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研究生: 許書維
Hsu, Shu-Wei
論文名稱: 聚(3-己烷基噻吩) /碳六十衍生物為主動層之異質接面結構有機太陽能電池特性研究
Studies of organic solar cells using poly(3-hexylthiophene) /fullerene derivative bulk heterojunction
指導教授: 鄭弘隆
Cheng, Horng-Long
學位類別: 碩士
Master
系所名稱: 理學院 - 光電科學與工程研究所
Institute of Electro-Optical Science and Engineering
論文出版年: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 129
中文關鍵詞: 有機太陽能電池塊材異質接面結構三元混和聚甲基丙烯酸甲酯聚芴有效共軛鏈長吸收光譜拉曼光譜
外文關鍵詞: Organic solar cells, Bulk heterojunction structure, Ternary blend, Polymethylmethacrylate, Polyfluorene–Green, Effective Conjugation length, Absorption spectroscopy, Raman spectroscopy
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  • 本研究在探討藉由改變主動層內三元高分子的混合比例對塊材異質接面結構有機太陽能電池的電特性之影響,其中以p型的聚(3-己烷基噻吩)(poly(3-hexylthiophene), P3HT)和n型的碳六十衍生物([6,6]-phenyl-C61-butyric acid methyl ester, PCBM)作為主動層的基本材料,並且與特定的高分子進行摻和。依所摻和的材料分類,可將實驗分為兩個部分,第一部分是摻和絕緣高分子的聚甲基丙烯酸甲酯 (Polymethylmethacrylate, PMMA),第二部分則是摻和螢光高分子的聚芴(Polyfluorene–Green, PF-G)。實驗中除了對主動層薄膜進行吸收光譜、拉曼光譜、X光繞射光譜、光致螢光光譜和原子力顯微鏡的分析外,太陽能電池元件也在AM1.5G且100 mW/cm2的模擬太陽光照射下進行電特性的量測。希望藉由摻和材料的加入,使主動層的結構形態改變,進而研究主動層結構形態與太陽能電池電特性之間的關係。
    在第一部分中,我們製作不同混合比例的P3HT:PCBM:PMMA主動層薄膜與有機太陽能電池元件。由吸收光譜與拉曼光譜的分析結果可知,將PMMA混入P3HT:PCBM薄膜後,P3HT鏈之有效共軛鏈長的長短分佈較具一致性,使主動層的薄膜均勻性獲得提升;X光繞射光譜則指出PMMA對P3HT結晶區域並無重大影響,而在P3HT:PCBM主動層薄膜內摻和重量百分比為2.4 %的PMMA能使元件的光電轉換效率上升1.5倍。
    在第二部分中,我們選用共軛高分子PF-G做為摻和材料,且研究摻和PF-G對P3HT:PCBM主動層薄膜結構的影響和由此影響所產生的太陽能電池電特性變化。P3HT:PCBM薄膜在加入PF-G後,P3HT鏈之有效共軛鏈長的長短分佈變的較為均勻,且從X光繞射光譜的結構分析可知PMMA對P3HT結晶區域並無重大影響,但PF-G的摻和會改善PCBM、PF-G和 P3HT非結晶區域的混和程度。螢光光譜指出,當主動層內的PF-G重量百分比在14%以上,則可在PF-G與P3HT間成功的產生能量轉移。最終我們沒能觀察到P3HT:PCBM:PF-G薄膜的混和比例和太陽能電池電特性的直接關係,元件電性並沒有隨著PF-G摻和比例的不同而有規律性的變化。

    This study investigates the ways in which the change in the composition of ternary polymer blends affects the photovoltaic properties of bulk-heterojunction-type organic solar cells (OSCs). The ternary polymer blended active layers were prepared from a p-type poly(3-hexylthiophene) (P3HT) and an n-type fullerene derivative (i.e., [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)), which were mixed with the specific polymers. The study can be divided into the following two parts: 1) the blending polymer or the insulating polymer, i.e., polymethylmethacrylate (PMMA), and 2) a fluorescent polymer, i.e., polyfluorene-green (PF-G). The active layers were investigated using absorption spectroscopy, Raman spectroscopy, x-ray diffraction (XRD), photoluminescence spectroscopy, and atomic force microscopy. The electrical parameters of the OSC devices were measured under simulated sunlight with an AM 1.5G filter at 100 mW/cm2. We studied the correlation between the morphology of the active layers and the photovoltaic properties of the solar cells.
    In part 1, we fabricated P3HT:PCBM:PMMA thin films with various compositions for the active layer of OSC devices. The absorption and Raman spectral data reveal the fact that introducing the PMMA into the P3HT:PCBM blends results in a narrower distribution of effective conjugation length (Leff) for the P3HT chains, thereby improving the degree of film homogeneity. Structural analysis using XRD suggests that the incorporation of PMM does not alter the crystalline domain of P3HT in the blends. The power conversion efficiency of the OSC device was enhanced by a factor of 1.5 by adding 2.4 wt% PMMA into the P3HT:PCBM active layer.
    In part 2, we studied the effects of adding the conjugated polymer PF-G on the structure of the P3HT:PCBM films and the resulting relevant photovoltaic properties in the OSC devices. When the PF-G was incorporated into the P3HT:PCBM blended films, the distribution of the Leff of the P3HT chains were more uniform, and no significant changes were observed in the P3HT crystalline region according to the structural analysis. However, the addition of PF-G into the P3HT:PCBM blends could improve the compatibility of the P3HT amorphous chains, PCBM, and PF-G. We observed a considerable energy transfer process between P3HT and PF-G upon the addition of over 14 wt% of PF-G into the P3HT:PCBM blends. Finally, we did not observe a direct relationship between the compositions of the P3HT:PCBM:PF-G blends and the photovoltaic properties of the OSC devices.

    中文摘要..........................................................................I Abstract..............................III 誌謝.........................................................V 目錄..............................................................................VII 表目錄.........................................................................XI 圖目錄.........................................................................XIII 第一章 緒論與理論基礎............................................1 1-1 前言......................................................................................1 1-2 有機太陽能電池的發展......................................................4 1-3 有機太陽能電池的工作原理..............................................7 1-4 有機太陽能電池的等效電路..............................................9 1-5 有機太陽能電池的特性參數.............................................11 1-5-1 開路電壓....................................................................................11 1-5-2 短路電流....................................................................................11 1-5-3 填充因子....................................................................................12 1-5-4 轉換效率....................................................................................12 1-6 太陽光頻譜........................................................................13 1-7 研究目的............................................................................14 第二章 在主動層摻和絕緣高分子對有機太陽能電池特性變化之研究.....................................20 2-1 前言....................................................................................20 2-2 實驗方法............................................................................22 2-2-1 實驗材料.................................................................................22 2-2-2 主動層溶液配製.....................................................................23 2-2-3 主動層溶液混合比例.............................................................23 2-2-4 元件製作流程.........................................................................24 2-3 元件電性量測....................................................................27 2-3-1 校正太陽光模擬器.................................................................27 2-3-2 J-V特性曲線量測....................................................................27 2-4 薄膜與光學特性分析儀器................................................28 2-4-1 紫外-可見光分光光譜儀.......................................................28 2-4-2 微拉曼光譜儀.........................................................................28 2-4-3 X光繞射光譜儀......................................................................28 2-5 結果與討論........................................................................29 2-5-1 紫外-可見光分光光譜儀分析...............................................29 2-5-2 微拉曼光譜儀分析.................................................................30 2-5-3 X光繞射光譜儀分析..............................................................32 2-5-4 有機太陽能電池電性.............................................................33 2-6 結語....................................................................................34 第三章 在主動層摻和螢光高分子對有機太陽能電池特性變化之研究.....................................62 3-1 前言....................................................................................62 3-2 實驗方法............................................................................64 3-2-1 實驗材料.................................................................................64 3-2-2 主動層材料的溶液配製.........................................................65 2-2-3 主動層材料的混合比例.........................................................65 3-2-4 元件製作流程.........................................................................66 3-3 元件電性量測....................................................................67 3-3-1 校正太陽光模擬器.................................................................67 3-3-2 J-V特性曲線量測....................................................................67 3-4 薄膜與光學特性分析儀器................................................67 3-4-1 紫外-可見光分光光譜儀.......................................................67 3-4-2 微拉曼光譜儀.........................................................................67 3-4-3 X光繞射光譜儀......................................................................67 3-4-4 原子力顯微鏡.........................................................................68 3-4-5 螢光光譜儀系統.....................................................................68 3-4-6 時間解析光致螢光光譜.........................................................68 3-5 結果與討論........................................................................69 3-5-1 紫外-可見光分光光譜分析...................................................69 3-5-2 光致螢光光譜分析.................................................................70 3-5-3 螢光激發光譜分析.................................................................71 3-5-4 時間解析光致螢光光譜分析.................................................73 3-5-5 微拉曼光譜分析.....................................................................74 3-5-6 X光繞射光譜分析..................................................................75 3-5-7 原子力顯微鏡量測結果分析.................................................75 3-5-8 有機太陽能電池電性.............................................................76 3-6 結語....................................................................................77 第四章 總結.................................................................122 參考文獻.......................................................................124

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