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系統識別號 U0026-1507201414100300
論文名稱(中文) 使用三乙醇胺作為錯合劑電沉積二硒化銅鋁、銅銦鋁硒薄膜之研究
論文名稱(英文) Study of electrodeposition of CuAlSe2 and Cu(In,Al)Se2 thin films with triethanolamine as the complexing agent
校院名稱 成功大學
系所名稱(中) 化學系
系所名稱(英) Department of Chemistry
學年度 102
學期 2
出版年 103
研究生(中文) 陳建廷
研究生(英文) Chien-Ting Chen
學號 l36014231
學位類別 碩士
語文別 中文
論文頁數 94頁
口試委員 指導教授-黃守仁
口試委員-蘇世剛
口試委員-李賢哲
中文關鍵字 二硒化銅鋁  銅銦鋁硒  電沉積  鍛燒  吸收係數 
英文關鍵字 CuAlSe2  Cu(In,Al)Se2  electrodeposition  annealing  absorption coefficient. 
學科別分類
中文摘要 本實驗以電沉積方式,在含氯化物的水溶液中添加三乙醇胺(Triethanolamine,TEA)作為錯合劑,將二硒化銅鋁 (CuAlSe2,CAS)、以及銅銦鋁硒 (Cu(In,Al)Se2,CIAS)電沉積於ITO玻璃基板上。實驗變因包含:各個離子組成濃度、鍛燒溫度與時間、TEA濃度、電沉積電位、電沉積時間,其中鍍製二硒化銅鋁薄膜最佳條件為 5mM CuCl2 +30 mM AlCl3 + 22 mM SeO2 + 0.2 M TEA,在pH=2.50下鍛燒300 °C/1.0 hr。
不同沉積電位會影響實驗的電流密度、粒徑大小、膜厚、能隙。薄膜的晶格結構、組成比例、表面形貌,分別利用X光粉末繞射儀、能量分散式光譜儀、掃描式電子顯微鏡來進行分析。在X光粉末繞射儀分析上,薄膜特徵峰值強度會隨上述變因而有些微不同,而從能量分散式光譜儀發現薄膜中Se原子比例的偏低會導致利用公式計算出來的能隙有降低的趨勢。
薄膜的光學性質上,利用紫外光/可見光/近紅外光光譜儀來進行分析,利用測量穿透度、折射度然後經過公式計算出來的吸收係數也不相同。整體上薄膜吸收係數皆達到104 cm-1,表示薄膜具很強的吸收太陽光的特性是良好的吸收材料。
英文摘要 In our experiments, CAS and CIAS were deposited on ITO glass from chloride electrolytes by the method of co-electrodeposition. The parameters include: individual ion concentration, annealing temperature and annealing time, TEA concentration, deposition potential and deposition time. Among all conditions, the optimum condition was 5 mM CuCl2 + 30 mM AlCl3 + 22 mM SeO2 + 0.2 M TEA deposited at pH 2.50 and then under annealing at 300 °C for 1.0 hr.

Current density, particle size, thickness and band gap were found to be affected by the deposition potential. The crystal structure, compositions and morphologies of the deposited thin films were determined by X-ray powder diffractometer, energy dispersive spectrometer and scanning electron microscope, respectively. X-ray diffraction patterns revealed the peak intensities of the deposits were altered when the parameters mentioned above changed. From the analysis of EDS, the atomic ratios of Se in the films of deposits were discovered lower than the stoichiometric ratio. This phenomenon would narrow down the band gap, which can be calculated from formulas.

To investigate the optical properties, transmittance and reflectance of the films could be examined by UV-VIS-NIR-Spectrophotometer, and it would cause different absorption coefficients which were calculated from formulas. Overall, the absorption coefficient of the deposited films was as high as 104 cm-1, demonstrates that the films are potential absorbing materials because it possesses strong sunlight-absorbing characteristics.
論文目次 摘要 I
Extend abstract II
誌謝 X
目錄 XI
表目錄 XV
圖目錄 XVI
第一章 緒論 1
1.1 前言 1
1.2 太陽能電池簡介 4
1.2.1 太陽光譜 4
1.2.2 光電轉換原理 7
1.2.3 太陽能電池工作原理 9
1.2.4 太陽能電池種類 10
1.3 研究動機 13
第二章 實驗基礎理論與原理 15
2.1 二硒化銅鋁(CuAlSe2)薄膜半導體簡介 15
2.2 電化學原理 16
2.2.1 循環伏安法 (Cyclic Voltammetry,CV) 17
2.2.2 定電位電解法 (Chronoamperometry,CA) 18
2.2.3 定電流電解法 (Chronopotentiometry) 20
2.3 I-III-VI族半導體薄膜製備方式 21
2.3.1物理氣相沉積法 (Physical Vapor Deposition,PVD) 21
2.3.2化學氣相沉積法 (Chemical Vapor Deposition,CVD) 22
2.3.3濺鍍 (Sputtering) 23
2.3.4化學水浴沉積法 (Chemical Bath Deposition,CBD) 24
2.3.5原子層磊晶法法 (Atomic Layer Deposition,ALD) 25
2.3.6電化學沉積法法 (Electrochemical Deposition,ED) 25
2.4 電鍍液酸鹼值選擇 26
第三章 實驗方法、儀器設備 29
3.1 實驗流程 29
3.1.1 ITO玻璃前處理 30
3.1.2 電鍍液CAS、CIAS配製 30
3.1.3 電沉積CAS、CIAS薄膜 30
3.1.4 薄膜性質分析 31
3.2 實驗步驟 33
3.3 實驗藥品 34
第四章 結果與討論 35
4.1 循環伏安法分析(Cyclic Voltammetry) 35
4.1.1 單一元素銅 (Cu)之CV Diagram 35
4.1.2 單一元素鋁 (Al)之CV Diagram 39
4.1.3 單一元素硒 (Se)之CV Diagram 40
4.1.4 三元素銅 (Cu)+鋁 (Al)+硒 (Se)之CV Diagram 42
4.2 鍛燒前後CuAlSe2薄膜差異探討 44
4.3 化學計量分析 (Stoichiometric Analysis) 48
4.3.1 個別離子濃度對薄膜組成的影響 48
4.3.2 鍛燒時間/ 溫度對薄膜組成的影響 51
4.3.3 錯合劑濃度對薄膜組成的影響 54
4.4 電沉積二硒化銅鋁薄膜 56
4.4.1 不同沉積電位下CuAlSe2薄膜 56
4.4.2不同沉積電位下CuAlSe2薄膜之XRD圖 58
4.4.3不同沉積電位下CuAlSe2薄膜之Transmittance圖 60
4.4.4不同沉積電位下CuAlSe2薄膜之吸收係數圖 61
4.4.5不同沉積電位下CuAlSe2薄膜之能隙圖 62
4.4.6不同沉積電位下CuAlSe2薄膜之SEM圖 64
4.4.7不同沉積電位下CuAlSe2薄膜之晶格常數 65
4.4.8不同沉積時間下CuAlSe2薄膜 66
4.4.9不同沉積時間下CuAlSe2薄膜之XRD圖 68
4.4.10不同沉積時間下CuAlSe2薄膜之Transmittance圖 70
4.4.11不同沉積時間下CuAlSe2薄膜之吸收係數圖 71
4.4.12不同沉積時間下CuAlSe2薄膜之能隙圖 71
4.4.13不同沉積時間下CuAlSe2薄膜之SEM圖 74
4.5 電沉積銅銦鋁硒薄膜 76
4.5.1 不同沉積電位下Cu(In,Al)Se2薄膜 76
4.5.2 不同沉積電位下Cu(In,Al)Se2薄膜之XRD圖 78
4.5.3不同沉積電位下Cu(In,Al)Se2薄膜之吸收係數圖 79
4.5.4不同沉積電位下Cu(In,Al)Se2薄膜之能隙圖 81
4.5.5不同沉積電位下Cu(In,Al)Se2薄膜之SEM圖 85
第五章 結論 87
參考文獻 89
附錄 93
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