新型三苯胺类光敏染料和空穴传输材料的合成与性能研究

发布时间：2018-05-31 11:21

本文选题：染料敏化太阳能电池 + 光敏染料　；参考：《天津大学》2014年博士论文

【摘要】：N,N,N’,N’-四苯基-4,4’-联苯二胺(TPB)及其衍生物是一类性能优良的光电材料,常应用在有机电致发光器件(OLED),有机场效应晶体管(OFET),有机光导器件(OPC)中。本文选用TPB为结构骨架,设计和合成一系列三苯胺类纯有机染料和小分子HTM,并将这些化合物分别应用在DSCs和PSCs中,光电转换效率分别达到5.15%和13.10%。设计合成了六个具有D-π-A分子结构的新型三苯胺类有机光敏染料,利用MS、1H NMR、13C NMR和HRMS对中间体和染料进行了结构表征。量子化学计算结果表明染料分子的HOMO能级主要分布在TPB基团上,LUMO能级主要分布在拉电子基团氰基乙酸及其相连的π桥上,证明了三苯胺染料分子结构设计的合理性。研究了三苯胺染料在溶液中的光物理性质,分析了结构对染料光物理性质的影响。在TiO_2薄膜上,其中五个染料的ICT吸收峰仅发生1nm~15nm的红移或蓝移;电化学测试表明,染料D1-D6的LUMO能级值处于-2.28eV~-3.32eV之间,HOMO能级值处于-5.33eV~-5.65eV之间,可以同时满足电子的注入和氧化态染料的还原。测试了染料在TiO_2膜上的吸附量,揭示了染料结构与吸附量、吸附形态之间的关系。通过J-V和IPCE测试,系统表征了三苯胺染料敏化的DSSC的光电转换性能,探讨了影响电池性能参数差异的因素。其中染料D4的电池由于其较宽的IPCE响应范围和较高的光电流,而获得了最高的光电转换效率5.15%。设计合成了两个新型的HTM(TPBS和TPBC),并应用在钙钛矿型太阳能电池中。循环伏安测试结果表明,通过引入供电子结构对TPB进行修饰,不仅能够调节材料的能级,而且可以提高材料的玻璃化转变温度、空穴迁移率以及电池的性能。在非掺杂条件下,TPBC的电池效率最高,为13.10%,开路电压为942 mV,短路电流为19.32 mA/cm2,填充因子为0.72。电化学交流阻抗测试表明,TPBC作为HTM应用在钙钛矿电池中能更有效地抑制电子复合,因此具有较高的开路电压。时间分辨光致发光衰减测试表明,CH3NH3PbI3/TPBC的荧光衰减寿命较小,因此TPBC具有较强的空穴传输能力。TPBS和TPBC具有合成简单、成本低廉的特点,并且其性能可以和spiro-OMeTAD媲美,说明了以TPB为核心结构的小分子空穴传输材料在非掺杂钙钛矿太阳能电池中具有巨大的应用前景。
[Abstract]:As a kind of optoelectronic materials with excellent properties, NNNNP- TPBs and their derivatives are often used in organic electroluminescent devices (OLEDX), airport effect transistors (OFETT), organic photoconductive devices (OPC). In this paper, a series of triphenylamine pure organic dyes and small molecule HTM were designed and synthesized by using TPB as the structural skeleton. These compounds were used in DSCs and PSCs respectively. The photoelectric conversion efficiency reached 5.15% and 13.10% respectively. Six novel triphenylamine organic Guang Min dyes with D- 蟺 -A molecular structure were designed and synthesized. The intermediates and dyes were characterized by NMR and HRMS. The results of quantum chemical calculation show that the HOMO energy levels of dye molecules are mainly distributed on the TPB group and its connected 蟺 -bridge, which proves the rationality of the molecular structure design of trianiline dyes. The photophysical properties of trianiline dyes in solution were studied and the effect of structure on the photophysical properties of dyes was analyzed. In TiO_2 films, the ICT absorption peaks of five dyes only exhibit red shift or blue shift of 1nm~15nm, and the electrochemical measurements show that the LUMO energy level of dye D1-D6 is between -2.28 EV and 3.32 EV, and that of Homo is between -5.33 EV and 5.65 EV. Both the electron injection and the reduction of the oxidized dyes can be satisfied at the same time. The amount of dye adsorbed on TiO_2 membrane was measured, and the relationship between dye structure and adsorption capacity and adsorption morphology was revealed. The photoelectric conversion properties of DSSC sensitized with trianiline dyes were systematically characterized by J-V and IPCE measurements. The factors affecting the performance parameters of the cells were discussed. Because of its wide IPCE response range and high photocurrent, the dye D4 battery achieves the highest photoelectric conversion efficiency of 5.15. Two new types of HTM(TPBS and TPBCC have been designed and synthesized and used in perovskite solar cells. The cyclic voltammetry results show that by introducing the power supply substructure to modify the TPB, not only the energy level of the material can be adjusted, but also the glass transition temperature, the hole mobility and the performance of the cell can be improved. The cell efficiency is 13.10mV, the open-circuit voltage is 942 MV, the short-circuit current is 19.32 Ma / cm ~ 2 and the filling factor is 0.72%. Electrochemical impedance measurements show that HTM can effectively inhibit electron recombination in perovskite cells, so it has a high open circuit voltage. The time-resolved photoluminescence attenuation test shows that the fluorescence decay lifetime of Ch _ 3NH _ 3PbI _ 3 / TPBC is relatively small, so TPBC has strong hole transport capability. TPBS and TPBC have the advantages of simple synthesis and low cost, and their properties are comparable to those of spiro-OMeTAD. It is shown that the small molecule hole-transport material with TPB as the core structure has a great application prospect in the undoped perovskite solar cells.
【学位授予单位】：天津大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TQ610.1;TM914.4

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