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CN111718367B - 一种有机发光材料及其制备方法与应用 - Google Patents

一种有机发光材料及其制备方法与应用 Download PDF

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CN111718367B
CN111718367B CN202010736332.1A CN202010736332A CN111718367B CN 111718367 B CN111718367 B CN 111718367B CN 202010736332 A CN202010736332 A CN 202010736332A CN 111718367 B CN111718367 B CN 111718367B
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toluene
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王辉
李建行
李明
徐迪
付远航
李龙
朱新财
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

本发明公开了一种有机发光材料，结构通式如式I所示：
Figure DDA0002605109110000011
其中，Ar1、Ar2、Ar3、Ar4、R1各自独立地选自氢、氘、烷基、芳基、杂芳基和及任意组合；a为1‑4的整数。本发明通过选择特定的杂环组合，得到的有机发光材料在用于有机电致发光器件后，可以提高空穴的传输效率，很好地阻挡了激子，使能级搭配契合，使器件中空穴和电子达到了均衡，从而可以使得降低器件的起动电压以及提高器件的发光效率和寿命。

Description

一种有机发光材料及其制备方法与应用
技术领域
本发明涉及有机发光材料技术领域，更具体的说是涉及一种有机发光材料及其制备方法与应用。
背景技术
有机电致发光器件具有全固态结构，有机电致发光材料是构成该器件的核心和基础，新材料的开发是推动电致发光技术不断进步的源动力。对原有材料制备和器件优化也是现在有机电致发光产业的研究热点，为制作效率高的有机发光器件，研究者逐渐把器件内的有机物层的机构从单层变为了多层结构。把有机电致发光器件设计为多层结构式是由于空穴和电子的迁移速度不同，适当的设计出空穴注入层，空穴传输层、激子阻挡层、发光层、空穴阻挡层、电子传输层及电子注入层，提高了空穴和电子的传输效率，使器件中空穴和电子达到了均衡，从而提高了发光效率。
但现阶段的空穴传输层、激子阻挡层或具备空穴传输层又具备激子阻挡层还存在迁移率不够快、能级和能量搭配不好、空穴的传输效率不高及不能很好的阻挡激子等问题，从而导致有机电致发光器件的起动电压高、效率低和器件寿命短等现象。
为此，能够提供一种性能优良的高效有机发光材料是本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明提供了一种有机发光材料及其制备方法与应用，本发明通过选择特定的杂环组合，得到的有机发光材料在用于有机电致发光器件后，可以提高空穴的传输效率，很好地阻挡了激子，使能级搭配契合，使器件中空穴和电子达到了均衡，从而可以使得降低器件的起动电压以及提高器件的发光效率和寿命。
为了达到上述目的，本发明采用如下技术方案：
一种有机发光材料，所述有机发光材料的分子结构通式如式I所示：
Figure BDA0002605109100000021
其中，Ar1、Ar2、Ar3、Ar4、R1各自独立地选自氢、氘、烷基、芳基、杂芳基或任意组合；
1≤a≤4，且a为整数。
优选地，R1与其所在环上其他取代基形成C6～C14芳环基团或C4～C18杂芳环基团；
或，R1与所在环形成C6～C14芳环基团或C4～C18杂芳环基团。
优选地，所述芳基为苯、联苯、三联苯、萘、蒽和芴中的一种或任意组合。
优选地，所述杂芳基为C3～C8的杂芳基。
优选地，所述烷基基为C1～C6的烷基。
具体地，所述有机电致发光材料选自以下结构中的任意一种：
Figure BDA0002605109100000031
Figure BDA0002605109100000041
Figure BDA0002605109100000051
Figure BDA0002605109100000061
Figure BDA0002605109100000071
Figure BDA0002605109100000081
上述所述一种有机发光材料的制备方法，包括如下步骤：
(1)在氮气保护下，将化合物A、化合物B、甲苯和叔丁醇钠混合均匀后，再依次添加三(二亚苄基丙酮)二钯和50％三叔丁基膦，然后在110℃下回流24h，反应完成后得反应液，冷却至室温，经层析、浓缩、淋洗、烘干后，得到中间体C；其中，所述化合物A、所述化合物B和所述中间体C的结构如下：
Figure BDA0002605109100000082
(2)在氮气保护下，在所述中间体C中依次加入化合物D、甲苯和叔丁醇钠混合均匀后，再依次添加三(二亚苄基丙酮)二钯和50％三叔丁基膦，然后在110℃下回流24h，反应完成后得反应液，冷却至室温，析出沉淀，经抽滤、淋洗、烘干后，得到有机发光材料；其中，所述化合物D的结构如下：
Figure BDA0002605109100000083
优选地，步骤(1)中所述化合物A、所述化合物B、所述叔丁醇钠、所述三(二亚苄基丙酮)二钯和所述50％三叔丁基膦的质量比为10:8.7:10.2:0.33:0.36，所述化合物A与所述甲苯的质量体积比为1g:20ml。
优选地，步骤(2)所述中间体C、所述化合物D、所述叔丁醇钠、所述三(二亚苄基丙酮)二钯和所述50％三叔丁基膦的质量比为9.5:5.48:6.1:0.19:0.22，且所述中间体C与所述甲苯的质量体积比为9.5g:200ml。
优选地，所述化合物A和化合物C中的X1、X2为卤素。
优选地，X1、X2为氯，溴。
优选地，所述层析的展开剂体积为二氯甲烷：石油醚＝2:1。
优选地，所述50％三叔丁基膦是三叔丁基膦和二甲苯配制而成。
上述一种有机发光材料的应用，其特征在于，上述所述的有机发光材料或上述所述制备方法制备的有机发光材料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：第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层；所述有机物层部分或全部包含上述所述的有机发光材料或上述所述制备方法制备的有机发光材料。
优选的，所述有机物层包括第一空穴传输层、第二空穴传输层或激子阻挡层，所述空穴传输层和激子阻挡层包含所述有机发光材料。
经由上述的技术方案可知，与现有技术相比，本发明的有益效果如下：本发明通过选择特定的杂环组合，得到的有机发光材料在用于有机电致发光器件后，可以提高空穴的传输效率，很好地阻挡了激子，使能级搭配契合，使器件中空穴和电子达到了均衡，从而可以使得降低器件的起动电压以及提高器件的发光效率和寿命，适于推广与应用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例提供了一种有机发光材料，其化学结构式为发明内容中的式L006，该有机发光材料的制备方法的反应路线如下：
Figure BDA0002605109100000101
其具体的制备方法包括以下步骤：
1)在氮气保护体系下，称取化合物A-06(35.52mmol，10g)，化合物B-06(35.52mmo1，8.7g)入反应体系中，加入200ml甲苯，加入10.2g叔丁醇钠，置换一次氮气，氮气保护下加入0.33g三(二亚苄基丙酮)二钯和0.36g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料A-06无剩余，然后冷却到25℃，用100g无水硫酸钠将反应液干燥，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝2:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体C-06(9.5g，产率为60％)；
中间体C-06的HPLC纯度大于99％。其质谱计算值为445.95，测试值为446.0，其元素分析计算值为C:80.80％；H:4.52％；Cl:7.95；N:3.14％；O:3.59％；元素分析测试值为：C:80.80％；H:4.50％；Cl:7.98；N:3.15％；O:3.60％。
2)在氮气保护体系下，称取中间体C-06(21.3mmol，9.5g)，化合物D-06(22.36mmo1，5.48g)入反应体系中，加入200ml甲苯，加入6.1g叔丁醇钠，置换一次氮气，氮气保护下加入0.19g三(二亚苄基丙酮)二钯和0.22g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料C-06无剩余，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用150ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到类白色粉末的有机发光材料L006(7.25g，产率为52％)。该有机发光材料的HPLC纯度大于99.5％，其质谱计算值为654.81，测试值为654.80；其元素分析计算值为：C:88.04％；H:5.23％；N:4.28％；O:2.44％元素分析测试值为：C:88.0％；H:5.20％；N:4.30％；O:2.45％。
实施例2
本实施例提供了一种有机发光材料，其化学结构式为发明内容中的式L033该有机发光材料的制备方法的反应路线如下：
Figure BDA0002605109100000111
其具体的制备方法包括以下步骤：
1)在氮气保护体系下，称取化合物A-33(35.52mmol，10g)，化合物B-33(35.52mmo1，10.14g)入反应体系中，加入200ml甲苯，加入10.2g叔丁醇钠，置换一次氮气，氮气保护下加入0.33g三(二亚苄基丙酮)二钯和0.36g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料A-33无剩余，然后冷却到25℃，用100g无水硫酸钠将反应液干燥，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝3:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体C-33(11.1g，产率为64.3％)；该中间体C-33的HPLC纯度大于99％；其质谱计算值为486.01；测试值为486.00。其元素分析计算值为：C:81.55％；H:4.98％；N:2.88％；Cl:7.29％；O:2.30元素分析测试值为：C:81.50％；H:5.00％；N:2.90％；Cl:7.30％；O:2.30。
2)在氮气保护体系下，称取中间体C-33(22.84mmol，11.1g)，化合物D-33(23.98mmo1，5.88g)入反应体系中，加入200ml甲苯，加入6.6g叔丁醇钠，置换一次氮气，氮气保护下加入0.2g三(二亚苄基丙酮)二钯和0.23g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料C-33无剩余，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用320ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到类白色粉末的有机发光材料L033(14.28g，产率为49％)；该有机发光材料的HPLC纯度大于99.5％；其质谱计算值为694.88；测试值为694.90。其元素分析计算值为：C:88.15％；H:5.51％；N:4.03％；O:2.30％；测试值为：C:88.18％；H:5.50％；N:4.00％；O:2.33％。
实施例3
本实施例提供了一种有机发光材料，其化学结构式为发明内容中的式L089，该有机发光材料的制备方法的反应路线如下：
Figure BDA0002605109100000131
其具体的制备方法包括以下步骤：
1)在氮气保护体系下，称取化合物A-89(30.16mmol，10g)，化合物B-89(30.16mmo1，7.4g)入反应体系中，加入200ml甲苯，加入8.7g叔丁醇钠，置换一次氮气，氮气保护下加入0.28g三(二亚苄基丙酮)二钯和0.31g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料A-89无剩余，然后冷却到25℃，用100g无水硫酸钠将反应液干燥，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入200ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝3:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体C-89(8.8g，产率为59％)；该中间体C-89的HPLC纯度大于99％；其质谱计算值为496.01；测试值为496.0。其元素分析计算值为：C:82.33％；H:4.47％；Cl:7.15；N:2.82％O:3.23％；元素分析测试值为C:82.30％；H:4.50％；Cl:7.18；N:2.80％O:3.25％。
2)在氮气保护体系下，称取中间体C-89(17.74mmol，8.8g)，化合物D-89(18.63mmo1，4.57g)入反应体系中，加入180ml甲苯，加入5.1g叔丁醇钠，置换一次氮气，氮气保护下加入0.16g三(二亚苄基丙酮)二钯和0.18g的50％三叔丁基膦，氮气保护下110℃回流24h，TLC点板监测原料C-89无剩余，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用250ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到类白色粉末的有机发光材料L089(6g，产率为48％)；该有机发光材料的HPLC纯度大于99.5％；其质谱计算值为704.84；测试值为704.8。其元素分析计算值为：C:88.61％；H:5.15％；N:3.97％；O:2.27％；测试值为：C:88.60％；H:5.18％；N:3.96％；O:2.25％；。
因结构通式为发明内容中的式I的其他化合物的制备方法的合成路线和原理均与上述所列举的实施例1～3的相同，所以在此不再穷举，本发明又选取8个化合物(发明内容中的式L005、L016、L020、L037、L046、L058、L078、L096)作为实施例，其对应质谱测试值和分子式如下表1所示。
表1 L005、L016、L020、L037、L046、L058、L078、L096的质谱测试值和分子式表
化合物的结构式 分子式 质谱计算值 质谱测试值 终产品产率
L005 C52H36N2O 704.87 704.90 46％
L016 C67H46N2O 895.12 895.10 48％
L020 C48H32N2O2 668.80 668.80 49％
L037 C57H42N2O 770.98 771.00 49％
L046 C50H34N2O 678.84 678.80 51％
L058 C51H38N2O 694.88 694.90 52％
L078 C54H34N2OS2 791.00 791.00 48％
L096 C52H34N2O2 718.86 718.90 49％
本发明实施例还提供了一种采用上述实施例提供的有机发光材料制备得到的有机电致发光器件，其中，该有机电致发光器件包括第一电极、第二电极以及至少一层设置在所述第一电极与第二电极之间的有机物层。
其中，有机物层可包含空穴注入层，空穴传输层、激子阻挡层、发光层、空穴阻挡层、电子传输层及电子注入层中一种或多种。
根据所使用的材料，本发明实施例提及的有机电致发光器件可为顶部发光型、底部发光型或双面发光型。另外，本发明实施例提供的有机发光材料还可用于利用与有机电致发光器件相似的原理的有机电子器件，譬如有机太阳能电池、有机光导体、有机晶体管等。
具体的，上述有机电致发光器件的制备方法可参照实施例4。
实施例4
该实施例提供了一种有机电致发光器件的制备方法，其包括以下步骤：
(1)将涂层厚度为
Figure BDA0002605109100000151
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30min，用蒸馏水反复清洗2次，超声波洗涤10min，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5min，接着，将ITO衬底安装在真空气相沉积设备的衬底夹持器上。将HI001引入到所述真空气相沉积设备的单元中，并且随后将所述设备的腔室中的压力控制为10-7托，此后，向所述单元施加电流以蒸发上述引入的材料，由此在ITO衬底上形成厚度为/>
Figure BDA0002605109100000152
的第一空穴注入层。接着，将HAT-CN引入所述真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第一空穴注入层上形成厚度为/>
Figure BDA0002605109100000153
的第二空穴注入层。接着，将如下的化合物HT001引入到真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第二空穴注入层上形成厚度为/>
Figure BDA0002605109100000154
的第一空穴传输层。接着，将化合物L006引入到真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第一空穴传输层上形成厚度为/>
Figure BDA0002605109100000161
的第二空穴传输层。此后，将化合物RH001引入到真空气相沉积设备的一个单元中作为主体，并且将化合物Ir(piq)2acac中的一种引入到另一个单元中作为掺杂剂。两种材料以不同速率蒸发且以按主体和掺杂剂的总量计重量3％的掺杂量沉积以在第二空穴传输层上形成厚度为/>
Figure BDA0002605109100000162
的发光层。随后，将ET001引入到一个单元中，并且Liq引入到另一单元中。使两种材料以相同速率蒸发，并且各自以50重量％的掺杂量沉积，以在发光层上形成厚度为/>
Figure BDA0002605109100000163
的电子输送层。随后，将Liq在电子传输层上沉积成厚度为/>
Figure BDA0002605109100000164
的电子注入层之后，通过另一个真空气相沉积设备在电子注入层上沉积厚度为/>
Figure BDA0002605109100000165
的Al阴极。由此，即可得到有机电致发光器件。用于制造OLED装置的所有材料在使用之前都通过在10-4托下真空升华而纯化。
其中，第一空穴注入层化合物HI001和第二空穴注入层化合物HAT-CN结构式为：
Figure BDA0002605109100000171
Figure BDA0002605109100000172
其中，第一空穴传输层化合物物HT001结构式为；
Figure BDA0002605109100000173
其中，主体物质化合物RH001和掺杂物质化合物Ir(piq)2acac的结构式为：
Figure BDA0002605109100000181
其中，电子传输层ET001和电子传输层和电子注入层Liq的化合物结构式为
Figure BDA0002605109100000182
参照上述实施例4提供的方法，分别选用化学结构式为式L033、L089、L005、L016、L020、L037、L046、L058、L078、L089、L096的有机发光材料替代结构式为式L006的有机发光材料进行蒸镀，并制备得到相应的有机电致发光器件。
对比例1
该对比例提供了一种有机电致发光器件，该有机电致发光器件的制备方法与实施例4的唯一区别在于，该有机电致发光器件的是采用现有有机化合物HT002替代L006进行蒸镀。
其中HT002化合物的结构式为：
Figure BDA0002605109100000191
将上述实施例4和对比例1得到的有机电致发光器件分别采用KEITHLEY 2400型源测量单元和PR670分光辐射亮度计及寿命测试仪测试其驱动电压、发光效率以及T95寿命等性能，其测试结果如下表2所示。
表2实施例4和对比例1测试结果
Figure BDA0002605109100000192
Figure BDA0002605109100000201
表2可以看出，使用本发明提供有机化合物做的有机电致发光器件与使用比较化合物对比例1做的有机电致发光器件相比，驱动电压明显降低，电流效率和寿命得到显著提高。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (6)

1.一种有机发光材料，其特征在于，所述有机发光材料的结构为：
Figure FDF0000024854800000011
2.一种权利要求1所述有机发光材料的制备方法，其特征在于，包括如下步骤：
(1)在氮气保护下，将化合物A、化合物B、甲苯和叔丁醇钠混合均匀后，再依次添加三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成后得反应液，冷却至室温，经层析、浓缩、淋洗、烘干后，得到中间体C；其中，所述化合物A、所述化合物B和所述中间体C的结构如下：
Figure FDF0000024854800000012
其中，X1和X2各自独立地选自氯或溴；
(2)在氮气保护下，在所述中间体C中依次加入化合物D、甲苯和叔丁醇钠混合均匀后，再依次添加三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成后得反应液，冷却至室温，析出沉淀，经抽滤、淋洗、烘干后，得到有机发光材料；其中，所述化合物D的结构如下：
Figure FDF0000024854800000021
其中，Ar1、Ar2、Ar3、Ar4各自独立地选自芳基；
且a＝1，R1为氢；
所述芳基为苯、联苯、萘和芴中的一种或任意组合。
3.根据权利要求2所述的一种有机发光材料的制备方法，其特征在于，步骤(1)中所述化合物A、所述化合物B、所述叔丁醇钠、所述三(二亚苄基丙酮)二钯和所述50％三叔丁基膦的质量比为10:8.7:10.2:0.33:0.36，所述化合物A与所述甲苯的质量体积比为1g:20ml。
4.根据权利要求2所述的一种有机发光材料的制备方法，其特征在于，步骤(2)所述中间体C、所述化合物D、所述叔丁醇钠、所述三(二亚苄基丙酮)二钯和所述50％三叔丁基膦的质量比为9.5:5.48:6.1:0.19:0.22，且所述中间体C与所述甲苯的质量体积比为9.5g:200ml。
5.一种有机发光材料的应用，其特征在于，权利要求1所述的有机发光材料或权利要求2-4任一所述制备方法制备的有机发光材料在制备有机电致发光器件中的应用。
6.一种有机电致发光器件，包括：第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层；其特征在于，所述有机物层包含权利要求1所述的有机发光材料或权利要求2-4任一所述制备方法制备的有机发光材料。
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