13的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b替换为化合物5-b,收率51.3%,ESI-MS(m/z)(M+):理论值855.03,实测值856.19,元素分析结果(分子式C64H42N2O):理论值C,C,89.90;H,4.95;N,3.28;O,1.87;实测值C,89.91;H,4.95;N,3.28;O,1.87。
实施例6:
有机电致发光化合物17的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b替换为化合物6-b,收率54.5%,ESI-MS(m/z)(M+):理论值764.95,实测值764.70,元素分析结果(分子式C58H40N2):理论值C,91.07;H,5.27;N,3.66;实测值C,91.08;H,5.27;N,3.66。
实施例7:
有机电致发光化合物19的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b替换为化合物7-b,收率51.6%,ESI-MS(m/z)(M+):理论值795.00,实测值796.43,元素分析结果(分子式C58H38N2S):理论值C,87.63;H,4.82;N,3.52;S,4.03;实测值C,87.63;H,4.83;N,3.52;S,4.02。
实施例8:
有机电致发光化合物23的制备方法如下:
制备方法与实施例7基本相同,区别在于,将实施例7中的化合物7-d替换为化合物8-d,收率52.2%,ESI-MS(m/z)(M+):理论值829.09,实测值830.48,元素分析结果(分子式C60H36D6N2S):理论值C,86.92;H,5.83;N,3.38;S,3.87;实测值C,86.93;H,5.83;N,3.38;S,3.88。
实施例9:
有机电致发光化合物25的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-b替换为化合物9-b,收率47.8%,ESI-MS(m/z)(M+):理论值870.10,实测值870.57,元素分析结果(分子式C66H43D3N2):理论值C,91.10;H,5.68;N,3.22;实测值C,91.11;H,5.68;N,3.22。
实施例10:
有机电致发光化合物33的制备方法如下:
制备方法与实施例1基本相同,区别在于,将实施例1中的化合物1-a替换为化合物10-a,收率48.3%,ESI-MS(m/z)(M+):理论值778.94,实测值778.72,元素分析结果(分子式C58H38N2O):理论值C,89.43;H,4.92;N,3.60;O,2.05;实测值C,89.43;H,4.92;N,3.60;O,2.06。
实施例11:
有机电致发光化合物37的制备方法如下:
制备方法与实施例10基本相同,区别在于,将实施例10中的化合物10-d替换为化合物11-d,收率46.0%,ESI-MS(m/z)(M+):理论值879.05,实测值880.13,元素分析结果(分子式C66H42N2O):理论值C,90.18;H,4.82;N,3.19;O,1.82;实测值C,90.18;H,4.82;N,3.20;O,1.82。
实施例12:
有机电致发光化合物42的制备方法如下:
制备方法与实施例10基本相同,区别在于,将实施例10中的化合物10-b替换为化合物12-b,收率50.9%,ESI-MS(m/z)(M+):理论值811.05,实测值812.44,元素分析结果(分子式C61H38D6N2):理论值C,90.33;H,6.21;N,3.45;实测值C,90.34;H,6.21;N,3.44。
实施例13:
有机电致发光化合物49的制备方法如下:
制备方法与实施例10基本相同,区别在于,将实施例10中的化合物10-b替换为化合物13-b,收率51.9%,ESI-MS(m/z)(M+):理论值764.95,实测值764.57,元素分析结果(分子式C58H40N2):理论值C,91.07;H,5.27;N,3.66;实测值C,91.07;H,5.28;N,3.66。
实施例14:
有机电致发光化合物51的制备方法如下:
制备方法与实施例10基本相同,区别在于,将实施例10中的化合物10-b替换为化合物14-b,收率47.7%,ESI-MS(m/z)(M+):理论值795.00,实测值796.38,元素分析结果(分子式C58H38N2S):理论值C,87.63;H,4.82;N,3.52;S,4.03;实测值C,87.63;H,4.83;N,3.52;S,4.03。
实施例15:
有机电致发光化合物58的制备方法如下:
制备方法与实施例10基本相同,区别在于,将实施例10中的化合物10-b替换为化合物15-b,收率43.1%,ESI-MS(m/z)(M+):理论值1039.35,实测值1040.27,元素分析结果(分子式C79H62N2):理论值C,91.29;H,6.01;N,2.70;实测值C,91.29;H,6.00;N,2.70。
实施例16:
有机电致发光化合物69的制备方法如下:
制备方法与实施例11基本相同,区别在于,将实施例11中的化合物11-a替换为化合物16-a,收率45.7%,ESI-MS(m/z)(M+):理论值929.11,实测值930.06,元素分析结果(分子式C70H44N2O):理论值C,90.49;H,4.77;N,3.02;O,1.72;实测值C,90.49;H,4.77;N,3.02;O,1.73。
实施例17:
有机电致发光化合物81的制备方法如下:
制备方法与实施例16基本相同,区别在于,将实施例16中的化合物16-b、16-d分别替换为化合物17-b、17-d,收率52.1%,ESI-MS(m/z)(M+):理论值815.01,实测值816.40,元素分析结果(分子式C62H42N2):理论值C,91.37;H,5.19;N,3.44;实测值C,91.38;H,5.19;N,3.44。
实施例18:
有机电致发光化合物87的制备方法如下:
制备方法与实施例16基本相同,区别在于,将实施例16中的化合物16-b、16-d分别替换为化合物18-b、18-d,收率50.3%,ESI-MS(m/z)(M+):理论值879.15,实测值880.23,元素分析结果(分子式C64H38D6N2S):理论值C,87.44;H,5.73;N,3.19;S,3.65;实测值C,87.45;H,5.73;N,3.20;S,3.65。
实施例19:
有机电致发光化合物99的制备方法如下:
制备方法与实施例3基本相同,区别在于,将实施例3中的化合物3-a替换为化合物19-a,收率45.4%,ESI-MS(m/z)(M+):理论值905.09,实测值906.61,元素分析结果(分子式C68H44N2O):理论值C,90.24;H,4.90;N,3.10;O,1.77;实测值C,90.24;H,4.90;N,3.10;O,1.78。
实施例20:
有机电致发光化合物130的制备方法如下:
制备方法与实施例2基本相同,区别在于,将实施例2中的化合物2-b替换为化合物20-b,收率53.0%,ESI-MS(m/z)(M+):理论值778.94,实测值778.80,元素分析结果(分子式C58H38N2O):理论值C,89.43;H,4.92;N,3.60;O,2.05;实测值C,89.42;H,4.92;N,3.60;O,2.05。
实施例21:
有机电致发光化合物143的制备方法如下:
制备方法与实施例20基本相同,区别在于,将实施例20中的化合物20-d替换为化合物21-d,收率51.7%,ESI-MS(m/z)(M+):理论值828.99,实测值828.29,元素分析结果(分子式C62H40N2O):理论值C,89.83;H,4.86;N,3.38;O,1.93;实测值C,89.83;H,4.86;N,3.38;O,1.94。
本发明实施例1-21中的化合物1-a~21-a的来源如下:
本发明实施例1-21中的化合物1-b~21-b的来源如下:
本发明实施例1-21中的化合物1-d~21-d的来源如下:
材料性质测试:
测试本发明实施例1-21中的有机电致发光化合物1、2、3、6、13、17、19、23、25、33、37、42、49、51、58、69、81、87、99、130、143的玻璃化温度Tg和热失重温度Td,结果如表1所示:
注:热失重温度Td是在氮气气氛中失重5%的温度,在TGA N-1000热重分析仪上进行测定,测定时氮气流量为10mL/min,玻璃化温度Tg由示差扫描量热法(DSC,德国耐驰公司DSC204F1示差扫描量热仪)测定,升温速率10℃/min。
表1:
由上表1可知,本发明有机电致发光化合物具有较高的Tg值和Td值,说明其具有优良的热稳定性,作为有机电致发光材料应用于有机电致发光器件中,可以有效延长有机电致发光器件的使用寿命,获得更佳的使用效果。
器件性能测试:
应用例1:
采用ITO作为反射层阳极基板材料,并依次用水、丙酮、N2等离子对其进行表面处理;
在ITO阳极基板上方,沉积厚度为10nm的HAT-CN形成空穴注入层(HIL);
在空穴注入层(HIL)上方蒸镀NPD形成厚度为100nm的空穴传输层(HTL);
在空穴传输层(HTL)上方真空本发明实施例1制备的有机电致发光化合物1,形成厚度为8nm的电子阻挡层(EBL);
将ADN作为蓝光主体材料、BD-1作为蓝光掺杂材料(BD-1用量为ADN重量的5%)以不同速率蒸发在空穴传输层(HTL)上形成厚度为20nm的发光层;
将HB-1蒸镀到发光层上得到厚度为20nm的空穴阻挡层(HBL);
将ET-1作为电子传输层材料(ET)蒸镀到空穴阻挡层(HBL)上得到厚度为30nm的电子传输层(ETL),在电子传输层(ETL)上方蒸镀厚度为2nm的LiQ形成电子注入层(EIL);
此后将镁(Mg)和银(Ag)以9:1的比例混合蒸镀得到厚度为15nm的阴极,在上述阴极封口层上沉积50nm厚度的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2-21
分别以本发明实施例2-21中的有机电致发光化合物2、3、6、13、17、19、23、25、33、37、42、49、51、58、69、81、87、99、130、143作为电子阻挡层材料,其他部分与应用例1一致,据此制作出应用例2-21的有机电致发光器件。
对照例
对照例与应用例1区别在于,使用EB-1作为电子阻挡层材料,其余与应用例1相同。
分别测试应用例1-21及对照例所制备的有机电致发光器件,测试结果如表1所示。
表2:
由上表2可知,将本发明有机电致发光化合物应用于有机电致发光器件中,作为电子阻挡层材料使用,器件发光效率得到较大幅度提升,启动电压下降,功耗相对降低。
将对照例及应用例1、2、5、6、7、10、14所制备的有机电致发光器件进行发光寿命测试,得到发光寿命T97%数据(发光亮度降低至初始亮度97%的时间),测试设备为TEO发光器件寿命测试***。结果如表3所示:
表3:
实验组 | 电流密度(mA/cm<sup>2</sup>) | T97%/h |
对照例 | 10 | 312 |
应用例1 | 10 | 344 |
应用例2 | 10 | 350 |
应用例5 | 10 | 348 |
应用例6 | 10 | 353 |
应用例7 | 10 | 359 |
应用例10 | 10 | 340 |
应用例14 | 10 | 342 |
由上表3可知,将本发明有机电致发光化合物应用于有机电致发光器件中,作为电子阻挡层材料使用,器件使用寿命得到很大程度提升,所以具有很广阔的应用前景。
Claims (12)
2.如权利要求1所述的有机电致发光化合物,其特征在于,Ar1、Ar2相同或不同,各自独立的为苯基、联苯基、吡啶基、嘧啶基、三嗪基、蒽基、萘基、菲基、氧芴基、硫芴基、咔唑基、N-苯基咔唑基、芴基、9,9-二甲基芴基、9,9-二苯基芴基、9-甲基-9-苯基芴基、9,9'-螺二芴基;
所述苯基、联苯基、吡啶基、嘧啶基、三嗪基、蒽基、萘基、菲基、氧芴基、硫芴基、咔唑基、N-苯基咔唑基、芴基、9,9-二甲基芴基、9,9-二苯基芴基、9-甲基-9-苯基芴基、9,9'-螺二芴基为未取代或其中的至少一个氢被氘、C1-C4的烷基、C1-C4的氘代烷基、苯基、氰基取代。
3.如权利要求2所述的有机电致发光化合物,其特征在于,当Ar1、Ar2同时为苯基时,m、n不同时为1。
4.如权利要求1所述的有机电致发光化合物,其特征在于,L为亚萘基或亚蒽基。
8.一种如权利要求1-5中任一项所述的有机电致发光化合物在制备有机电致发光器件中的应用。
9.一种有机电致发光器件,其特征在于,包括相对设置的阳极和阴极,以及设于所述阳极和所述阴极之间的功能层;所述功能层含有如权利要求1-5中任一项所述的有机电致发光化合物。
10.如权利要求7所述的有机电致发光器件,其特征在于,所述功能层包括:空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层,所述空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层中的至少一层含有如权利要求1-5中任一项所述的有机电致发光化合物。
11.如权利要求8所述的有机电致发光器件,其特征在于,所述空穴传输层、电子阻挡层、发光层中的至少一层含有如权利要求1-6中任一项所述的有机电致发光化合物。
12.一种OLED显示设备,其特征在于,含有如权利要求7所述的有机电致发光器件。
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CN115626915A (zh) * | 2022-11-14 | 2023-01-20 | 吉林奥来德光电材料股份有限公司 | 发光辅助材料及其制备方法、发光器件和发光装置 |
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