FeS2(Pyrite) 擁有地球含量豐富、無毒性組成元素、合宜的能隙(約0.95 eV)及高吸收係數(α>105 cm−1)等特性，適合作為薄膜太陽能電池吸收層材料，且以其高吸收係數，理論上極薄的厚度(低於100 nm)即可使用，然而因其純相晶體難被合成，目前的應用仍然有限。
本論文我們藉由化學合成法合成出高品質、似立方體的Pyrite以及鈷摻雜的Pyrite奈米顆粒，其平均顆粒尺寸約為50~100 nm，由於初合成之Pyrite顆粒過大且傾向聚集成大於100 nm之團聚物，因此無法將其製作成小於50 nm的平整連續薄膜。
為解決此問題，我們採用高轉速珠磨法來擊碎並分散Pyrite奈米顆粒，經過珠磨參數如珠磨轉速、Pyrite與分散劑(油胺)的比重的調整後，我們獲得最佳的珠磨參數並得到懸浮良好的Pyrite奈米顆粒懸浮液，並以此分散液旋轉塗佈出膜厚約為30 nm的Pyrite薄膜。珠磨最佳參數為濃度1 wt.% Pyrite混合液、珠磨轉速2500 rpm、Pyrite/Oleylamine重量比5、研磨40 分鐘。
最後，於硫氛圍下針對旋轉塗佈好的薄膜進行熱處理，以去除殘存於膜上之分散液及薄膜缺陷。並進行熱處理後薄膜的微結構與光電性質研究，發現微量鈷元素摻雜後的Pyrite薄膜，由原先P型轉變為N型。不論是否有摻雜鈷元素，兩者薄膜的載子濃度皆大於1017cm-3且光吸收係數於波長低於700 nm時大於2×〖10〗^5 cm-1。

Iron pyrite (FeS2) is a promising photovoltaic absorber due to its earth abundance, non-toxic composition element, infrared band gap (Eg = 0.95 eV), and excellent photoabsorption characteristic (α>105 cm−1), which make it possible to allow the use of very thin (less than 100 nm) absorption layers. However, its use has been hindered because phase-pure pyrite nanocrystals are difficult to be synthesized.
In this work, by the means of chemical method, we synthesized cube-like Pyrite nanoparticles (NPs) and Co-doped Pyrite NPs with high quality and both of their size are around 50 to 100 nm. Since the NPs are big and tend to agglomerate to a size over 100 nm, they are unable to form smooth, continuous ultrathin films with thickness less than 50nm.
To solve this problem, bead mill at high milling speed was applied to smash the NPs into smaller pieces and then dispersed the agglomerate to yield well-dispersed pyrite NPs inks. After revising experimental parameters such as rotation speeds of rotor blade and weight ratio (WR) of Pyrite and surfactant(Oleylamine), we obtained the optimal experimental parameters to fabricate films with thickness about 30 nm by spin coating. The parameters are 1 wt. % pyrite slurry, rotor blade rotation speed at 2500 rpm, WR (Pyrite/OLA) of 5 and milling for 40 mins.
Eventually, we annealed the as-deposited Pyrite thin films under sulfur atmosphere in order to remove the surfactant and defects. Moreover, we investigated the microstructures and optoelectronic properties of these films, finding that Pyrite thin films transfer from P-type to N-type after doping a small amount of Cobalt. Also, the analytical result shows that both of their carrier concentration are above 1017 cm-3 and their photoabsorption coefficient are above 2×〖10〗^5 cm-1 for wavelength below 700 nm.

第一章 緒論 1
1.1 前言 1
1.2 研究背景 2
1.3 研究動機與實驗目的 7
第二章 文獻回顧 11
2.1 太陽能電池原理 11
2.2 FeS2(Pyrite)之晶體結構及物理特性 13
2.3 FeS2(Pyrite)薄膜的製程背景 15
2.3.1 FeS2(Pyrite)粉末法 16
2.3.2 Precursor硫化法 17
2.3.3 化學反應法 17
2.4 鈷摻雜FeS2(Pyrite)薄膜的製程背景 20
2.5 珠磨法介紹 21
2.5.1 珠磨法原理 22
2.6 動態光散射原理(DLS, Dynamic Light Scattering) 26
2.6.1 自相關函數 28
2.6.2 相關函數的後續演算 30
2.6.3 水化動力學半徑(hydrodynamic radius) 32
第三章 實驗方法與步驟 33
3.1 實驗流程 33
3.1.1 合成與摻雜實驗 33
3.1.2 珠磨實驗 33
3.1.3 薄膜製作熱處理及其光電性質調查 34
3.2 使用藥品 37
3.3 純 Pyrite 合成方法 37
3.4 Co摻雜之Pyrite 合成方法 38
3.5 珠磨法 39
3.5.1 珠磨裝置使用方法 39
3.5.2 珠磨法參數 40
3.6 各分析試片製備方法 42
3.6.1 素玻璃/矽基板清洗 42
3.6.2 XRD試片製備 42
3.6.3 SEM試片製備 44
3.6.4 Raman 試片製備 45
3.6.5 Hall measurement試片製備 45
3.6.6 UV-Vis試片製備 45
3.6.7 AFM試片製備 46
3.6.8 硫氛圍熱處理之試片製備 46
3.6.9 TEM試片製備 46
3.6.10 動態光散射粒徑分析(DLS) 的樣品製備 46
3.7 使用儀器之介紹 47
3.7.1 加熱攪拌器 47
3.7.2 離心機 47
3.7.3 珠磨機 47
3.7.4 粒徑分析儀 48
3.7.5 旋轉塗佈機 48
3.7.6 X-Ray 繞射分析儀 48
3.7.7 掃描式電子顯微鏡 49
3.7.8 場發射掃描穿透式球差修正電子顯微鏡 49
3.7.9 微拉曼光譜儀系統 50
3.7.10 紫外－可見光光學儀 50
3.7.11 霍爾量測系統 50
3.7.12 原子力顯微鏡 51
第四章結果與討論 52
4.1 FeS2 (Pyrite)奈米顆粒合成分析及選用 54
4.1.1 FeS2 (Pyrite) 奈米顆粒的XRD、SEM、SEM-EDS分析 54
4.1.2 FeS2 (Pyrite) 奈米顆粒的Raman分析 60
4.1.3 FeS2 (Pyrite) 奈米顆粒的TEM分析 61
4.1.4 Pyrite新舊合成法之優缺點比較 63
4.2 鈷摻雜之FeS2 (Pyrite) 奈米顆粒合成分析及選用 63
4.2.1 鈷摻雜FeS2 (Pyrite)奈米顆粒的XRD、SEM、SEM-EDS的分析 64
4.2.2 鈷摻雜之FeS2 (Pyrite) 奈米顆粒的TEM分析 67
4.3 珠磨法應用於FeS2(Pyrite)奈米顆粒磨碎及分散 69
4.3.1 溼式研磨溶劑及分散劑的選用 69
4.3.2 分散劑劑量對Pyrite珠磨混合液之影響 69
4.3.3 珠磨轉速對濃度0.13 wt.% Pyrite珠磨混合液之影響 82
4.3.4 分散劑劑量對濃度1 wt.%的Pyrite混合液珠磨的影響 88
4.3.5 濃度1 wt.%的Pyrite混合液珠磨參數之選用 97
4.3.6濃度1 wt.%的鈷摻雜Pyrite混合液珠磨的參數選用 97
4.3.7 未摻雜/鈷摻雜之Pyrite懸浮液製作 101
4.3.8 選用懸浮液樣品之XRD分析 102
4.3.9珠磨參數選用之TEM分析 103
4.3.10 未摻雜/鈷摻雜之Pyrite混合液珠磨參數分析 107
4.4薄膜製作、熱處理及其光電性質調查 108
4.4.1 掃描電子顯微鏡(SEM)分析 108
4.4.2 原子力顯微鏡(AFM)分析 110
4.4.3 霍爾量測(Hall measurement) 113
4.4.4 紫外－可見光之光學分析(UV-Vis) 115
結論 117
參考文獻 119

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