CN111170956A - 一种含苯并恶唑和噻唑基团的空穴传输材料组成物及应用 - Google Patents
一种含苯并恶唑和噻唑基团的空穴传输材料组成物及应用 Download PDFInfo
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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Abstract
本发明公开了空穴传输材料相关技术领域的一种含苯并恶唑和噻唑基团的空穴传输材料组成物及应用，包括具有以下结构式I的化合物：
其中，R1‑R4分别独立地表示为氢、卤素、‑OH和C1‑C6烷氧基；Ar1和Ar2分别独立地选自取代或者未取代的C6‑C30芳基、取代或者未取代的C3‑C30杂芳基、三芳香胺基、咔唑基；X选自O或S；具有较高的热分解温度，显示出良好的热稳定性；合成方法简单，成本低廉，适合商业化生产；具有合适的能级，较高的氧化电位，有利于钙钛矿电池获得较高的开路电压。
Description
技术领域
本发明涉及空穴传输材料相关技术领域，特别涉及一种含苯并恶唑和噻唑基团的空穴传输材料组成物及应用。
背景技术
太阳能作为世界上最丰富的能源资源，一年的太阳辐射能量是世界上化石燃料已知储量的成百上千倍。而且太阳能是一种用之不竭，取之不尽的清洁能源，但是困难在于如何以有效且廉价的方式转化利用太阳能。目前，以有机太阳能电池(OPV)、染料敏化太阳能电池(DSSCs)、钙钛矿太阳能电池(PSCs)为代表的新一代太阳能电池展现出了广阔的发展前景。
自2009年钙钛矿材料首次作为感光材料用于太阳能电池以来，由于钙钛矿太阳能电池具有较宽的吸收光谱、较高的载流子迁移率、制备工艺简单，可以制备柔性、透明等优点，其效率在短短几年内已经突破了20％，钙钛矿太阳电池的基本组成部分包括：透明导电玻璃基底(TCO)、电子传输层(ETL)、钙钛矿层、空穴传输层(HTL)、金属电极。空穴传输层对钙钛矿太阳能电池效率提升有着至关重要的影响，性能优异的空穴传输层对于光生空穴的提取和传递具有明显的提升作用，空穴传输材料可以改善界面，促进电子和空穴在功能界面分离，减少电荷负荷，提高电池性能。传统小分子空穴传输材料Spiro-OMeTAD合成路线复杂，提纯困难，因此还需要继续开发效率高，稳定性好，成本低的空穴传输材料。
发明内容
针对现有技术存在的传统小分子空穴传输材料Spiro-OMeTAD合成路线复杂，提纯困难的技术问题，本发明提供一种含苯并恶唑和噻唑基团的空穴传输材料组成物及应用。
为实现上述目的，本发明的技术方案为：
一种含苯并恶唑和噻唑基团的空穴传输材料组成物，包括具有以下结构式I的化合物：
其中，R1-R4分别独立地表示为氢、卤素、-OH和C1-C6烷氧基；Ar1和Ar2分别独立地选自取代或者未取代的C6-C30芳基、取代或者未取代的C3-C30杂芳基、三芳香胺基、咔唑基；X选自O或S。
优选的，Ar1和Ar2中至少有一处为三芳香胺基。
进一步的，R1和R4分别独立地选自C1-C8烷氧基。
优选的，为下列结构式1-14的化合物：
进一步的，所述化合物的中间体包括具有以下结构式Ⅱ：
一种上述任一项所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，将所述含苯并恶唑和噻唑基团的空穴传输材料组成物经过处理应用于光生空穴的提取和传递领域。
进一步的，所述处理包括真空蒸镀法、分子束蒸镀法、溶剂处理法、喷墨打印法中的一种或多种。
优选的，所述溶剂处理法包括浸涂法、旋涂法、棒涂法中的一种或多种。
上述任一项所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，光生空穴的提取和传递领域包括钙钛矿电池、有机太阳能电池、有机电致发光器件、有机薄膜晶体管、有机光感受器中的一种或多种。
本发明具有以下优点：
1.具有较高的热分解温度，显示出良好的热稳定性；
2.合成方法简单，成本低廉，适合商业化生产；
3.具有合适的能级，较高的氧化电位，有利于钙钛矿电池获得较高的开路电压。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为化合物1的1HNMR谱图；
图2为化合物1的1HNMR低场放大谱图；
图3为化合物1的高分辨质谱图；
图4为化合物1的HOMO能级；
图5为化合物1的LUMO能级；
图6为化合物1在二氯甲烷溶液中的紫外吸收图；
图7为化合物1在二氯甲烷溶液中的荧光光谱；
图8为目标化合物的循环伏安曲线。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，在以下说明中，省略了对公知结构、技术及操作的描述，以避免不必要地混淆本发明的概念。另外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
为了更详细叙述本发明，特举以下例子，但是不限于此。
实施例1中间体的合成
氮气保护下，在瓶中加入甲苯400ml，加入叔丁醇钠40g，对甲氧基苯胺20g，9，9-二甲基-2-溴芴36.97g，三叔丁基膦甲苯溶液(10％)4.4g，三(二亚苄基丙酮)二钯0.37g，升温至温度90℃。升温回流反应3小时，点板分析。冷却，加入150g水，搅拌1h，静置分层，有机相用无水硫酸镁干燥，过滤，浓缩，用石油醚重结晶，得产品40.7g。
实施例2化合物的制备，按以下制备路径为例：
氮气保护下，在反应瓶中加入甲苯20mL，叔丁醇钠0.82g，中间体1.8g，2-(3，5-二溴苯)苯并恶唑1g，三叔丁基膦甲苯溶液(10％)0.24g，三(二亚苄基丙酮)二钯0.02g，升温回流反应2h。反应液浓干，直接过分离柱，得0.28g黄色产品。
如图1和图2所示，1HNMR(400MHz，CDCl3，δ)：7.65-7.67(m，1H)；7.52-7.59(m，6H)，7.44-7.46(m，1H)，7.36-7.38(d，J＝7.2Hz，2H)，7.23-7.32(m，6H)，7.11-7.14(m，6H)，6.70-7.02(m，2H)，6.89-6.91(m，1H)，6.81-6.83(m，4H)，3.78(s，6H)，1.38(s，12H)。
如图3所示，HRMS(ESI,m/z):[M+H]+：822.3706。
本领域技术人员可在不需要进行创造性劳动的基础上，结合本发明实施例的教导与现有技术和自身经验，自行实施，获取包括上述14种结构式的化合物在内的更多的实施方式。
实施例3化合物的理论模拟计算
用密度功能理论方法(DFT)来模拟就算目标化合物的空间最优化结构和它们的前沿能级轨道如图4和图5，理论计算出来的HOMO值为4.68eV，LUMO值为1.33eV。
实施例4化合物的光化学物理性质测试
在1*10-5mol/L二氯甲烷溶液中测试化合物1的紫外吸收的最大吸收峰为415nm(如图6)，紫外－可见吸收光谱(UV-Vis)采用VarianCary200紫外－可见光谱仪测定；最大荧光发射光谱为517nm(如图7)，荧光光谱采用PerkinElmerLS55荧光光谱仪测定。
实施例5化合物的电化学性质测试
化合物1的电化学性质由电化学循环伏安法(CV)来测试，实验仪器由辰华CHI660E电化学工作站，这种方法是以用二氯甲烷作为溶剂，0.1M四丁基六氟磷酸铵作为电解质，铂片电极作为工作电极，铂丝电极作为对电极，饱和Ag/AgCl作为参比电极。图8是目标化合物的循环伏安曲线。计算得到化合物的氧化电位为0.83V，其HOMO为5.27eV。
本发明技术方案中所列示的其他结构式的化合物的合成路径与实验条件与上述实施例所示相同，本领域技术人员可在不需要付出创造性劳动的基础上，结合自身经验与现有技术自行实施。
经过本发明制备所得的产物具有较高的热分解温度，显示出良好的热稳定性；本发明中提出的技术方案的合成方法简单，成本低廉，适合商业化生产；制备产物具有合适的能级，较高的氧化电位，有利于钙钛矿电池获得较高的开路电压。
以上结合附图详细描述了本发明的较佳具体实施例，但本发明不限于所描述的实施方式。应当理解，本领域的普通技术在不脱离本发明原理和精神的情况下，无需创造性劳动就可以根据本发明的构思作出诸多变化、修改、替换和变型。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (9)
1.一种含苯并恶唑和噻唑基团的空穴传输材料组成物，其特征在于：包括具有以下结构式I的化合物：
其中，R1-R4分别独立地表示为氢、卤素、-OH和C1-C6烷氧基；Ar1和Ar2分别独立地选自取代或者未取代的C6-C30芳基、取代或者未取代的C3-C30杂芳基、三芳香胺基、咔唑基；X选自O或S。
2.根据权利要求1所述的含苯并恶唑和噻唑基团的空穴传输材料组成物，其特征在于：Ar1和Ar2中至少有一处为三芳香胺基。
3.根据权利要求1所述的含苯并恶唑和噻唑基团的空穴传输材料组成物，其特征在于：R1和R4分别独立地选自C1-C8烷氧基。
4.根据权利要求1所述的含苯并恶唑和噻唑基团的空穴传输材料组成物，其特征在于：为下列结构式1-14的化合物：
5.根据权利要求1～4任一项所述的含苯并恶唑和噻唑基团的空穴传输材料组成物，其特征在于：所述化合物的中间体包括具有以下结构式Ⅱ：
6.一种如权利要求1～5任一项所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，其特征在于：将所述含苯并恶唑和噻唑基团的空穴传输材料组成物经过处理应用于光生空穴的提取和传递领域。
7.根据权利要求6所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，其特征在于：所述处理包括真空蒸镀法、分子束蒸镀法、溶剂处理法、喷墨打印法中的一种或多种。
8.根据权利要求7所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，其特征在于：所述溶剂处理法包括浸涂法、旋涂法、棒涂法中的一种或多种。
9.根据权利要求6～8任一项所述的含苯并恶唑和噻唑基团的空穴传输材料组成物的应用，其特征在于：所述光生空穴的提取和传递领域包括钙钛矿电池、有机太阳能电池、有机电致发光器件、有机薄膜晶体管、有机光感受器中的一种或多种。
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