| 摘要: | 本研究以雙噻吩並吡咯 (dithienopyrrole, DTP)及環戊烷二噻吩 (cyclopentadithiophene, CDT)為核心，開發出數種有機電洞傳輸材料，並以自主裝方式搭配NiOx製成元件，應用於錫鈣鈦礦太陽能電池 (TPSC) 中。
本論文第一系列研究中，以DTP為核心，一端接上推電子基團三苯胺，另一端接上拉電子基團氰乙酸乙烯基 (ethyl cyanoacetate)、丙二腈 (malononitrile)、以及氰基膦酸 (cyano phosphonic acid)作為錨定基團，製備出六種小分子材料 : DTP-MN-b8 (1)、DTP-MN-b16 (2)、DTP-CA-b8 (3)、DTP-CA-b16 (4)、DTP-PA-b8 (5)以及DTP-PA-b16 (6)，其中DTP-PA-b8的光電轉換效率已有達到8.7%，其他材料的效率也在5.9%-7.2%之間，與目前以SAM製備之TPSC之最高效率8.3%相比，已是不錯的表現。
第二部分研究中，我們以CDT為核心，開發出四種X-shaped之有機電洞傳輸材料，這些材料在核心兩端接上推電子基三苯胺，並於另外兩端接上錨定基團氰乙酸乙烯基、丙二腈、氰甲基膦酸二乙酯 (diethyl cyanomethylphosphonate)以及氰基膦酸，再以苯環延長共軛長度，合成出DPCDT-MN (7)、DPCDT-CA (8)、DPCDT-PE (9)及DPCDT-PA (10)分子。
上述材料之電化學及光學性能 ( HOMO / LUMO 與 Eg ) 已藉由DPV及UV-Vis測定；材料之熱穩定性則透過TGA與DSC檢測，這些新開發的有機分子材料正在進行其相關元件之優化研究。
;In this study, various dithienopyrrole (DTP) and cyclopentadithiophene (CDT)-based donor-acceptor (D-A) type self-assembled monolayers (SAMs) were developed as dopant-free hole transport materials (HTMs), deposited on NiOx film, and applied in inverted tin-based perovskite solar cells (TPSCs).
In the first part of our research, DTP was used as the central core. One end of the core was functionalized with triphenylamine (TPA) as an electron-donating group, while the other end was modified with electron-withdrawing groups, namely cyanoacetic acid (CA), malononitrile (MN), and cyano phosphonic acid (PA), as anchoring groups. As a result, six small molecule materials were synthesized: DTP-MN-b8 (1), DTP-MN-b16 (2), DTP-CA-b8 (3), DTP-CA-b16 (4), DTP-PA-b8 (5), and DTP-PA-b16 (6). The single crystal structure of DTP-CA-b8 was obtained, showing that the planar nature of the DTP core with a long alkyl chain (branch C8H17) relative to the anchoring group facilitates easy molecular alignment and stacking, thereby promoting the formation of a uniform SAM layer on the NiOx/ITO substrate. Among all the SAMs studied, TPSCs fabricated with a combination of DTP-PA-b8 SAM and NiOx exhibited the highest hole mobility and the slowest charge recombination, achieving a high-power conversion efficiency (PCE) of 8.7%, due to the greater absorption energy and stronger chemical bonding of the PA unit compared to the other anchoring units. Compared to the current highest PCE of 8.3% for TPSCs prepared via self-assembled monolayers (SAM), these results are promising.
In the second part of our research, CDT was used as the core to synthesize four X-shaped self-assembled monolayers (SAMs). These molecules had two TPA groups attached at both ends of this core, and two anchoring groups at the other ends. Additionally, phenyl groups were inserted to extend the conjugation length. As a result, four small molecule materials were synthesized: DPCDT-MN (7), DPCDT-CA (8), DPCDT-PE (9), and DPCDT-PA (10).
The electrochemical and optical properties (HOMO/LUMO and Eg) of these materials were measured using differential pulse voltammetry (DPV) and UV-Vis spectroscopy. Thermal stability was assessed using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Optimization of these newly developed organic molecular materials for device applications is currently underway. |
