CN110272377B - 红绿蓝热活化延迟荧光材料，其合成方法及应用 - Google Patents
红绿蓝热活化延迟荧光材料，其合成方法及应用 Download PDFInfo
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Abstract
本发明涉及有机发光材料技术领域，具体涉及一种红绿蓝热活化延迟荧光材料，其合成方法及应用；所述红绿蓝热活化延迟荧光材料具有如下通式：
；本发明提供的红绿蓝热活化延迟荧光材料结构新颖，具有较低单三线态能级差，快速的反向系间窜越常数(kRISC)以及高的光致发光量子产率(PLQY)。热活化延迟荧光材料特性显著，使用寿命长，能够应用于量产的基于电致发光的显示和发光设备结构中。
Description
技术领域
本发明涉及有机发光材料技术领域，具体涉及一种红绿蓝热活化延迟荧光材料，其合成方法及应用。
背景技术
有机电致发光二极管(Organic Light Emitting Diode，简称OLED)，由美籍华裔教授邓青云等人发明的一种由电极/发光层/电极结构构成的三明治型器件。当有电流通过时，强电场会驱动器件电极中间的有机发光层发光。基于OLED的电致发光现象，OLED在信息显示和固体照明等领域有广泛应用。
有机发光材料的不断更新大大推动了OLED技术的发展。一般而言，荧光材料为第一世代，过渡金属配合物磷光材料为第二世代。作为第一世代的荧光材料虽然寿命较长，但发光效率低，在OLED中单重态和三重态的激子比例为 1:3，内部量子效率理论上限仅25％，极大的限制了荧光电致发光器件的应用。作为第二代的过渡金属配合物磷光材料，其单重态(singlet state)可藉由系统间跨越(intersystem crossing；ISC)移转至三重态(triplet state)，内部量子效率几近100％，但是磷光材料中需要采用Ir、Pt等贵重稀有金属进行掺杂，材料成本较高，寿命较短。
热活化延迟荧光(TADF)材料是一类新型低成本高效率的有机发光材料，被称为第三世代有机发光材料。通过巧妙的分子设计，使得分子具有较小的最低单三重能级差(ΔEST)，能够将三线态激子通过热激发反系间窜越转化为单线态激子辐射发光，从而突破传统荧光材料激子利用率25％的理论极限，实现100％的发光量子效率。由于涉及激子从三线态向单线态反系间窜越的过程，TADF材料通常表现出光化学的长寿命荧光现象(延迟荧光)，延迟荧光寿命可达到微秒至毫秒数量级，明显区别于传统荧光材料。TADF材料结合了有机荧光材料稳定性好以及过渡金属配合物磷光材料发光效率高的优点，具有广泛的应用前景，是目前的科研热点之一。
对于热活化延迟荧光材料而言，快速的反向系间窜越常数(kRISC)以及高的光致发光量子产率(PLQY)是制备高效率OLED的必要条件。目前，同时具备快速反向系间窜越常数(kRISC)以及高光致发光量子产率(PLQY)等特性，且能够应用于量产有机电致发光器件结构中的红绿蓝热活化延迟荧光材料还有待开发。
发明内容
本发明的首要目的在于提供一种红绿蓝热活化延迟荧光材料，发光效率高、使用寿命长。
为实现上述目的，本发明采用的技术方案如下：
一种符合如下通式的红绿蓝热活化延迟荧光材料：
其中，R为
中的一种。
本发明的另一个目的在于提供一种如上所述的红绿蓝热活化延迟荧光材料的合成方法，在惰性气体保护下，原料1和原料2在钯催化剂作用下发生 Buchwald–Hartwig偶联反应，得到所述红绿蓝热活化延迟荧光材料；
所述原料1的结构式如下：
所述原料2选自所述原料2选自咔唑、吩噁嗪、二甲基二苯胺中的一种；
所述原料1、原料2的投料比为1:(1～3)。
优选的，所述Buchwald–Hartwig偶联反应的反应温度为80～160℃，反应时间为12～48小时。
优选的，所述Buchwald–Hartwig偶联反应的反应溶剂为经过无水无氧处理的甲苯；所述钯催化剂选自醋酸钯、硝酸钯、硫酸钯、氯化钯中的至少一种。
优选的，所述Buchwald–Hartwig偶联反应结束后，需要对所得反应产物依次进行冷却、萃取、柱层析分离，得到红绿蓝热活化延迟荧光材料。
本发明的又一个目的在于提供一种如上所述的红绿蓝热活化延迟荧光材料或根据如上所述的合成方法制备出的红绿蓝热活化延迟荧光材料在有机电致发光中的应用。更具体的来说，本发明所述红绿蓝热活化延迟荧光材料可直接用于电致热激活延迟荧光器件的发光层，也可以作为发光客体材料，掺杂在能级匹配的主体材料中构成电致发光器件的发光层，或将所述热活化延迟荧光蓝光材料作为发光主体材料，掺杂在能级匹配的客体材料中构成电致发光器件的发光层。
具体的，所述电致热激活延迟荧光器件，包括叠加设置的衬底层、发光层和阴极层，所述发光层所用发光材料为上述红绿蓝热活化延迟荧光材料或根据上述合成方法制备出的红绿蓝热活化延迟荧光材料。
优选的，所述电致热激活延迟荧光器件还包括成形于衬底层上的空穴注入层，成形于空穴注入层上的传输层，以及设置于发光层和阴极层之间的电子传输层。
本发明还提供一种发光装置，包括前述的电致热激活延迟荧光器件。
本发明的有益效果在于：提供一种结构新颖的红绿蓝热活化延迟荧光材料，具有较低单三线态能级差，快速的反向系间窜越常数(kRISC)以及高的光致发光量子产率(PLQY)。热活化延迟荧光材料特性显著，使用寿命长，能够应用于量产的基于电致发光的显示和发光设备结构中。此外，本发明提供的合成方法简便易行，合成效率高。
附图说明
图1为本发明实施例1～3所得化合物1～3的分子轨道图；
图2为本发明实施例1～3所得化合物1～3在室温下，正己烷溶液中的光致发光光谱；
图3为本发明应用实施例中电致热激活延迟荧光器件的结构示意图。
具体实施方式
以下结合实施例1～3和应用实施例1～3来对本发明作进一步的说明。
实施例1：红绿蓝热活化延迟荧光材料的合成
合成路线如下：
向100mL二口瓶中加入原料1(1.47g，5mmol)，咔唑(1.00g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v， 2:1)分离纯化，得蓝白色粉末1.6g，产率84％。
所得产物，即化合物1的核磁氢谱数据为：1H NMR(300MHz,CD2Cl2,δ): 8.55(d,J＝6.9Hz,2H),7.93(d,J＝6.0Hz,2H),7.35-7.18(m,4H),2.50(s,6H). MS(EI)m/z:[M]+calcd for C22H14F3NO2,381.10；found,381.08.
实施例2：红绿蓝热活化延迟荧光材料的合成
合成路线如下：
向100mL二口瓶中加入原料1(1.47g，5mmol)，吩噁嗪(1.01g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v， 2:1)分离纯化，得绿色粉末1.5g，产率76％。
所得产物，即化合物2的核磁氢谱数据为：1H NMR(300MHz,CD2Cl2,δ): 7.14(d,J＝6.3Hz,2H),7.05-6.96(m,6H),2.50(s,6H).MS(EI)m/z:[M]+calcd for C22H14F3NO3,397.09；found,397.08.
实施例3：红绿蓝热活化延迟荧光材料的合成
合成路线如下：
向100mL二口瓶中加入原料1(1.47g，5mmol)，二甲基二苯胺(1.10g，6 mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL 冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷， v:v，2:1)分离纯化，得红色粉末1.6g，产率76％。
所得产物，即化合物3的核磁氢谱数据为：1H NMR(300MHz,CD2Cl2,δ): 7.15(d,J＝6.9Hz,4H),7.09(d,J＝6.6Hz,2H),2.50(s,6H),2.32(s,6H).MS(EI) m/z:[M]+calcdfor C22H20F3NO2,381.10；found,381.08.
实施例1～3所得化合物1～3的分子轨道图如附图1所示，由图1可以看出化合物1～3的HOMO与LUMO分布。具体来说，HOMO分布在电子给体上， LUMO分布在电子受体上，HOMO与LUMO具有较大的分离，如此可确保分子具有较小的单三线态能级。
采用对实施例1～3所得化合物1～3的电化学能级等参数进行测定，结果如下表1所示：S1通过室温荧光光谱测定，T1通过低温(77K)磷光光谱仪测定， HOMO与LUMO通过电化学氧化还原测定。
表1:化合物1～3的最低单重态(S1)、最低三重态能级(T1)、电化学能级
检测实施例1～3所得化合物1～3在室温下，正己烷溶液中的光致发光光谱，结果如图2所示。在图2中，从左到右所示波形分别为化合物1、化合物2 和化合物3的光致发光光谱图。由图2可以看出：化合物1～3随着电子给体的给电子能力增加，发光分子的电荷转移态能量越来越低，在光谱上表现为其对应的光谱逐渐红移。
应用实施例1:电致热激活延迟荧光器件
一种电致热激活延迟荧光器件，可按本领域已知方法制作，如按参考文献(Adv.Mater.2003,15,277.)公开的方法制作。具体方法为：在经过清洗的导电玻璃(ITO)衬底上，高真空条件下依次蒸镀HATCN，TCTA,主体材料：TADF 客体，TmPyPB，1nm的LiF和100nm的Al。
所述电致热激活延迟荧光器件的结构为：参阅附图3，包括衬底层1，在衬底层1上成形的空穴注入层2，在空穴注入层2上成形的传输层3，在传输层3 上成形的发光层4，在发光层4上成形的电子传输层5，在电子传输层5上成形的阴极层6。所述衬底层1采用玻璃或导电玻璃(ITO)，空穴注入层2采用 HATCN，传输层3采用TCTA，发光层4所用材料为本实施例1所得化合物1，传输层5采用TmPyPB，阴极层6采用氟化锂/铝。形成如下结构的器件1：ITO/HATCN(2nm)/TCTA(35nm)/DPEPO：化合物1(2％20nm)/TmPyPB(40 nm)/LiF(1nm)/Al(100nm)。
应用实施例2:电致热激活延迟荧光器件
采用应用实施例1的方法，不同之处在于，所述发光层4所用材料为本实施例2所得化合物2，形成如下结构的器件2：ITO/HATCN(2nm)/TCTA(35 nm)/mCBP：化合物2(6％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)。
应用实施例3:电致热激活延迟荧光器件
采用应用实施例1的方法，不同之处在于，所述发光层4所用材料为本实施例3所得化合物3，形成如下结构的器件3：
ITO/HATCN(2nm)/TCTA(35nm)/CBP：化合物3(10％40nm)/TmPyPB(40 nm)/LiF(1nm)/Al(100nm)。
对应用实施例1～3所得器件1～3的性能进行测试。器件的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400 Sourcemeter、Keithley 2000Currentmeter)完成的，电致发光光谱是由法国JY 公司SPEX CCD3000光谱仪测量的，测量环境为室温，大气环境。得到测试结果如表2所示：
表2:器件的性能测试数据
Claims (10)
1.一种符合如下通式的红绿蓝热活化延迟荧光材料：
其中，R为
中的一种。
2.一种根据权利要求1所述的红绿蓝热活化延迟荧光材料的合成方法，其特征在于：在惰性气体保护下，原料1和原料2在钯催化剂作用下发生Buchwald–Hartwig偶联反应，得到所述红绿蓝热活化延迟荧光材料；
所述原料1的结构式如下：
所述原料2选自咔唑、吩噁嗪、二甲基二苯胺中的一种；
所述原料1、原料2的投料比为1:(1～3)。
3.根据权利要求2所述的红绿蓝热活化延迟荧光材料的合成方法，其特征在于：所述Buchwald–Hartwig偶联反应的反应温度为80～160℃，反应时间为12～48小时。
4.根据权利要求2所述的红绿蓝热活化延迟荧光材料的合成方法，其特征在于：所述Buchwald–Hartwig偶联反应的反应溶剂为经过无水无氧处理的甲苯；所述钯催化剂选自醋酸钯、硝酸钯、硫酸钯、氯化钯中的至少一种。
5.根据权利要求2所述的红绿蓝热活化延迟荧光材料的合成方法，其特征在于：所述Buchwald–Hartwig偶联反应结束后，需要对所得反应产物依次进行冷却、萃取、柱层析分离，得到红绿蓝热活化延迟荧光材料。
6.一种根据权利要求1所述的红绿蓝热活化延迟荧光材料或根据权利要求2-5中任一项所述的合成方法制备出的红绿蓝热活化延迟荧光材料在有机电致发光中的应用。
7.根据权利要求6所述的应用，其特征在于：应用于电致热激活延迟荧光器件中。
8.根据权利要求7所述的应用，其特征在于：所述电致热激活延迟荧光器件包括叠加设置的衬底层(1)、发光层(4)和阴极层(6)，发光层(4)所用发光材料为权利要求1所述的红绿蓝热活化延迟荧光材料或根据权利要求2-5中任一项所述的合成方法制备出的红绿蓝热活化延迟荧光材料。
9.根据权利要求8所述的应用，其特征在于：所述电致热激活延迟荧光器件还包括成形于衬底层(1)上的空穴注入层(2)，成形于空穴注入层(2)上的传输层(3)，以及设置于发光层(4)和阴极层(6)之间的电子传输层(5)。
10.一种发光装置，其特征在于：包括权利要求7-9中任一项所述的电致热激活延迟荧光器件。
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