Synthesis and Properties of Organic Dyes for Dye-Sensitized Solar Cells and Zinc Porphyrins for Polymer Solar Cells

[[abstract]]本論文主要分成兩個部分，分別探討有機光敏劑應用於染料敏化太陽能電池以及鋅紫質共聚高分子應用於有機光伏特太陽能電池。 有機光敏劑部份使用 Sonogashira cross-coupling 合成一系列含? (Anthrance) 取代基的有機光敏劑，分子設計上主要探討長碳鏈在染料中所扮演的角色，分成兩個部分，其一：施體分別使用 N,N-dimethylnaphthalen-1-amine、N,N-dioctylnaphthalen-1-amine，加入長碳鏈後，一方面增加溶解度，另一方面則研究施體端的長碳鏈能否在二氧化鈦與電解液之間形成阻擋層 (Blocking layer)，減少電荷結合 (Charge recombination) 所形成的暗電流，進而增加開路電壓。其二：在 π-bridge 加入1,4-Didodecybenzene，同樣研究是否能在電解液與二氧化鈦之間形成阻擋層以及在染料側邊加上長碳鏈是否能減少分子堆疊的現象。利用染料吸附在二氧化鈦上的紫外光-可見光吸收光譜可以觀察分子堆疊的情形，藉由側鏈 1,4-Didodecybenzene 的加入，沒有明顯的減少光譜變寬的現象，但由於共軛長度的增加，有效提升了吸光範圍以及莫爾吸收係數。 有機光伏特太陽能電池部份加入鋅紫質單體共聚合，利用紫質獨特的光譜特性在可見光400nm~500nm 的波段擁有很強的吸光能力，補足了共聚高分子 Por0FBT 在該波段的吸光不足。鋅紫質單體部分，分別在 Zn(OR)4BPP 的大環 meso 位置接上N,N-dimethylaniline、以及未接任何取代基進行比較，命名分別為 Por1664FBT、Por1521FBT。在共聚物的分子設計上面利用 D-π-A 的概念，?吩 (Thiophene) 基團做為推電子基，?二唑 (Thiadiazole) 基團為拉電子基。在共聚物與 PC71BM 最佳比例的條件下，以共聚高分子 Por1521FBT 效率最佳，達到 4.16% 。[[abstract]]There are two main parts in this thesis. In the first part, we synthesized a series of metal free organic dyes based on anthracene for dye-sensitized solar cell by using Sonogashira cross-coupling method. In order to investigate the roles ofalkyl chains in the enhanced photovoltaic performance of the dyes. We used N,N-dimethylnaphthalen-1-amine and N,N-dioctylnaphthalen-1-amine substituent as electron-donating groups . We expected that when the dyes fully cover the TiO2 nanoparticle surface could form a blocking layer between TiO2 nanoparticle and the electrolyte, which will reduce charge recombination then enhance the open-circuit voltage. In order to investigate the dye aggregation on TiO2 nanoparticle, we synthesized π-bridge group with 1,4-Didodecybenzene substituent. Based on the experimental results, we demonstrated that 1,4-Didodecybenzene substituent could not decrease dye aggregation remarkably. In other hand, 1,4-Didodecybenzene substituent could also reduce charge recombination. In the second part, we synthesized a series of zinc(II) porphyrin monomer for porphyrin-contained polymer solar cell. Por0FBT is a low band gap polymer which had a strong absorption in the near-IR region, but had a weak absorption in the 400nm~550nm. In order to enhance the Pro0FBT absorption in 400nm~550nm, we used zinc (II) porphyrin monomer named、Me2-PE1-Br2 and PE1-Br2 as blue-light harvesting dopants. Among these, the PE1-Br2 porphyrin-contain copolymer, named Por1521BET, has the highest performance η= 4.16% .[[note]]碩