CN106432251B - 六臂星状有机发光材料及其有机电致发光器件 - Google Patents
六臂星状有机发光材料及其有机电致发光器件 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D487/12—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 three hetero rings
- C07D487/14—Ortho-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
本发明公开了一种六臂星状有机发光材料及其有机电致发光器件。本发明的六臂星状有机发光材料的结构由式(I)表示，利用以咔唑为代表的P‑型基团，通过N‑对位C原子与三聚咔唑连接，再以其Sp3杂化的N原子为linkage连接以二氰基苯为代表的N‑型基团，从而形成六臂的、高度有序、均三维结构的各向同性分子，并利用烷基链或烷氧基链助溶，既保持了小分子结构明确的优点，又具备树枝和聚合物良好的溶解性和浸润性，更有利于溶液加工成膜。本发明的电致发光器件，发光层采用喷墨打印制作，并将六臂星状有机发光材料作为主体发光材料或客体掺杂材料应用在有机电致发光器件的发光层，获得了纯正的红光发射。
Description
技术领域
本发明涉及电致发光技术领域，具体来说是涉及一种六臂星状有机发光材料及基于该材料的有机电致发光器件。
背景技术
自1990年剑桥大学 Friend 研究小组用旋涂法（spin coating）制备了第一个基于聚苯撑乙烯(PPV)的单层聚合物发光器件（PLED）以来，人们一直致力于研究开发可溶液加工的有机电致发光器件（OLEDs）。真空蒸镀因发展周期长、工艺成熟，仍是有机电致发光器件的主流制造方式。
但是，包含金属掩膜（FMM）的蒸镀制程在高PPI和大尺寸化问题上遭遇瓶颈，且严重的材料浪费致使产品定价居高不下。与真空蒸镀相比，喷墨打印作为目前全彩显示最主要的溶液加工制程，因其材料利用率高，制备条件温和，更兼容大尺寸和柔性基板而具备更低的成本优势，将成为补充或替代蒸镀法OLED制造方案。
制约喷墨打印技术发展的因素主要有两个：一是高性能溶液加工类型的有机材料及其墨水技术；二是高精度、高产能打印设备及可靠的生产监控系统。
就材料而言，它决定了产品的性能和竞争力。可用于喷墨打印的OLED材料与蒸镀类材料并无本质上的区别。对于蒸镀制程，限于目前的真空能力，为避免材料变质，其分子量不可能无限制增大，而喷墨打印材料除性能外，还要考虑其可溶性、张力（墨水）以及界面性质。以PPV、PVK为代表的聚合物材料最早被应用于溶液加工OLED，其可溶性较好，且成膜性较佳，其缺点是由于聚合物分子量无法精确控制，重现性差，且离子除杂困难，这些问题极大地影响了OLED器件的性能及寿命。
2012年以来，小分子组件成为溶液加工器件的新宠，Lee等人利用蒸镀小分子制备“磷光”旋涂器件，达到18.0%的外量子效率。但因为小分子存在成膜性差，容易去润湿，其流体特性高度依赖于溶剂的问题，开发溶解性佳、成膜性好且器件可靠的小分子材料仍是一个巨大的挑战。
发明内容
本发明的目的是提供一种具有良好的光电性能、成膜性和溶解性，并且制备简便，能用于喷墨打印法制作有机电致发光器件的六臂星状有机发光材料。
本发明的另一个目的是提供一种基于上述六臂星状有机发光材料的有机电致发光器件。
为达到上述目的，本发明采取的技术方案是提供一种六臂星状有机发光材料，具有式（I）所示的结构通式：
其中R1选自苯、氟苯、氰基苯、硝基苯、萘、联苯、氰基芴、吡啶、喹啉、异喹啉、苯基咪唑、嘧啶、二苯基三嗪、三唑、砜或磷酰基中的一种；R2选自带有烷基的苯、萘、蒽、芘、芴、三苯胺、咔唑或N-苯基咔唑。
所述的氟苯、氰基苯或硝基苯都是1～5取代；所述的烷基是1～20个碳原子的烷基或1～20个碳原子的烷氧基，优选1～8个碳原子的烷基或1～8个碳原子的烷氧基。
本发明的六臂星状有机发光材料以三聚咔唑为核心（core），以三聚咔唑三个Sp3杂化的N原子为linkage，同时分别连接R1作为受体（acceptor unit）；3、8、13位同时分别连接R2作为供体（donor unit），R2连接烷基以助溶，从而形成六臂的、高度有序，均三维结构的各向同性分子，既保持了小分子结构明确的优点，又具备树枝和聚合物良好的溶解性和浸润性，更有利于溶液加工成膜。
本发明的六臂星状有机发光材料为具备热致延迟荧光（TADF）特性，可以利用传统荧光分子跃迁禁阻的三线态激子来发光，以提高电致发光器件效率，其根本原因则在于该六臂星状有机发光材料具有较小的△EST，满足三线态能量向单线态逆向窜越（RISC），从而提高辐射发光效率。
本发明还提供了基于所述的六臂星状有机发光材料的有机电致发光器件，六臂星状有机发光材料作为主体发光材料或客体掺杂材料用作有机电致发光器件的发光层。
所述的有机电致发光器件还包括基底、透明阳极、有机功能层和金属阴极，有机功能层中至少有一层为发光层，有机功能层还包括空穴/电子注入及传输材料，所述的空穴/电子注入及传输材料为咔唑、芳胺、苯并咪唑或金属配合物。
由于六臂星状有机发光材料为可溶液化的TADF材料，而TADF材料本身具备双极（bipolar）特性，其作为发光层必将大大改善两种载流子的注入和传输能力，从而有效地降低器件的启亮电压。同时，由于器件发光层不含贵重金属，利用溶液加工方式又避免了材料浪费，可大大降低成本。
附图说明
图1是本发明六臂星状有机发光材料M1的3D球棍模型。
图2是本发明六臂星状有机发光材料M1的轨道分布图。
图3是本发明六臂星状有机发光材料M1在THF溶液的荧光发射光谱。
图4是本发明六臂星状有机发光材料M1作为发光主体的有机电致发光器件的结构示意图及各层所用功能材料的结构式。
图5是本发明六臂星状有机发光材料M1作为掺杂客体的有机电致发光器件的结构示意图及各层所用功能材料的结构式。
具体实施方式
以下实施例是对本发明的进一步说明，不是对本发明的限制。
实施例1：六臂星状有机发光材料M1的制备：
将化合物吲哚-2-酮4g（30 mmol），三氯氧磷30 mL加入两口烧瓶中，氮气氛围下升温至回流搅拌反应8 h。反应结束冷却到室温，将反应溶液搅拌下缓慢倒入到冰水中淬灭，用2M NaOH溶液调至中性后，将固体减压抽滤并用甲醇20mL洗涤固体得到棕色粗产物，使用丙酮重结晶后得到三聚咔唑2.2g，产率63%。MS (ESI-TOF): m/z: 345.1034。1H NMR (400MHz, DMSO-d 6 )：δ/ppm, 11.86 (s, 3H), 8.66 (d, 3H), 7.71 (d, 3H), 7.41-7.28 (m,6H)。
氮气氛围下，将1 g（2.9 mmol）三聚咔唑，0.1 g 氢化钠（3.6 mmol）加入20 mL无水四氢呋喃中搅拌溶解，冰浴下加入3,5-二氰基氟苯1.4 g（9.5 mmol）反应30 min，后缓慢升温至回流反应过夜。反应结束后冷却到室温，倒入100 mL水中淬灭，再以20 mL*3 二氯甲烷萃取并干燥，柱层析方法纯化粗产品产品（流动相石油醚：二氯甲烷=3:1）得到白色固体0.7 g，产率35%。 将此产物0.6 g（0.83 mmol）溶于20mL二氯甲烷，加入碳酸钾0.6 g （4.3mmol），氮气氛围下，缓慢滴加0.3 mL溴素，常温搅拌反应24 h。反应结束后缓慢加入饱和亚硫酸钠溶液50 mL除掉未反应完的溴素。分液后将有机层干燥浓缩得到淡黄色粗产品。粗产品以柱层析方法（流动相石油醚：二氯甲烷=3:1）纯化，得到白色的溴代前体固体0.68 g，产率85%。 MALDI-TOF:m/z: 958.98。1H NMR (400 MHz, CDCl3)：δ/ppm, 7.97 (s, 6H), 7.83(d, 3H), 7.72 (s, 3H), 7.51(s, 3H), 7.25(d, 3H)。
氮气氛围下，将0.4 g（0.42 mmol）溴代前体，0.38 g（1.4 mmol）叔丁基咔唑，0.2g叔丁醇钠加入20 mL甲苯溶液搅拌溶解，再向反应液中加入0.02 g（0.07 mmol）四三苯基磷钯和0.15 mL 1M 三叔丁基膦的甲苯溶液，后升温到100 ℃反应过夜。反应结束后，将反应液倒入水中淬灭，并使用二氯甲烷（30 mL*3）进行萃取，干燥有机相后旋转蒸发掉溶剂，粗产品以柱层析方法（流动相石油醚：二氯甲烷=2:1）纯化，得到白色固体六臂星状有机发光材料M1 0.27g，产率41%。MALDI-TOF: m/z :1555.83。1H NMR (CDCl3, 400 MHz):δ=8.95(d, 3H); 8.36 (d, 3H); 7.94-7.98 (m, 12H); 7.86 (d, 3H); 7.62 (d, 6H); 7.51-7.55 (m, 6H); 7.11 (d, 3H); 1.35 (s, 54H)。
六臂星状有机发光材料M1的3D球棍模型如图1所示，可以看出叔丁基咔唑和m-二氰基苯有较大的二面角，高度扭曲的结构有利于减小△EST，提高逆隙间窜越能力，从而有效提高发光效率。
运用密度泛函理论（DFT），针对六臂星状有机发光材料M1，利用Gaussian 09的B3LYP/6-31G(d)机组，优化并计算得到了六臂星状有机发光材料M1的分子前线轨道的分布情况，如图2所示，从图2可以明显看出，分子的HOMO和LUMO分别排布在不同的基团（Unit）上，实现了完全的分离，这有助于减小隙间能差△EST，从而提高逆隙间窜越能力。同时，利用上述模拟方法计算获得了M1的能量数据，具体数据如表1所示：
表1六臂星状有机发光材料M1的性质数据
从表1可以看出六臂星状有机发光材料M1的HOMO和LUMO能级分别为-5.57 eV和-2.53 eV，E g为3.04 eV；M1的激发单线态能量S1为1.98 eV，激发三线态能量T1为1.97 eV，两者之间的能量之差△E ST仅为0.01 eV，小于0.2 eV，因此将六臂星状有机发光材料M1作为发光材料时，可以实现RISC，即三线态激子逆向系间窜越转变成单线态激子发光。
利用荧光发射分析法得到了M1在四氢呋喃溶液中的荧光发射光谱，如图3所示，六臂星状有机发光材料M1的主发射峰值为628 nm，为饱和红光发射。基于含时密度泛函理论(TDDFT)，借助爱因斯坦自发辐射公式计算了辐射速率常数，从而推算出六臂星状有机发光材料M1的荧光寿命τ为2.57 μs，比传统荧光材料的荧光寿命高出3个量级，表明六臂星状有机发光材料M1分子具有很好的延迟荧光性质（一般来说，τ大于1μs就符合“延迟荧光”效果）。
实施例2：将六臂星状有机发光材料M1作为主体发光材料的非掺杂型有机电致发光器件：
本实施例的有机电致发光器件包括：1.玻璃衬底层；2.透明阳极(ITO) ；3.空穴注入层为聚(3,4-亚乙二氧乙基噻吩)-聚(苯乙烯磺酸) (PEDOT:PSS) ；4.发光层为M1；5.电子传输层为1,3,5-三[(3-吡啶级)-3-苯基]苯 (TmPyPB)；6.金属阴极（Al/LiF），如图4所示。
采用Spectroscan PR705光谱仪和Keithley 236电流电压源测量系统检测该器件的性能，结果如表2所示：
表2 M1作为发光主体的有机电致发光器件的性能数据
以六臂星状有机发光材料M1作为主体发光材料的非掺杂器件取得了3.4%的最大外量子效率，这主要得益于材料扭曲强度大，规整度高的立体构型，以及外围高度支化的烷基链，有效地减弱了由π-π堆积（π-π stacking）导致的激子淬灭问题，从而获得了较为满意的器件性能。此外，底发射色坐标为(0.67, 0.32)，非常接近于标准红光的色坐标（0.67,0.33）。
实施例3：将六臂星状有机发光材料M1作为发光客体的掺杂型有机电致发光器件：
本实施例的有机电致发光器件将M1作为发光客体，聚合物材料PVK为主体的掺杂器件结构如图5所示，包括：1.玻璃衬底层；2.透明阳极(ITO) ；3.空穴注入层为聚(3,4-亚乙二氧乙基噻吩)-聚(苯乙烯磺酸) (PEDOT:PSS) ；4.发光层为PVK: M1或者DCJTB；5.电子传输层为1,3,5-三[(3-吡啶级)-3-苯基]苯 (TmPyPB)；6.金属阴极（Al/LiF）
采用Spectroscan PR705光谱仪和Keithley 236电流电压源测量系统检测该器件的性能，结果如表3所示：
表3 M1作为掺杂客体的有机电致发光器件的性能数据
以经典聚合物材料PVK为主体，以六臂星状有机发光材料M1为发光客体的掺杂型器件取得了4.6%的最大外量子效率，与非掺杂型器件相比又有了进一步地提升，表明掺杂方式可以更好地避免π-π堆积效应。
同经典红光发光材料4-(二氰基亚甲基)-2-叔丁基-6-(1,1,7,7-四甲基久罗尼定基-4-乙烯基)-4H-吡喃（DCJTB）的掺杂参比器件（reference）相比，M1器件有大幅度的性能改善。这主要得益于M1自身的TADF特性，利用传统荧光分子（如DCTJB）跃迁禁阻的三线态激子来发光，从而提高了器件效率。同时，M1器件在色坐标上远优于DCJTB，更接近于标准红光的色坐标（0.67, 0.33），为非常纯正的红光发射。
Claims (4)
1.一种六臂星状有机发光材料，其特征在于，该材料为式M1所示的化合物：
。
2.基于权利要求1所述的六臂星状有机发光材料的有机电致发光器件，其特征在于：六臂星状有机发光材料作为非掺杂型发光材料或客体发光材料用作有机电致发光器件的发光层。
3.如权利要求2所述的有机电致发光器件，其特征在于：所述的有机电致发光器件还包括基底、透明阳极、有机功能层和金属阴极，有机功能层中至少有一层为发光层，有机功能层还包括空穴/电子注入及传输材料。
4.如权利要求3所述的有机电致发光器件，其特征在于：所述的空穴/电子注入及传输材料为咔唑、芳胺、苯并咪唑或金属配合物。
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