CN115215893A - 一种联萘类深蓝光有机材料及其制备方法和应用 - Google Patents
一种联萘类深蓝光有机材料及其制备方法和应用 Download PDFInfo
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- CN115215893A CN115215893A CN202210924683.4A CN202210924683A CN115215893A CN 115215893 A CN115215893 A CN 115215893A CN 202210924683 A CN202210924683 A CN 202210924683A CN 115215893 A CN115215893 A CN 115215893A
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- binaphthyl
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
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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,尤其涉及一种联萘类深蓝光有机材 料及其制备方法和应用。
背景技术
有机电致发光器件(Organic light-emitting devices,OLEDs)具有高发光效率、宽视角、低成本、快响应,高色纯度、节能等特点,因此在全彩显示和 固态照明领域的潜在应用引起了广泛关注。研究开发新型有机电致发光材料 对于实现高性能有机电致发光器至关重要。
在OLEDs研究中,红、绿、蓝三基色材料是实现全彩显示的必备条件。 蓝光材料不仅自身可以作为蓝发光材料,还可以通过色转换介质技术获得红 光和绿光。经过近几十年的发展,用于制作性能优良的有机电致发光器件的 红、绿光材料因其寿命长,发光效率高、性能稳定,基本满足规模化生产需 求及应用。而蓝光材料因具有较宽的能隙带,电荷注入能垒大,导致发光效 率低、热稳定性低、易结晶、成膜性差、化学纯度低等技术缺陷,因此要实 现稳定性好、效率高的蓝光材料还是一个比较大的挑战。目前,已报道的深 蓝光材料更是非常稀少,而深蓝光材料不仅可以实现更宽广的色域,还可以 有效降低显示器和照明设备的功耗。
发明内容
为了克服现有技术的缺点和不足,本发明的目的在于提供一种联萘类深 蓝光有机材料及其制备方法和应用,本发明的联萘类深蓝光有机材料以1,1′- 联萘为骨架结构,在其4,4′-位置引入三芳胺、四苯基硅或芴官能团。扭曲的 联萘骨架结构能有效抑制固态分子间的堆积获得无定型材料,还能控制分子 的共轭长度获得深蓝光有机材料。因此本发明的联萘类深蓝光有机材料具有 高热稳定性、成膜性好、化学纯度高和发光效率高等优点。
为实现上述目的,本发明采用如下技术方案:
一种联萘类深蓝光有机材料,所述联萘类深蓝光有机材料的分子结构通 式为:
其中,R1、R2为各自独立地选自三苯胺基、9,9-二甲基-2-芴基和四苯硅基 中的任意一种。
优选的,所述联萘类深蓝光有机材料为以下化学结构式中一种以上:
本发明提供了一种所述的联萘类深蓝光有机材料的制备方法,包括如下 步骤:
步骤S1:将化合物1、化合物2和碱源置于三口烧瓶中,加入有机溶剂, 搅拌混合均匀,氮气置换三口烧瓶中的空气。
步骤S2:加入催化剂,氮气置换三口烧瓶中的空气。
步骤S3:缓慢升温至回流反应6~10小时,经后处理得到所述联萘类衍生 物。
合成路线如下:
优选的,步骤S1中所述化合物1由4,4'-二溴-1,1'-联萘和所述R1基团的 硼酸制备得来。
优选的,步骤S1中所述化合物1、化合物2、碱源的摩尔比为1:(1-1.3): (2-4)。
优选的,步骤S2中所述催化剂的加入量为化合物1质量的4%-6%。
优选的,步骤S1中所述的有机溶剂为四氢呋喃、甲苯、1,4-二氧六环和 N,N-二甲基甲酰胺中的任意一种。
优选的,步骤S2所述催化剂为四(三苯基膦)钯或[1,1'-双(二苯基膦基)二 茂铁]二氯化钯。
本发明还公开了一种所述的联萘类深蓝光有机材料在有机电致发光器件 中的应用,所述的联萘类深蓝光有机材料在所述有机电致发光器件中用作有 机发光材料或空穴传输材料。
本发明还公开了一种有机电致发光器件,所述的有机电致发光器件包括 作为有机发光材料或空穴传输材料的权利要求1所述的联萘类深蓝光有机材 料。
本发明的设计合成策略选择联萘单元控制共轭长度从而获得高性能的深 蓝光有机材料。通过在联萘骨架的4,4′-位置引入三芳胺、四苯基硅或芴发色 团获得具有发光和空穴传输双重功能的新型材料。选择联萘作为新型材料的 骨架是由于其能够限制分子重结晶从而形成无定型材料。四苯基硅官能团具 有大的空间位阻效应以及通过隔断共轭结构获得高的三重态能级材料,另外, 其弱的吸电子能力能提高整个分子的电子传输能力。芴官能团能提高分子的 热稳定性和膜的形态稳定性。
与现有技术相比,本发明具有如下优点和有益效果:
(1)本发明的联萘类深蓝光有机材料以联萘为骨架结构,因联萘中自由旋 转的萘环以及联萘骨架和支链间的空间位阻,可以大大减少固态分子间的堆 积,同时也可抑制分子的重结晶,从而获得成膜性好及形态稳定的新型深蓝 光有机材料。
(2)本发明的联萘类深蓝光有机材料通过在1,1′-联萘的4,4′-位置变换不 同的芳香族取代基,调节发光材料的发光峰位置,获得新型深蓝光有机材料。
(3)本发明的联萘类深蓝光有机材料具有高的玻璃化温度和分解温度,进 而促进器件的性能和寿命。
(4)将本发明制备的联萘类深蓝光有机材料BNS和BNF应用于非掺杂的 OLED中,获得深蓝光发射器件,启动电压低,发光效率高。
附图说明
图1为联萘类深蓝光有机材料BFS、BNS和BNF的核磁共振氢谱图;
图1a为实施例1制备的联萘类深蓝光有机材料BFS的核磁共振氢谱图;图 1b为实施例2制备的联萘类深蓝光有机材料BNS的核磁共振氢谱图;图1c 为实施例3制备的联萘类深蓝光有机材料BNF的核磁共振氢谱图。
图2为联萘类深蓝光有机材料BFS、BNS和BNF的核磁共振碳谱图;
图2a为实施例1制备的联萘类深蓝光有机材料BFS的核磁共振碳谱图;图 2b为实施例2制备的联萘类深蓝光有机材料BNS的核磁共振碳谱图;图2c 为实施例3制备的联萘类深蓝光有机材料BNF的核磁共振碳谱图。
图3为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF的热 力学曲线图;图3a为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和 BNF的差示扫描量热曲线(DSC)图;图3b为实施例1-3制备的联萘类深蓝光 有机材料BFS、BNS和BNF的热失重曲线(TGA)图。
图4为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF的归 一化紫外-可见吸收光谱图。
图5为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF的归 一化发射光谱图;图5a为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS 和BNF在二氯甲烷溶液(10- 5mol/L)中归一化荧光发射光谱图;图5b为实施例 1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF在薄膜态下的归一化荧 光发射光谱图;图5c为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS 和BNF在二氯甲烷溶液(10-5mol/L)中,温度77K下的归一化低温磷光发射光谱图。
图6为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF的氧 化曲线图。
图7为实施例1-3制备的联萘类深蓝光有机材料BFS、BNS和BNF的 HOMO和LUMO分布图。
图8为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为发 光材料的非惨杂器件的电流密度-电压-亮度曲线。
图9为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为发 光材料的非惨杂器件的电流效率-亮度曲线。
图10为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为 发光材料的非惨杂器件的外量子效率-亮度曲线。
图11为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为 发光材料的非惨杂器件的归一化电致发光强度-波长曲线。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面对本发明 的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于 充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施, 本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明 不受下面公开的具体实施例的限制。
下面结合附图对本发明实施例一种联萘类深蓝光有机材料及其制备方法 和应用进行详细的描述。
实施例1联萘类深蓝光有机材料BFS
一种联萘类深蓝光有机材料BFS,其结构如下:
所述联萘类深蓝光有机材料BFS的制备方法,包括如下步骤:
步骤一,三苯基-4-溴苯基硅烷(1)的制备:
250mL三口烧瓶中加入10.0g(0.04mol)1,4-二溴苯和140ml无水四氢 呋喃,开启磁力搅拌,用乙醇/干冰浴冷却到-78℃,在氮气保护下,缓慢滴加 17.2ml(2.5M)正丁基锂,维持体系的温度在-78℃下反应1小时后。快速加 入13.8g(0.05mol)三苯基氯硅烷,在此温度下继续反应2小时,升至室温 反应12小时以上。减压浓缩,得到粗品用硅胶(200-400目)作固定相,石油 醚作洗脱机柱层析,得白色固体12.1g,收率:67.7%,mp:161.2-164.4℃。
化合物1核磁共振氢谱和元素分析结果如下:
1H NMR(400MHz,CDCl3,TMS)δ:7.64–7.49(m,8H);7.46–7.34(m,11 H)。Anal.calcd.for C24H19BrSi(%):C,69.39;H,4.61.Found:C,69.73;H,3.57。
步骤二,4-(三苯基硅烷)苯硼酸(2)的制备:
250ml三颈瓶中加入11.5g(0.03mol)化合物1和120ml无水四氢呋喃, 开启磁力搅拌,通氮气除氧并用乙醇/干冰浴冷却到-78℃,半小时后逐滴滴加 14.5ml(2.5M,0.04mol)正丁基锂,维持反应在-78℃下反应1小时,然后快 速加入9.5ml(0.08mol)三甲基硼酸酯,在此温度下继续4小时,升至室温。 用冰盐浴冷却到0℃,缓慢滴加126ml(2.0M)盐酸,升至室温继续反应6小 时;用乙醚萃取3次合并有机相,减压蒸干,所得固体用硅胶(200-400目)作 固定相,石油醚和乙酸乙酯(体积比:4:1)作洗脱机柱层析,获得白色固体 9.1g,收率:85.5%,mp:231-234℃。
化合物2核磁共振氢谱分析结果如下:
1H NMR(400MHz,CDCl3)δ8.19(d,J=8.0Hz,1H),7.70(dt,J=14.1,7.6 Hz,2H),7.63–7.54(m,8H),7.47–7.35(m,10H)。
步骤三,4,4′-二溴-1,1′-联萘(3)的制备:
将3.05g(0.012mol)联萘、96ml氯仿加入到150ml三颈瓶中,开启磁 力搅拌,用冰盐浴冷却至0℃,在避光条件下缓慢滴加2.9ml(0.056mol)溴, 滴加完毕后在0℃下继续反应4小时。用NaHSO3水溶液淬灭,用氯仿萃取 三次,有机相依次NaHSO3水溶液、2mol的氢氧化钠水溶液和去离子水洗涤, 有机相用无水硫酸钠干燥减压蒸干,所得固体用氯仿重结晶,获得白色针状 晶体3.1g,收率:62.6%,mp:210.5-211.5℃。
化合物3核磁共振氢谱分析结果如下:
1H NMR(500MHz,CDCl3)δ8.39(d,J=8.5Hz,2H),7.93(d,J=7.5Hz,2 H),7.64–7.61(m,2H),7.37–7.33(m,6H)。
步骤四,2-[4′-溴(1,1′-联萘)-4-]-9,9-二甲基芴(4)的制备:
将1.99g(4.8mmol)化合物3、1.0g(4.2mmol)9,9-二甲基芴-2-硼酸、30ml 甲苯、10ml乙醇和5.04ml(2.5M)碳酸铯水溶液加入到100ml三颈瓶中, 通氮气除氧30分钟后,快速加入0.24g(0.21mmol)四三苯基磷钯,继续通 氮气30min,然后加热回流5小时,冷却至室温后过滤,液相减压蒸馏,所 得固体用硅胶(200-400目)作固定相,石油醚和乙酸乙酯(40:1)作洗脱机柱层 析,获得化合物4(白色粉末)1.40g,收率:63.4%。
化合物4核磁共振氢谱分析结果如下:
1H NMR(400MHz,CDCl3)δ8.10(d,J=8.4Hz,1H),7.97(dd,J=8.4,4.4 Hz,2H),7.89(d,J=8.0Hz,1H),7.83–7.81(m,1H),7.68(d,J=0.8Hz,1H), 7.63–7.29(m,13H),1.58(s,6H)
步骤五,化合物BFS的制备:
将1.00g(1.9mmol)化合物4、0.79g(2.09mmol)化合物2、30ml甲苯、10 ml乙醇和2.28ml(2.5M)碳酸铯水溶液加入到100ml三颈瓶中,通氮气除氧 30分钟后,快速加入0.11g(0.95mmol)四三苯基磷钯,继续通氮气30min, 然后加热回流12小时,冷却至室温后过滤,液相减压蒸,所得固体用硅胶 (200-400目)作固定相,石油醚和乙酸乙酯(50:1)作洗脱机柱层析,获得化合 物BFS(白色粉末)1.05g,收率:70.6%。
图1a为实施例1制备的联萘类深蓝光有机材料BFS的核磁共振氢谱图;
图2a为实施例1制备的联萘类深蓝光有机材料BFS的核磁共振碳谱图,其核 磁和元素分析结果如下:
1H NMR(600MHz,CDCl3)δ8.10(dd,J=19.2,8.4Hz,2H),7.89(d,J= 7.8Hz,1H),7.82(d,J=7.2Hz,1H),7.76(d,J=7.2Hz,2H),7.69–7.58(m,16 H),7.50–7.32(m,16H),1.58(s,6H).13C NMR(151MHz,CDCl3)δ153.91, 140.62,139.97,138.29,138.01,136.45,134.27,133.28,133.10,131.85,131.59, 129.72,129.13,127.98,127.55,127.35,127.09,126.59,126.38,125.93,124.63, 122.70,120.13,119.82,47.04,42.01,27.16.Anal.calcd.for C59H44Si(%):C, 90.73;H,5.68.Found:C,90.13;H,6.12。
实施例2,联萘类深蓝光有机材料BNS
一种联萘类深蓝光有机材料BNS,其结构如下:
所述联萘类深蓝光有机材料BNS的制备方法,包括如下步骤:
步骤一,4-(4′-溴-[1,1′-联萘]-4)-9,9-二甲基芴(5)制备:
将1.57g(3.80mmol)化合物3、1.0g(3.46mmol)4-(二苯胺)苯硼酸、30ml 甲苯、10ml乙醇和4.15ml(2.5M)碳酸铯水溶液加入到100ml三颈瓶中, 通氮气除氧30分钟后,快速加入0.20g(0.17mmol)四三苯基磷钯,继续通 氮气30min,然后加热回流5小时,冷却至室温后过滤,液相减压蒸馏,所 得固体用硅胶(200-400目)作固定相,石油醚和乙酸乙酯(40:1)作洗脱机柱层 析,获得化合物5(白色粉末)1.30g,收率:65.2%。
化合物5核磁共振氢谱分析结果如下:
1H NMR(400MHz,CDCl3)δ8.37(d,J=8.4Hz,1H),8.13(d,J=8.4Hz,1 H),7.91(d,J=7.6Hz,1H),7.60(ddd,J=8.4,6.8,1.2Hz,1H),7.55–7.28(m, 15H),7.24–7.21(m,5H),7.09–7.05(m,2H)。
步骤二,化合物BNS的制备:
将1.00g(1.73mmol)化合物5、0.79g(2.09mmol)化合物2、30ml甲苯、 10ml乙醇和2.08ml(2.5M)碳酸铯水溶液加入到100ml三颈瓶中,通氮气 除氧30分钟后,快速加入0.10g(0.87mmol)四三苯基磷钯,继续通氮气30 min,然后加热回流12小时,冷却至室温后过滤,液相减压蒸,所得固体用 硅胶(200-400目)作固定相,石油醚和乙酸乙酯(50:1)作洗脱机柱层析,获得 化合物BFS(白色粉末)0.62g,收率:42.3%。
图1b为实施例2制备的联萘类深蓝光有机材料BNS的核磁共振氢谱图;
图2b为实施例2制备的联萘类深蓝光有机材料BNS的核磁共振碳谱图;其 核磁、高分辨质谱和元素分析结果如下:
1H NMR(600MHz,CDCl3)δ8.13(d,J=8.4Hz,1H),8.07(d,J=8.4Hz,1 H),7.75(d,J=7.8Hz,2H),7.68–7.55(m,16H),7.48–7.42(m,14H),7.33–7.30 (m,5H),7.24–7.22(m,4H)7.06(t,J=7.2Hz,2H).13C NMR(151MHz,CDCl3) δ147.81,147.13,136.51,136.39,134.70,134.27,133.25,133.08,131.58,130.98, 129.72,129.36,127.98,127.58,127.54,127.05,126.57,126.45,126.39,126.33, 125.95,125.89,125.84,124.61,123.29,123.03.HRMS calcd for C62H46NSi [M+H]+:832.3394.Found:832.3388.Anal.calcd.for C62H45NSi(%):C,89.49;H, 5.45;N,1.68.Found:C,88.47;H,5.79;N,1.73。
实施例3,联萘类深蓝光有机材料BNF
一种联萘类深蓝光有机材料BNF,其结构如下:
所述联萘类深蓝光有机材料BNS的制备方法如下:
将1.00g(1.73mmol)化合物5、0.46g(1.91mmol)9,9-二甲基芴-2-硼酸、 30ml甲苯、10ml乙醇和2.08ml(2.5M)碳酸铯水溶液加入到100ml三颈瓶 中,通氮气除氧30分钟后,快速加入0.10g(0.87mmol)四三苯基磷钯,继 续通氮气30min,然后加热回流12小时,冷却至室温后过滤,液相减压蒸, 所得固体用硅胶(200-400目)作固定相,石油醚和乙酸乙酯(50:1)作洗脱机柱 层析,获得化合物BFS(白色粉末)1.10g,收率:91.9%。
图1c为实施例3制备的联萘类深蓝光有机材料BNF的核磁共振氢谱图;
图2c为实施例3制备的联萘类深蓝光有机材料BNF的核磁共振碳谱图;其 核磁、高分辨质谱和元素分析结果如下:
1H NMR(600MHz,CDCl3)δ8.13(dd,J=15.6,8.4Hz,2H),7.89(d,J= 7.2Hz,1H),7.82(d,J=6.6Hz,1H),7.69(s,1H),7.64–7.57(m,7H), 7.50–7.31(m,13H),7.24(t,J=7.2Hz,6H),7.07(t,J=7.2Hz,2H),1.58(s,6 H).13C NMR(151MHz,CDCl3)δ153.91,147.81,140.57,139.86,138.44,138.10, 137.86,134.70,133.32,131.85,131.78,130.99,129.36,129.13,127.57,127.34, 127.10,126.60,126.47,126.40,125.93,125.84,124.62,123.28,123.03,122.69, 120.13,119.81,47.04,27.28.HRMS calcd for C53H40N[M+H]+:690.3155.Found: 690.3154.Anal.calcd.for C53H39N(%):C,92.27;H,5.70;N,2.03.Found:C, 91.30;H,5.71;N,2.35。
下面对实施例1、实施例2和实施例3制备的联萘类深蓝光有机材料BFS、 BNS和BNF进行性能测试。
(1)热力学性质
由DSC曲线图3a可知,实施例1-3制备的三个深蓝光有机材料BFS、 BNS和BNF都具有较高玻璃转化温度(Tg>140℃)。Tg越高,有利于蒸镀制备 OLED器件过程中形成均匀的非晶态薄膜以及器件工作时的热稳定性。
由TGA曲线图3b可知,实施例1-3制备的三个深蓝光有机材料BFS、 BNS和BNF都具有较高的热分解温度(Td>440℃)。如此高的热分解温度保证 了它们在真空蒸镀过程中的稳定性。
(2)光物理性能
由紫外-可见吸收光谱图4可知,实施例1-3制备的三个深蓝光有机材料 BFS、BNS和BNF有相似的吸收轮廓,其主要有两个吸收带,217-263nm范 围内的窄吸收带归因于联萘骨架的π-π*跃迁所致;363-397nm范围内的宽吸 收带归因于三芳胺的n-π*跃迁或芳香烃的π-π*跃迁所致。根据紫外-可见吸收 光谱的起始吸收波长计算其光学带隙分别为3.27eV,3.13eV和3.12eV。
图5a为实施例1-3制备的三个深蓝光有机材料BFS、BNS和BNF在二 氯甲烷溶液(10-5mol/L)中的荧光发射光谱,三个深蓝光材料的最大发射波长分 别为416nm、453nm和454nm,都属于深蓝光发射。与BFS相比,BNS和BNF 发射峰发生了轻微的红移,这可能是由于三芳胺官能团的强电子供体特征。
图5b为实施例1-3制备的三个深蓝光有机材料BFS、BNS和BNF在薄 膜态下荧光发射光谱图,三个深蓝光材料的最大发射波长分别为419nm、436 nm和442nm,都属于深蓝光发射。对比图5a和5b可知,在薄膜状态下BFS 的发射光谱相比于在二氯甲烷溶液中的发射有轻微的红移,这可能是固态堆 积效应所致。在薄膜状态下BNS和BNF的发射光谱相比于在二氯甲烷溶液中 的发射发生了蓝移,这可能是由分子间激基复合物的形成所致,这种现象是由高度扭曲的刚性结构和分子的空间位阻引起的,有助于减少聚集态的分子 间相互作用。根据荧光发射光谱最大吸收波长计算其单线态能级分别为2.98 eV、2.74eV和2.73eV。
图5c为实施例1-3制备的三个深蓝光有机材料BFS、BNS和BNF在二 氯甲烷溶液(10-5mol/L)中,温度77K下的归一化低温磷光发射光谱图,根据 磷光发射光谱最大发射波长计算其三线态能级分别为2.73eV、2.73eV和2.51 eV。
(3)电化学性能
图6为实施例1-3制备的三个深蓝光有机材料BFS、BNS和BNF的氧化 曲线图,根据氧化曲线的起始氧化电位可计算其HOMO能级分别为-6.23eV、 -6.09eV和-5.95eV,根据HOMO和光学带隙之差可计算其LUMO能级分别 为-2.96eV、-2.96eV和-2.47eV。
(4)理论计算
为了更好的理解实施例1-3制备的三个深蓝光有机材料BFS、BNS和
BNF 的电子结构与光学性能之间的关系,基于B3LYP/6-3G(d)基组利用密度泛函理论方法模拟得到了优化的分子几何结构和前沿分子轨道。由图7优化的分 子几何结构可知,三个深蓝光有机材料BFS、BNS和BNF两个萘环之间的二 面角分别为69.6°,70.6°和70.2°,由于萘环之间的自由旋转,三个深蓝光有 机材料呈现扭曲的非平面结构,从而导致更好的共轭限制;三个有机材料的 骨架和支链之间的二面角范围为54.0–55.9°,这可能是骨架与支链间的严重空 间排斥所致,三个有机材料扭曲的几何结构可通过阻止分子堆积抑制红移以 及提高提高分子的形态稳定性。
由图7的前沿分子轨道电子云分布可知,BFS的HOMO和LUMO能级 的电子云几乎全部分布在联萘骨架和芴官能团上,这种HOMO和LUMO能 级电子云的重叠有利于高效发光。BNS和BNF的HOMO能级电子云主要分 布在三芳胺官能团上,一小部分延伸到联萘骨架上,这可能是由三芳胺的强 供电子特征所致。相反,BNS的LUMO能级电子云主要分布在联萘骨架上, BNF的LUMO能级电子云分布在联萘骨架和芴官能团上,这可能是缺电子的 联萘骨架和芴官能团所致。这种HOMO和LUMO能级电子云一定程度的分 离有利于载子的平衡传输。计算得到BFS、BNS和BNF的HOMO/LUMO能 级分别为-5.40/-1.31eV,-4.93/-1.25eV和-4.92/-1.27eV。
(5)有机电致发光器件性能
下面对实施例2和3制备的联萘类深蓝光有机材料BNS和BNF进行器 件性能测试,将其作为发光材料,采用真空蒸镀法制备非掺杂有机电致发光 器件,器件结构如下:ITO/HAT-CN(30nm)/NPB(50nm)/BNS、BNF(50 nm)/Alq3(15nm)/LiF(1nm)/Al。
上述提及的各材料的具体分子结构如下:
图8为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为发 光材料的非惨杂器件的电流密度-电压-亮度曲线。
图9为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为发 光材料的非惨杂器件的电流效率-亮度曲线。
图10为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为 发光材料的非惨杂器件的外量子效率-亮度曲线。
图11为实施例2和3制备的联萘类深蓝光有机材料BNS和BNF作为 发光材料的非惨杂器件的归一化电致发光强度-波长曲线。
器件性能测试的具体数据见表1。
表1器件性能测试的具体数据
由表1可知,选用本发明的有机材料作为OLED器件的发光材料,对比 已有材料的应用的OLED器件,器件的启动电压低,发光效率高等优点,在 OLED器件应用上有很大的应用价值和商业价值。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受所述 实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、 修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护 范围之内。
Claims (10)
4.根据权利要求3所述的联萘类深蓝光有机材料的制备方法,其特征在于,步骤S1中所述化合物1由4,4’-二溴-1,1’-联萘和所述R1基团的硼酸制备得来。
5.根据权利要求3所述的联萘类深蓝光有机材料的制备方法,其特征在于,步骤S1中所述化合物1、化合物2、碱源的摩尔比为1:(1-1.3):(2-4)。
6.根据权利要求3所述的联萘类深蓝光有机材料的制备方法,其特征在于,步骤S2中所述催化剂的加入量为化合物1质量的4%-6%。
7.根据权利要求3所述的联萘类深蓝光有机材料的制备方法,其特征在于,步骤S1中所述的有机溶剂为四氢呋喃、甲苯、1,4-二氧六环和N,N-二甲基甲酰胺中的任意一种。
8.根据权利要求3所述的联萘类深蓝光有机材料的制备方法,其特征在于,步骤S2所述催化剂为四(三苯基膦)钯或[1,1'-双(二苯基膦基)二茂铁]二氯化钯。
9.一种如权利要求1或2任一项所述的联萘类深蓝光有机材料在有机电致发光器件中的应用,其特征在于,所述的联萘类深蓝光有机材料在所述有机电致发光器件中用作有机发光材料或空穴传输材料。
10.一种有机电致发光器件,其特征在于,所述的有机电致发光器件包括作为有机发光材料或空穴传输材料的权利要求1所述的联萘类深蓝光有机材料。
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