臺灣博碩士論文加值系統

本研究以Stille coupling reaction成功合成二種含苯並二噻吩-苯并噻二唑分子衍生物給體-受體交錯型共軛高分子P1、P2，並當作活性層之電子給體材料。本論文分成三部份，第一部分為合成太陽能電池元件構造層材料：活性層(ative layer)材料。第二部分利用紅外線光譜（FT-IR）料之分子量及其聚合分佈指數值 (PDI)，以紫外-可見光光譜 (UV- Vis)及螢光光譜 (PL)觀察光電材料之光學性質及能隙後，可由循環伏安圖譜 (CV)估算出光電材料之最高滿軌域 (HOMO)能量及最低空軌域 (LUMO)能量，並以熱示差掃瞄卡計 (DSC)分析出材料之熱性質。第三部分使用上述合成的光電材料應用於高分子本體異質結太陽能電池元件，並進行光電轉換效率的量測。並討論以不同Polymer：PCBM 混摻比例和不同退火溫度對其太陽能電池元件效率之影響。合成之P1、P2分別具有1.82 eV和1.80 eV的低能隙，分別具有350-900 nm的寬吸收範圍。在P1:PCBM混摻比例為1:2及退火溫度為150℃時，以P1和PCBM為活性層之本體異質結太陽能電池有最佳的短路電流密度3.34 mA/cm2，FF值36.1% 及光電轉換效率0.59％。在P2:PCBM混摻比例為1:1及退火溫度為175℃時，以P2和PCBM為活性層之本體異質結太陽能電池有最佳的元件表現，短路電流密度3.69 mA/cm2，FF值40.8%及光電轉換效率0.81％。

We have sucessfully synthesized two donor-acceptor alternating conjugated polymers P1 and P2 containing benzodithiophene and benzothiadiazole derivatives as the donor and acceptor units, respectively, for the donor materials of the active layer by Stille coupling reaction.
Our study was divided into three parts. The first part was to synthesize the donor materials of both types: P1 and P2. Subsequently, all synthesized optoelectronic materials were confirmed with FT-IR and NMR analyses. Molecular weights and polydispersity indices (PDI) were obtained by GPC. Optical properties were observed with UV-vis and photoiuminescence (PL) spectra. On the other hand, by the combination of band gap values from UV-vis spectroscopies with the oxidation-reduction potential values from cyclic voltammetry (CV), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values of both optoelectronic materials could be estimated. In addition, thermal properties of both synthesized materials were analyzed with thermogravimetric (TGA) and differential scanning calorimetry (DSC). The third part was the application of both of the synthesized materials in the active layers of polymer bulk heterojunction photovoltaic (BHJ) solar cells and the measurements of power conversion efficiency.
We studied the effects of different weight ratios of the Polymer : PCBM blends and different annealing temperatures on the performance of polymer solar cells using the blend (Polymer : PCBM) as active layers. Both P1、P2 exhibits a low band gap of 1.82 eV and 1.80 eV and broad absorption band from 350 to 900 nm, which allows it to absorb more available photons from sunlight. The bulk heterojunction polymer solar cell incorporating P1 and PCBM at a blend ratio of 1:2 and annealing temperature 150℃ exhibited the highest short-circuit current density of 3.34 mA/cm2 and a power conversion efficiency of 0.59%. The bulk heterojunction polymer solar cell incorporating P2 and PCBM at a blend ratio of 1:1 and annealing temperature 175℃ exhibited the highest short-circuit current density of 3.69 mA/cm2 and a power conversion efficiency of 0.81%.

目錄 I
表目錄 VII
圖目錄 VIII
摘要 1
ABSTRACT 2
第一章 緒論 1
1.1 前言 1
1.2 高分子太陽能電池 2
1.2.1 太陽能電池元件構造 2
1.2.2 電洞傳輸層簡介 3
1.2.3 活性層簡介 4
1.2.4太陽能電池工作原理 7
1.3 研究動機 7
第二章 理論基礎與文獻回顧 9
2.1太陽能電池輸出特性 9
2.2 低能隙活性層電子給體材料 14
2.2.1 給體-受體型共軛高分子之給體單元 16
2.2.2 給體-受體型共軛高分子之受體單元 18
2.2.3 含BDT給體結構特性 19
2.2.4 含BT受體結構特性 20
2.2.5 含氟BT受體結構特性 20
2.3 高效率太陽能電池元件製備條件探討 21
2.3.1 給體/受體材料添加比例的影響 21
2.3.2 退火條件的影響 22
2.3.2.1 熱退火 22
2.3.2.2 溶劑退火 23
第三章 實驗與方法 24
3.1 實驗目的與設計 24
3.1.1 給體-受體交錯型共軛高分子之設計 24
3.1.2 實驗流程 25
3.2 實驗藥品 25
3.3 儀器 29
3.3.1 一般儀器 29
3.3.2 分析儀器 29
3.4 實驗合成步驟 33
3.4.1 A1之受體單位的合成 37
3.4.1.1 4,7-dibromobenzo[c][1,2,5]thiadiazole (1)的合成 37
3.4.1.2 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (2)的合成 38
3.4.1.3 4,7-bis(5-bromothiophen-2-yl)benzo[c][1,2,5]thiadiazole (A1)的合成 39

3.4.2 單體A2的合成 40
3.4.2.1 5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (3)的合成 40
3.4.2.2 4,7-bis(5-bromothiophen-2-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole (A2)的合成 41
3.4.3 單體D1的合成 42
3.4.3.1 4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene (4)的合成 42
3.4.3.2 (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(trimethylstannane)的合成(D1) 43
3.4.4 高分子P1、P2的合成 44
3.4.2.1 高分子P1的合成 44
3.4.2.2 高分子P2的合成 45
3.5 元件製作 46
3.5.1 ITO玻璃基板之清洗與蝕刻 47
3.5.2 電洞傳輸層 47
3.5.3 活性層 48
3.5.4 金屬電極(Al) 48
第四章 結果與討論 49
4.1 高分子P1之結構鑑定、熱性質、表面型態及光電特性探討 49
4.1.1 高分子P1及其合成中間體、單體之1H NMR與13C NMR光譜分析 49
4.1.2 高分子P1合成之中間體、單體FTIR光譜 50
4.1.3 高分子P1之GPC鑑定 53
4.1.4 高分子P1之熱性質分析 54
4.1.5 高分子P1之紫外/可見光光譜特性分析 55
4.1.6 高分子P1之螢光光譜特性分析 58
4.1.7 高分子P1之循環伏安計量分析 61
4.1.8 P1:PCBM之混摻比例對元件性質影響 63
4.1.8.1 P1：PCBM於不同混摻比例之UV-Vis光譜 63
4.1.8.2 P1：PCBM混摻比例對元件特性影響 64
4.1.9 退火溫度對P1:PCBM元件性質之影響 66
4.1.9.1 P1：PCBM於不同退火溫度下之UV-Vis光譜 66
4.1.9.2 P1：PCBM於不同退火溫度下之PL光譜 67
4.1.9.3 P1：PCBM於不同退火溫度下之AFM分析 68
4.1.9.4 P1：PCBM之退火溫度對元件特性影響 71
4.1.9.5 P1：PCBM之退火溫度對EQE特性影響 73
4.2高分子P2之結構鑑定、熱性質、表面型態及光電特性探討 74
4.2.1 高分子P2及其合成中間體、單體之1H NMR與13C NMR光譜分析 75
4.2.2 高分子P2之合成中間體、單體FTIR光譜 75
4.2.3 高分子P2之GPC鑑定 77
4.2.4 高分子P2之熱性質分析 78
4.2.5 高分子P2之紫外/可見光光譜特性分析 79
4.2.6 高分子P2之螢光光譜特性分析 82
4.2.7 P2之循環伏安計量分析 85
4.2.8 P2之太陽能電池元件性質分析 86
4.2.8.1 P2：PCBM於不同混摻比例之UV-Vis光譜 87
4.2.8.2 P2：PCBM之混摻比例對元件特性影響 88
4.2.9 退火溫度對P2：PCBM元件性質之影響 90
4.2.9.1 P2：PCBM於不同退火溫度下之UV-Vis光譜 90
4.2.9.2 P2：PCBM於不同退火溫度下之PL光譜 91
4.2.9.3 P2：PCBM於不同退火溫度下之AFM分析 95
4.2.9.4 P2：PCBM之退火溫度對元件特性影響 95
4.2.9.5 P2：PCBM之退火溫度對EQE特性影響 97
4.3以高分子P1、P2與P3HT分別為活性層給體材料之太陽能電池元件性質比較 99
4.3.1 高分子P1、P2之分子量及熱性質分析比較 99
4.3.2 高分子P1、P2與P3HT之紫外光-可見光吸收光譜比較 101
4.3.3 高分子P1、P2與P3HT之能階比較 102
4.3.4 高分子P1、P2與P3HT分別之載子移動率性質比較 104
4.3.4 高分子P1、P2與P3HT分別為活性層給體材料之元件效率及材料特性比較 104
第五章 結論 107
參考文獻 108
附錄 113

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