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研究生:張尚霖
研究生(外文):Shang-LinChang
論文名稱:以共電鍍製備可撓曲式CIS太陽能電池之研究
論文名稱(外文):A study on co-electrodeposition CIS film for flexible Solar Cell Application
指導教授:李文熙
指導教授(外文):Wen-Hsi Lee
學位類別:碩士
校院名稱:國立成功大學
系所名稱:電機工程學系碩博士班
學門:工程學門
學類:電資工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:123
中文關鍵詞:電鍍銅銦硒薄膜軟性基板
外文關鍵詞:electrodepositionCuInSe2flexible solar cell
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本實驗首先在不銹鋼基板上生成不同厚度的氧化鋁阻絕層,以SIMS確認其阻絕能力後,在其上濺鍍一層鉬背電極,用四點探針測量其阻抗值以及使用AFM測定其表面粗糙度,以便與生成在玻璃上的鍍膜做比較。隨後對不同阻絕層厚度的基板做循環伏安法的電化學分析,了解在不同阻絕層厚度下的基板是否會造成與玻璃上不同的還原機制與差異,以方便控制日後的電鍍條件;改變電鍍溶液中的成份濃度並變化熱處理持溫時間,使用EDS確認其成分,並利用FE-SEM來觀察CIS薄膜表面的微結構變化,XRD來分析CuInSe2的結晶性強弱變化,並用拉曼光譜來做輔助有無二次相的存在。實驗結果顯示,氧化鋁層在300nm的時候已經可以有效的阻隔來自不銹鋼基板的鐵、鉻的擴散,且由AFM可得知隨著氧化鋁阻絕層的厚度漸增,其表面的粗糙度會慢慢變低。基板表面的粗糙度隨著氧化鋁厚度的變厚而降低,電阻率也隨之減小。由拉曼光譜以及XRD分析發現氧化鋁層較厚的基板在長時間退火之後較氧化鋁厚度薄的基板容易產生二次雜相,且結晶性不如氧化鋁厚度500nm的試片。由SEM表面結構分析可以發現氧化鋁厚度500nm的樣本在長時間的熱退火之後能夠產生晶界相當明顯的大顆粒結晶。
Stainless steel substrate will be sputtered with Al2O3 insulation layer by different thickness, examining by SIMS to confirm that Fe and Cr from substrate will not contaminate the whole solar cell. Atomic force microscope (AFM) and four point probe will be used to measure the roughness and the resistance of the Mo back-contact sputtered on the substrate.
Cyclic voltammetry (CV) was utilized to examine the reaction potential of the ions in the solution, and this made us know the mechanism of the co- eletrodeposition between substrates with different thickness of Al2O3 layer. Energy dispersive spectroscopy (EDS) was used to estimate the composition of the CuInSe2 thin films. In the meanwhile the microstructure was observed by Multi- functional Field-Emission Scanning Electron Microscope (FE-SEM). The crystal structure of the thin films was identified by powder x-ray diffraction (XRD). Raman spectroscopy was applied for analysis of second phase.
Based on SIMS analysis, the contamination of Fe and Cr stop by Al2O3 barrier with 300nm thickness. From AFM analysis and four point probe measurement, we know that the surface roughness and resistance will decrease while the barrier layer goes thicker. From Raman spectroscopy and XRD, we find that the substrate with thicker Al2O3 barrier layer is easy to generate second phase, and the crystal structure of CuInSe2 thin film is worse than the thinner one after long time annealing process. Substrate with 500nm Al2O3 barrier layer has better CuInSe2 structure than substrate with thicker Al2O3 layer.
第一章 緒論 1
1-1 前言 1
1-2 實驗動機與目的 4
第二章 文獻回顧 5
2-1 太陽電池工作原理[15] 5
2-2 二硒化銅銦薄膜介紹 11
2-3電鍍原理 13
2-3.1電化學之沉積 13
2-3.2 電流效率 15
2-3.3 電極介紹[23] 15
2-3.4 電鍍液組成介紹 17
2-4 不銹鋼基板之阻絕層 17
2-5 由X光繞射法分析薄膜內之殘餘應力 20
2-6 循環伏安法 22
2-7 二硒化銅銦形成之反應機制[31-34] 23
第三章 實驗方法與步驟 27
3-1 實驗材料 27
3-2實驗設備 28
3-2.1 恆電位儀 28
3-2.2 薄膜濺鍍系統(Sputtering System ) 29
3-2.3 磁石攪拌平台 31
3-2.4 高溫爐(Furnace) 31
3-3 鍍層分析儀器 32
3-3.1 α-step 膜厚計 32
3-3.2 四點探針 32
3-3.3 掃描式電子顯微鏡[43] (Scanning Electron Microscope;SEM) 33
3-3.4 能量分散光譜儀[43](Energy Dispersive Spectroscopy;EDS) 34
3-3.5 X-Ray 粉末繞射儀 (Powder X-ray Diffraction)[29] 35
3-3.6 拉曼光譜儀[43] 36
3-3.7 原子力顯微鏡 (Atomic Force Microscopy;AFM) 37
3-4 實驗流程與規劃 38
3-4.1清洗基板 39
3-4.2 反應式濺鍍:沉積氧化鋁層及熱處理 39
3-4.3 濺鍍鉬背電極 40
3-4.4 配置電鍍液 40
3-4.5 循環伏安法 (Cyclic Voltammetry) 40
3-4.6 電鍍CuInSe2 膜及參數調變 41
3-4.7 高溫爐熱處理合成CuInSe2 41
第四章 實驗結果與討論 42
4-1 不銹鋼基板與氧化鋁阻絕層 42
4-2 電化學分析 53
4-2.1 單元素電化學分析 53
4-2.2 雙元素電化學分析 57
4-2.3 銅銦硒三元電化學分析 58
4-3 薄膜組成成份分析及表面觀察 59
4-3.1 初鍍膜成分分析 59
4-3.2 熱處理時間變化之成分分析 71
4-4 薄膜晶體結構XRD分析 96
1. 氧化鋁厚度300nm不銹鋼鍍鉬基板之鍍層 96
2. 氧化鋁厚度500nm不銹鋼鍍鉬基板之鍍層 98
3. 氧化鋁厚度1um不銹鋼鍍鉬基板之鍍層 100
4. 氧化鋁厚度2um不銹鋼鍍鉬基板之鍍層 102
4-5 拉曼光譜分析 108
1. 氧化鋁厚度300nm不銹鋼鍍鉬基板之鍍層 108
2. 氧化鋁厚度500nm不銹鋼鍍鉬基板之鍍層 110
3. 氧化鋁厚度1um不銹鋼鍍鉬基板之鍍層 111
4. 氧化鋁厚度2um不銹鋼鍍鉬基板之鍍層 113
第五章 結論 119
第六章 參考文獻 121
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