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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 趙基揚(Chi-Yang Chao) | |
| dc.contributor.author | Chung-Hsiang Chao | en |
| dc.contributor.author | 趙崇翔 | zh_TW |
| dc.date.accessioned | 2021-06-15T04:10:52Z | - |
| dc.date.available | 2010-02-04 | |
| dc.date.copyright | 2010-02-04 | |
| dc.date.issued | 2010 | |
| dc.date.submitted | 2010-01-28 | |
| dc.identifier.citation | [1]Scientific American, Chinese version 2008, 72, 60-63.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/45252 | - |
| dc.description.abstract | 本論文是利用不同的聚合方式(GRIM、Universal GRIM、Suzuki偶合)合成含不同電子予體-受體比例的低能隙共聚高分子，以調整共聚高分子的電子結構與光物理特性。共聚高分子的電子予體為3-hexylthiophene (3HT)，而電子受體單元為2,3-diethylthieno[3,4-b]pyrazine (ETP)；每一個單元皆具有長碳鏈碗基做側鏈修飾，以提升共聚物的溶解度。以GRIM與Universal GRIM的方法僅能有效聚合P3HT，但並無法有效活化含有ETP的雙溴修飾單體，以致於無法得到含有ETP的共聚高分子；而藉由Suzuki偶合則成功的合成出3HT：ETP = 1：1~4：1 (P3HTETP-1-1 ~ -4-1)及fluorene與ETP的共聚高分子(PBF)。共聚高分子皆可溶解於trichlorobenzene中，溶解度隨著3HT比例的增加而增加。各共聚高分子的裂解溫度(Td)在271 ~ 446oC，且隨著3HT的含量上升而較穩定。
各共聚高分子在溶液中的紫外光/可見光的最大吸收(λsol, max)位於580 ~ 730nm，相較於P3HT(440nm)有明顯的紅移，可歸因於主鏈內顯著的電子予體-受體效應。光學能隙(Eg, opt)在1.27eV~1.77eV，隨著ETP比例的增加而下降。共聚高分子的固態吸收則較溶液吸收有不同程度的紅移，取決於共聚高分子的組成。由循環伏安測得各共聚物的電子最高填滿分子軌域(HOMO)在-4.64eV ~ -4.90eV、電子最低未填滿分子軌域(LUMO)在-2.69 eV~ -3.11eV；隨著ETP在共聚高分子內的比例上升，HOMO與LUMO分別上升及下降，但LUMO下降較HOMO上升明顯，電化學能隙(Eg, CV)為1.52 eV~ 2.19eV。這些低能隙的共聚高分子預期將可應用於高分子太陽能電池以提昇太陽光吸收的效率。 | zh_TW |
| dc.description.abstract | In this research, we employed GRIM, Universal GRIM and Suzuki coupling to synthesize low band conjugated copolymers consisting of electron-donating units (3-hexylthiophene, 3HT) and electron-accepting units (2,3-diethylthieno[3,4-b] pyrazine, ETP) in different ratios in order to adjust the electronic structure and photophysical properties of the copolymers. Each unit was decorated with long alkyl chains as side substitutions to enhance the solubility. GRIM and universal GRIM only successfully synthesized poly(3-hexylthiophene) (P3HT) but failed to synthesize any copolymers consisting of ETP owing to the failure in activating di-brominated monomers containing ETP. Copolymers containing 3HT and ETP in 1:1 to 4:1 molar ratio (P3HTETP-1-1 ~ -4-1) as well as fluorene and ETP (PBF) were successfully obtained via Suzuki coupling. These copolymers showed reasonable solubility in TCB while the solubility increased with increasing 3HT to ETP ratio. Decomposition temperatures ranges from 271oC to 446oC and the thermal stability enhanced with increasing 3HT content.
Absorption maxima of these copolymers in TCB solution were extended to longer wavelengths (565~690nm) compared to P3HT (440nm) due to strong intramolecular donor-acceptor interaction. Optical band gaps were 1.27eV~1.77eV, decreasing with increasing ETP ratio in the copolymers. The absorptions in solid state showed red shifts in different magnitudes in comparison with the absorptions in solution, depending on the composition of the copolymers. HOMO levels (-4.64eV ~ -4.90eV) and LUMO levels(-2.69eV ~ -3.11eV), obtained from cyclic voltametry, were raised and lowered respectively with increasing ETP ratio in the copolymer. The change in LUMO was more significant than that in HOMO. These ETP containing low band gap copolymers are potential candidates for polymer solar cells to enhance the light harvesting. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T04:10:52Z (GMT). No. of bitstreams: 1 ntu-99-R96527016-1.pdf: 2982962 bytes, checksum: 46b7b9d9e9cfd8310135be4f7d8a7bff (MD5) Previous issue date: 2010 | en |
| dc.description.tableofcontents | 致謝 I
摘要 II Abstract III 總目錄 V 圖索引 VII 表索引 IX 第一章、緒論 1 第二章、文獻回顧 5 2-1 導電高分子與太陽能電池工作原理和特性 5 2-1-1 工作原理 5 2-1-2 有機和無機太陽能電池之比較 7 2-1-3 特徵係數 9 2-1-4 能階調整與最適化 9 2-2 P3HT簡介 10 2-2-1 聚合規則排列P3AT的方式 12 2-2-2 鎳催化偶合聚合機制 14 2-2-3 規則排列比例之鑑定 15 2-2-4 紫外/可見光吸收特性 16 2-3 低能隙高分子設計原則 17 2-4 TP文獻回顧 20 2-5 聚合方式 26 2-5-1 Universal GRIM 27 2-5-2 Suzuki偶合 28 2-5-3 Stille偶合 29 2-6 研究動機 29 第三章、實驗方法 31 3-1 實驗藥品 31 3-2 實驗儀器 33 3-3 實驗步驟 34 3-3-1 單體合成 34 3-3-1-1 Br-3HT-Br合成 34 3-3-1-2 Br-ETP-Br合成 35 3-3-1-3 Br-3HT-ETP-3HT-Br合成 37 3-3-1-4 B-3HT-B合成 38 3-3-1-5 B-B3HT-B合成 38 3-3-1-6 B-F-B合成 39 3-3-2 GRIM聚合高分子 40 3-3-2-1 P3HT合成 40 3-3-2-2 PETP與P3HTETP合成 40 3-3-3 Universal GRIM聚合高分子 41 3-3-4 Suzuki偶合聚合高分子 42 3-4 特徵鑑定方法 43 第四章、結果與討論 44 4-1 單體合成與鑑定 44 4-1-1 Br-3HT-Br的合成 44 4-1-2 Br-ETP-Br合成 46 4-1-3 Br-3HT-ETP-3HT-Br的合成 50 4-1-4 B-3HT-B的合成 53 4-1-5 B-B3HT-B的合成 54 4-1-6 B-F-B的合成 55 4-2 GRIM聚合高分子 56 4-2-1 P3HT合成 56 4-2-2 PETP與P3HTETP之合成 59 4-3 Universal GRIM聚合高分子 59 4-3-1 P3HT合成 59 4-3-2 PETP與P3HTETP-2-1之合成 60 4-4 Suzuki偶合聚合高分子 62 4-5 熱裂解分析 63 4-6 光物理特性與電子結構 64 4-6-1 PETP與ETP的紫外/可見光光譜 64 4-6-2 共聚高分子的紫外/可見光光譜 65 4-6-3 電化學分析 69 第五章、結論 72 第六章、建議與未來工 73 第七章、參考文獻 74 | |
| dc.language.iso | zh-TW | |
| dc.title | 含3-hexylthiophene與2,3-diethylthieno[3,4-b]pyrazine之低能隙共聚高分子開發與研究 | zh_TW |
| dc.title | Low Bandgap Conjugated Copolymer containing 3HT and 2,3-dETP | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 98-1 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 林唯芳(Wei-Fang Su),戴子安(Chi-An Dai),陳錦地(Chin-Ti Chen) | |
| dc.subject.keyword | 低能隙共聚高分子,Poly(3-hexylthiophene),電子最高填滿分子軌域,電子最低未填滿分子軌域,高分子太陽能電池,電子結構工程, | zh_TW |
| dc.subject.keyword | low bandgap,conjugated copolymer,poly(3-hexylthiophene),HOMO,LUMO,polymer solar cell, | en |
| dc.relation.page | 75 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2010-01-28 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 材料科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 材料科學與工程學系 | |
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