CN111808076A - 一种电子传输空穴阻挡有机材料及其在薄膜发光二极管应用 - Google Patents
一种电子传输空穴阻挡有机材料及其在薄膜发光二极管应用 Download PDFInfo
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- CN111808076A CN111808076A CN201910290885.6A CN201910290885A CN111808076A CN 111808076 A CN111808076 A CN 111808076A CN 201910290885 A CN201910290885 A CN 201910290885A CN 111808076 A CN111808076 A CN 111808076A
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- Electroluminescent Light Sources (AREA)
Abstract
提供一种以A‑D‑A链接结构为核心的电子传输、空穴阻挡材料应用于薄膜半导体发光二极管,如有机发光二极管及量子点薄膜发光二极管,材料分子以呈双极性咔唑及其衍生物基团作为给电子中心,可以保持较高的三线态能级来保证激子阻挡能力。
Description
技术领域
本发明涉及有机半导体材料及其在半导体薄膜发光器件的应用,具体涉及有机半导体作为电子传输层、空虚阻挡层和发光层应用,可提高发光效率,延长器件工作寿命。
背景技术
随着多媒体技术的发展和信息社会的来临,对平板显示器性能的要求越来越高。近年新出现的三种显示技术:等离子显示器、场发射显示器和有机电致发光显示器(OLED),均在一定程度上弥补了阴极射线管(CRT)和液晶显示器(LCD)的不足。其中,OLED具有自主发光、低电压直流驱动、全固化、视角宽、颜色丰富等一系列的优点,与液晶显示器相比,OLED不需要背光源,视角大,功耗低,其响应速度比液晶显示器快1000倍,其制造成本却低于同等分辨率的液晶显示器,因此,有机电致发光二极管(OLEDs)平板显示作为新一代显示器和照明潜在应用而引起广泛注意,其应用前景十分广阔。有机电致发光器件是自发的发光器件,OLED发光的机理是在外加电场作用下,电子和空穴分别从正负两极注入后在有机材料中迁移、复合并衰减而产生发光。OLED的典型结构包括阴极层、阳极层,和位于这两层之间的有机薄膜层,有机薄膜层中可包括电子注入层、电子传输层、空穴阻挡层、空穴传输层、空穴注入层和有机发光层中的一种或几种功能层。自从EastmanKodakCompany的
C.W.Tang(C.W.Tang和S.A.Vans lyke,AppliedPhysics Letters,Volume 51,P913,1987)报导了低电压驱动的层叠型有机电致发光器件以来,人们对利用有机材料作为组成材料的有机电致发光器件已经进行了很多研究(U.S.Pat.Nos.5,141,671;4,539,507;6,020,078;5,935,720;5,972,247;5,593,788;4,885,211;5,059,862;5,104,740;5,069,975;5,126,214;5,389,444;6,165,383;6,245,449;6,861,162B2;6,833,202B2;Chen,ShiandTang,Macromol.Symp.,1997,125,1;Segura,Acta.Polym.,1998,49,319;MitschkeandBauerle,J.Mater.Chem.2000,10,1471)。然而,尽管有机电致发光的研究进展非常迅速,但是仍然有很多问题急需解决,如:外量子效率(EQE)的提高,色纯度更高的新材料的设计与合成、高效电子传输/空穴阻挡新材料的设计与合成等。对于有机电致发光器件来说,器件的发光量子效率是各种因素的综合反映,也是衡量器件品质的一个重要指标。一般来说,造成器件EQE低的一个主要原因,是由发光材料的电荷注入与传输不平衡引起的。同时,这种不平衡也严重地影响器件的稳定性,器件的色标,使器件达不到实用化的要求。如果不能达到平衡,则电流将作无效的(不发光)流动,或增加器件的工作电压。例如,如果我们不能使载流子的复合局域于器件内某些希望的区域(通常是发光层),而使之发生于容易猝灭的电极和工作物质的界面处,则器件发光的量子效率将大大降低。要克服这一困难必须使两个电极及工作物质界面层处的势垒有一种合理的安排。势垒的产生是因正(或负)电极的功函数与工作物质的离子化电位(或电子亲和能)间存在差异而引起的,为了要保证载流子的注入能在较低的驱动电压下进行,一般说来要求这些势垒不能太高。为此,必须对势垒的高低作一定的预测。但遗憾的是有关这些工作物质的离子化电位(IP)或电子亲和能(EA)在文献中报道甚少,而通过理论计算得到的数值一般比较分散,这就难以选择合适的电子传输/空穴阻挡新材料使之与电极材料相匹配。由于很多有机材料能有效地传输空穴,所以为了提高器件的发光效率,在很多情况下,往往在阴极一侧额外加一层电子传输/空穴阻挡层,以阻挡空穴传输,将载流子复合限制在发光层区域。2,9-二甲基-4,7-二苯基-1,10-邻二氮杂菲(BCP)和1,3,5-三(N-苯基-2-苯并咪唑)苯(TPBI)是广泛应用于电致发光器件中的电子传输/空穴阻挡材料,但其在器件中稳定性有待进一步提高。另外的空穴阻挡材料是双(2-甲基-8-羟基喹啉)(4一苯酚基)铝((II1)(BAIq)。其器件的寿命和稳定性都能得到显著改善,但是缺点是含有BAlq器件的发光效率比含有BCP(T.Watanabe et al.,Proc.SPIE2001,4105,175)器件的发光效率显著的低(约40%)。因此,尽管BAlq能够实现良好的寿命,但总的说来不是令人满意的空穴阻挡材料,其原因是所制备的器件效率太低。
发明内容
本发明的目的之一,是提供一种以A-D-A链接结构为核心的电子传输、空穴阻挡材料应用于薄膜半导体发光二极管,如有机发光二极管及量子点薄膜发光二极管,材料分子以呈双极性咔唑及其衍生物基团作为给电子中心,可以保持较高的三线态能级来保证激子阻挡能力。材料分子在咔唑9位氮原子上链接吸电子基团,已有不少报道,构成的是A-D结构模式,可以调节LUMO能级,适应不同器件结构需求,但往往会造成器件应用驱动电压升高,或是带来三线态降低而限制其应用。材料分子在咔唑的4位或3位上引入第二个吸电基团,可以灵活的调整HOMO能级而最大限度地保持原有的LUMO能级。综合以上三点设计思路,同时在咔唑或其衍生基团9-位与4位或3位上引入第二个、甚至第三个吸电基团,设计并合成了系列A-D-A链接结构化学物。本发明制作的器件具有良好的光电性能,能够满足面板制造企业的要求。
本发明解决上述技术问题的技术方案为:披露一种有机半导体化合物,采用双极性咔唑或其融合衍生物作为给电性基团,同时在其9位与另一其它位引入相同或不同的吸电性基团EWG1及EWG2构成有机半导体材料,其特征在于,包括具有符合式(1)所示的分子结构:
其中R1~R4可独立为H、碳原子数为小于18的烷基、碳原子数小于18的环烷基、碳原子数小于18的烷氧基、碳原子小于60的芳基、碳原子小于60的芳杂基、碳原子小于60的芳杂融合基;其中EWG1、EWG2均为N杂环类吸电性基团,两者可以相同也可以不相同。其特征在于,所述EWG1、EWG2选自如下结构式之一:
其中,R1-R11为H、碳原子数为小于18的烷基、碳原子数小于18的环烷基、碳原子数小于18的烷氧基、碳原子小于60的芳基、碳原子小于60的芳杂基、碳原子小于60的芳杂融合基。
根据本发明所述范围,在通式(1)与EW1、EW2组合中,有许多不同结构,具体所述的有机半导体化合物,包括但不限于如下结构:
以上有机化合物可以应用于半导体薄膜发光二极管,如有机发光二极管及量子点薄膜发光二极管,其特征是所述的半导体发光层中含有本发明所述结构的化合物作为电子传输空穴阻挡材料。
在研究荧光小分子化合物的电子结构时,电子间相互影响是非常重要的,密度泛函理论(DFT)已经被广泛用于研究π共轭体系,且采用DFT方法研究本公开的化合物的结果要比其他的方法更为准确。对所研究的化合物分子的基态、阳离子态和阴粒子态下的几何结构的优化,采用DFT//B3LYP/6-31G(d)的方法,这些化合物的激发态的优化几何结构采用DFT//B3LYP/6-31G(d)的方法获得的。在基态和激发态几何结构的基础上,采用含时密度泛函理论(TDDFT)方法计算了这些化合物的吸收和发射光谱。通过上述的计算方法,可以获得所研究化合物的各种性质,包括电离能IP,电子亲和势EA,重组能λ,最高占据轨道HOMO,最低占据轨道LUMO,能隙Eg。
以如上方法计算本发明具体实施方式中制备的两个化合物HOMO能级、LUMO能级,HOMO和LUMO的电子云分布,以及S1能级和T1能级。
表1.高斯计算结果
通常而言,引入吸电性基团可以同时使材料的HOMO/LUMO能级均降低,如果吸电基团与HOMO电子云分布的基团链接,则HOMO能级降低的幅度更大,LUMO能级降低的幅度更小,总体能隙增大;如果吸电基团与LUMO电子云分布的基团链接,则LUMO能级降低的幅度更大,HOMO能级降低的幅度更小,总体能隙变小;另一方面,引入供电性基团可以同时使HOMO/LUMO能级升高,如果供电性基团与HOMO电子云分布的基团链接,则HOMO能级提升的幅度更大,LUMO能级提升的幅度更小,总体能隙变小;如果供电性基团与LUMO电子云分布的基团链接,则LUMO能级提升的幅度更大,HOMO能级提升的幅度更小,总体能隙变大;
根据上述计算结果,本公开的技术方案的优点,在于可以根据OLED器件的实际需求,可以通过调整分子结构中的吸电基团的种类和位置进而调节整个分子的HOMO/LUMO/S1而获得较好的空穴/电子注入能力/能级匹配。作为电子传输、空穴阻挡材料,原则上LUMO与HOMO越深越有利于发挥功能作用,但考虑到电子迁移率及半导体特性,本发明所述的有机半导体LUMO≤-2.3eV,HOMO≤-5.6eV。
高斯计算得到的电子云分布情况如附图1-4所示,LUMO电子云主要分布在与咔唑N原子键接到吸电基团(acceptor)苯基三嗪上,HOMO电子云主要分布在供电子基团(donor)咔唑上,咔唑苯环上的另一吸电子基团(acceptor)三嗪或吡啶上基本没有电子云分布。化合物(6)的HOMO=-5.63eV,LUMO=-2.87eV,具有较深的LUMO,有利于电子传输;而HOMO较深,有利于空穴阻挡。通过在(6)中咔唑官能团上4位进行三嗪取代后形成化合物(41)分子后,使得HOMO下拉到HOMO=-6.02eV,这样基本不影响LUMO的能级(方便电子注入能级与发光层更佳匹配),而使得化合物(41)的HOMO更能有效的阻挡空穴,从而获得更优的电子传输空穴阻挡层材料。
本发明中的这类A-D-A链接体系中,其中一个于N链接的吸电基团用于控制LUMO能级位置,供电基团咔唑基用于控制HOMO能级位置,与咔唑苯环或其衍生物链接的吸电基团则用于调控HOMO能级。此A-D-A链接体系可以保持现有LUMO能级条件下,对HOMO进行调整而对LUMO能级位置影响极小,从而最大限度地保留原有的电子注入能力,单方面的提高材料的空穴阻挡能力。从而大大提高器件能级结构的调整便利性,有利于获得高性能的器件。
作为半导体薄膜发光二极管,一般特征是所述的半导体发光二极管由如下部分组成:
(a)一个阴极,
(b)一个阳极,
(c)一个夹心与阴极和阳极之间的有机半导体发光层,
(d)一个夹心与阴极与发光层之间的有机半导体电子传输、空穴阻挡层,
其特征在于所述的电子传输、空穴阻挡层直接与发光层接触,在这2层中至少有一层中含有本发明所述的有机半导体材料,包括:
目前薄膜半导体发光二极管主要是有机发光二极管和量子点薄膜发光二极管,此2类半导体发光二极管结构类似,只是所使用的发光层不同。有机发光二极管使用有机发光材料,通过溶液打印、旋涂或真空蒸镀;量子点发光二极管使用量子点半导体发光材料,通过溶液打印、旋涂成膜。由于本发明具有适合红光、绿光、蓝光等可见发光所要求的HOMO、LUMO能级,结合良好的电子注入、传输性能(较深的LUMO能级)和空穴阻挡性能(较深的HOMO能级),因此本发明所述的半导体材料可以适合发光二极管是有机半导体发光二极管和发光二极管是量子点半导体发光二极管(其中的发光层由量子点电致发光材料组成)。
薄膜半导体发光二极管可以作为指示灯应用,更重要是作为薄膜平板全色显示应用与照明应用,不仅作为刚性显示、照明器件,也可以作为柔性显示、照明器件应用。因此,本发明所述的电子传输、空穴阻挡材料可以实施应用在所述的领域。
附图说明
图1为电子传输空穴阻挡有机材料及其在薄膜发光二极管应用示意图。
图2为高斯计算化合物(41)HOMO电子云分布图。
图3为高斯计算化合物(41)LUMO电子云分布图。
图4为高斯计算化合物(6)HOMO电子云分布图。
图5为高斯计算化合物(6)LUMO电子云分布图。
图6为化合物(1)在THF中的光谱图。
图7为化合物(1)在DCM中测试对比通氮气与空气的光谱图。
图8为化合物(1)在PS薄膜中不同浓度下的光谱图。
图9为化合物(6)在THF中的光谱图。
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,下面结合实施例子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推广。因此本发明不受下面公开的具体实施例的限制。
实施例1:
TM-1的合成:
在2L干燥的三颈口圆底瓶中加入邻溴硝基苯101g(0.5mol),邻溴苯硼酸106.5g(0.53mol),K2CO3276g(2mol),Pd(pph3)411.56g(0.01mol),toluene800mL,乙醇200mL,水400mL,N2保护,110℃回流反应过夜;反应完成后,冷却至室温,分液水洗3次后,加入硅胶减压浓缩,用石油醚做洗脱剂过柱得到黄色固体66.5g,纯度98%。
TM-2的合成:
在500mL干燥的三颈口圆底瓶中加入TM-166.7g(0.24mol),PPh3217g(0.83mol),邻二氯苯400ml,氮气置换3次后,升温至180℃反应过夜,TLC监控反应完成后,冷却至室温,减压蒸馏除去大部分邻二氯苯后,加入DCM溶解拌硅胶过柱,最后得棕色固体50g,纯度98%。
TM-3的合成:
在1000mL干燥的三颈口圆底瓶中加入TM-249g(0.2mol),片呐醇酯76g(0.3mol),KOAc40g(0.4mol),Pd2(dba)33.7g(4mmol),S-Phos 3.3g(8mmol),Dioxane 600mL,N2置换三次后,升温至110℃,反应回流过夜,TLC监控反应完全后冷却至室温,减压浓缩至干后,加入DCM溶解拌硅胶粉过柱,过滤得黄色固体42g;
TM-4的合成:
在500ML干燥的三颈口圆底瓶中加入TM-342g(0.14mol),邻溴吡啶22g(0.14mol),K2CO339g(0.28mol),Pd(PPh3)43.2g(2.8mmol),甲苯140mL,乙醇70mL,水105mL,N2置换三次后,设置110℃反应回流过夜,TLC监控反应完成后,冷却至室温,减压浓缩有机相,加入DCM溶解,水洗三次后,加入硅胶拌样,通过柱色谱纯化得黄色固体25g,纯度98%;
TM-5的合成:
在100ML干燥的三颈口圆底瓶中加入间溴苯甲醛3.7g(20mmol),苯甲眯盐酸盐7g(50mmol),Na2CO311g(80mmol),CuCl0.8g(8mmol),甲苯50mL,设置90℃反应过夜,TLC监控反应完全后,水洗三次,然后用硅藻土过滤除去CuCl,浓缩有机相后加入乙醇反成淀得到粗品,粗品通过甲苯加乙醇反成淀的方式纯化得到白固体3.2g,纯度99%。
TM-6的合成:
在100ML干燥的三颈口圆底瓶中加入间溴苯甲醛3.7g(20mmol),苯甲眯盐酸盐7g(50mmol),Na2CO311g(80mmol),CuCl0.8g(8mmol),甲苯50mL,设置90℃反应过夜,TLC监控反应完全后,水洗三次,然后用硅藻土过滤除去CuCl,浓缩有机相后加入乙醇反成淀得到粗品,粗品通过甲苯加乙醇反成淀的方式纯化得到白固体4.5g,纯度99%。
TM-7的合成:
在500mL的烧瓶中加入1,2-苯二胺64.7g,吲哚2,3-二酮43.2g,加入430mL醋酸,回流过夜。反应完全后冷却至室温,NaOH水溶液中和,过滤,乙醇打浆,DMF一次重结晶,DMF二次重结晶,收率40%,HPLC 99.92%。
TM-8的合成:
称取10.95g对溴苯甲酰氯、9.15g邻氨基二苯胺溶于200ML的NMP中,在充放氮气3次后,设置温度为160℃,开启反应;反应完后,降温至室温,倒入水中后析出大量灰色固体,过滤,滤饼用甲醇打浆后得到14.2g棕灰色的固体粉末,收率81.6%,HPLC 98.9%。
TM-9的合成:
类似TM-8的合成步骤,称取10.95g间溴苯甲酰氯、9.15g邻氨基二苯胺溶于200ML的NMP中,在充放氮气3次后,设置温度为160℃,开启反应;反应完后,降温至室温,倒入水中后析出大量灰色固体,过滤,滤饼用甲醇打浆后得到13.2g棕灰色的固体粉末,收率78.6%,HPLC98.5%。
TM-10的合成:
称取5.08g对溴苯甲醛、3.78g联苯乙酮溶于130ML的甲苯中后,室温搅拌。称取1.4gNaOH溶于7ML乙醇,用恒压漏洞慢慢滴加如反应溶液中;反应完后,倒入水中,过滤,滤饼用乙醇冲洗数次得到淡黄色固体7.8g,收率98%,HPLC 96%。
称取7.8g上述黄色固体、3.0g苯甲眯盐酸盐溶于100ML的乙醇中后,室温搅拌。称取1.5gNaOH,分批多次加入到反应液中,最后充放氮气3次,设置温度为105℃,开启反应;反应完后,倒入水中,过滤,滤饼用甲醇冲洗数次得到乳白色固体3.3g,收率40%,HPLC 99%。
化合物1的合成:
在100mL干燥的三颈口圆底瓶中加入TM-40.61g(2.5mmol),2-氯-4,7-二苯基-1,3,5-三嗪1g(3.75mmol),tBuONa 0.48g(5mmol),Pd2(dba)30.05g(0.05mmol),t-Bu3PBF40.03g(0.1mmol);二氧六环30mL,N2保护,反应回流过夜,TLC监控反应完成后,冷却至室温后加入DCM和硅胶拌样,干法上样过柱纯化,得到0.25g白色固体,纯度99.3%。化学结构采用质谱GC-MS检测分子量,分子式C32H21N5分子量Mol.Wt计算为478.54,质谱M/e=475.2。
化合物2的合成:
在100mL干燥的三颈口圆底瓶中加入TM-41.2g(2.75mmol),TM-60.61g(2.5mmol),t-BuONa 0.48g(5mmol),Pd2(dba)30.05g(0.05mmol),t-Bu3PBF40.03g(0.1mmol);二氧六环30mL,N2保护,反应回流过夜,TLC监控反应完全后,加入DCM溶解,有机相水洗三次后加入硅胶拌样,以PE:EA=5:1为洗脱剂过柱,得白色固体0.25g,纯度99.3%,收率25%;化学结构采用质谱GC-MS检测分子量,分子式C38H25N5分子量Mol.Wt计算为551.64,质谱M/e=551.2,THF中的光谱图见附图5,在DCM中测试对比通氮气与空气的光谱图见附图6,在PS薄膜中不同浓度下的光谱图见附图7。
化合物3的合成:
在100mL干燥的三颈口圆底瓶中加入TM-40.42g(1.7mmol),TM-50.77g(2mmol),t-BuONa 0.48g(5mmol),Pd2(dba)30.05g(0.05mmol),t-Bu3PBF40.03g(0.1mmol);dioxane30mL,N2保护,反应回流过夜,TLC监控反应完成后,加入DCM稀释,水洗三次后,加入硅胶拌样,以PE:EA=5:1为洗脱剂过柱纯化得白色固体1g,纯度98.9%,化学结构采用质谱GC-MS检测分子量,分子式C38H25N5分子量Mol.Wt计算为551.64,质谱M/e=551.2,在THF中的光谱图如图8所示,PL:461nm。
使用类似的方法,获得其它化合物并列表如下:
表2.化合物的结构表征:
实施例2、OLED器件应用实例:
器件制备:
ITO玻璃(14Ω/□)经洗涤液、去离子水,丙酮超声清洗后以异丙醇清洗,最后于80℃下烘干30分钟,基片再在UV臭氧等离子体处理30分钟;在高真空下,厚度为的空穴注入材料HIL m-TDATA镀在ITO表面。之后,的NPB蒸镀在m-TDATA上作为HTL。作为发光层EML由CBP作为本体材料(器件7),采用共蒸发掺入发光材料Ir(ppy)3(8%重量),总厚度之后,BAlq或本发明中材料作为电子传输空穴阻挡层ETBL, 厚度Alq3作为电子传输层ETL。LiF作为电子注入层EIL,之后铝覆盖在EIL上做为封装及镜面反光面。最后OLED由玻璃盖加入吸潮剂,用环氧胶封装后进行测试。
OLED器件中所用的材料结构为:
表3:OLED器件结构(厚度埃):
表4:OLED器件性能(@1000nits)
器件 | ETHB材料 | 电压V | LECd/A | LT90%40mA/cm2对比 |
1对比 | BAlq | 4.5 | 38.9 | 1.0 |
2对比 | 无 | 4.3 | 36.8 | 0.95 |
3 | 化合物(3) | 4.3 | 43.2 | 1.13 |
4 | 化合物(6) | 4.3 | 43.2 | 1.15 |
5 | 化合物(9) | 4.3 | 45.5 | 1.20 |
6 | 化合物(10) | 4.3 | 45.9 | 1.22 |
7 | 化合物(11) | 4.2 | 42.5 | 1.20 |
8 | 化合物(12) | 4.2 | 43.5 | 1.20 |
9 | 化合物(16) | 4.3 | 50.5 | 1.20 |
10 | 化合物(18) | 4.3 | 52.5 | 1.08 |
11 | 化合物(28) | 4.2 | 51.5 | 1.23 |
12 | 化合物(41) | 4.3 | 51.5 | 1.05 |
13 | 化合物(61) | 4.3 | 50.5 | 1.05 |
14 | 化合物(61) | 4.2 | 55.5 | 1.25 |
15 | 化合物(11) | 4.2 | 57.5 | 1.25 |
对比器件1、2与其它使用本发明材料可看出,采用A-D-A模式所发明的电子传输、空穴阻挡材料具有很好的电子传输功能,不提高OLED器件驱动工作电压,不同于传统所使用的电子传输、空穴阻挡材料往往会带来电压的提高。由于保持了良好的电子传输性能,本发明的化合物又具有较深的HOMO能级,可以阻档可能过剩的空穴而促使增加OLED器件效率,作为电子传输空穴阻挡材料可以显著改善OLED发光效率LE,最高增加发光效率达42%;此外,使用本发明的OLED器件工作寿命增加5~25%。器件14与15使用本发明ETHB材料作为辅助主体材料掺入发光层,提高了器件效率、获得了寿命改善器件。
用上述揭示的技术内容对本发明技术方案做出许多可能的变动和修饰,或修改为等同变化的等效实施例。因此,凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰,均仍属于本发明技术方案的保护范围内。
Claims (6)
5.根据权利要求4所述的半导体发光二极管,其特征是所述的半导体发光二极管是有机半导体发光二极管,其中的发光层由有机电致发光材料组成。
6.根据权利要求4所述的半导体发光二极管,其特征是所述的半导体发光二极管是量子点半导体发光二极管,其中的发光层由量子点电致发光材料组成。
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