臺灣博碩士論文加值系統

本論文是研究銅鎵二硫（CuGaS2）薄膜在太陽能電池吸收層材料之應用。本實驗是利用球磨法(Ball Milling)來製備成銅鎵二硫前驅物漿料(Ink)，再以旋轉塗佈法(spin coating)將其漿料塗佈於基板上形成CGS2前驅層（precursor）薄膜，所用的前驅物是由CuS、Ga2S3等兩種化合物混合所形成，且可獨立調整兩種前驅物成分比例，以獲得不同的Cu/Ga比。再置於RTP爐管內進行(400-800℃)快速退火製程，藉由高溫擴散(diffusion)，製備出具黃銅礦（Chalcopyrite）結構特性之CGS2薄膜，使用非真空(non-vacuum)製程製備吸收層可大幅降低成本。而CGS2薄膜會隨著Cu含量的增加，半高寬變窄，晶粒尺寸會隨之變大；XRD之特徵峰會隨Cu含量增加向高角度（2θ）偏移。依原始組成Cu/Ga比將薄膜分為Cu-rich與Cu-poor兩種類型，利用X光繞射進行分析，結果顯示CGS2薄膜具有黃銅礦結構之結晶特性。本研究發展新方式製備CGS2前驅層，其熱處理時間不需太長，且可在不通入硒蒸氣或硒化氫等氣體下，基於實驗分析之結果，於熱處理溫度650℃、持溫10min，得到的黃銅礦結構之CGS2薄膜為佳。

The thesis is focused on the application of CuGaS2 for solar cell absorber layer materials. In this study, the nanoparticle ink is prepared using wet-ball milling, and then the ink is deposited on a substrate to form a precursor layer by spin coating. The ink consists of two compound powders, CuS and Ga2S3. By adjust Cu/Ga ratio of CuS to Ga2S3. The precursor layer is placed in RTA furnace, and then heated at the temperature between 400℃ and 800℃ to form the compound layer with chalcopyrite structure. Non-vacuum processing is capable of reducing the cost of manufacturing significantly. CGS2 thin film with the full width at half maximum becoming narrow as the Cu content increases. The mean crystallite size also increases when Cu/Ga ratio is increased. Some displacement towards higher diffraction angles is detected when the Cu content increases. According to the original composition of Cu/Ga ratio, the prepared precursor samples can be classified to two types: Cu-rich and Cu-poor samples based. Microstructural studies are carried out using X-ray diffractometer. The analysis result shows that these samples have chalcopyrite structure. We have developed a novel technique for fabricating CuGaS2 thin film without long heat treatment and selenization. Based on the analysis results of this experiment, CuGaS2 thin film with chalcopyrite structure can be obtained by heating at 650℃ for 10 minutes.

總目錄

中文摘要…………………………i
Abstract…………………………ii
致謝…………………………iii
總目錄…………………………iv
表目錄…………………………viii
圖目錄…………………………ix
第一章 簡介…………………………1
1.1 前言…………………………1
1.2 太陽能電池的分類…………………………6
1.2.1 非晶矽（Amorphous Silicon；a-Si）薄膜太陽能電池………6
1.2.2 非晶矽（a-Si）/ 微晶矽（μc-Si）堆疊薄膜太陽能電池………7
1.2.3 碲化鎘（CdTe）薄膜太陽能電池…………………………7
1.2.4 銅銦鎵硒（CIGS）薄膜太陽能電池…………………………7
1.3 CuGaS2特性…………………………9
1.4 研究動機…………………………9
第二章 理論基礎與文獻回顧…………………………18
2.1 太陽能電池工作原理…………………………18
2.2 銅銦硒薄膜太陽能電池…………………………20
2.3 銅銦鎵硒吸收層製程技術…………………………25
2.3.1 蒸鍍法…………………………26
2.3.2 硒化法…………………………27
2.3.3 塗佈法…………………………28
2.4 球磨粉碎原理及其方法…………………………28
2.4.1 球磨粉碎原理…………………………28
2.4.2 機械分散法…………………………30
2.4.3 化學分散法…………………………31
2.4.4 超音波分散法 …………………………31
2.5 影響球磨粉碎顆粒大小的變因…………………………32
2.6 快速退火RTP之熱輻射原理…………………………33
第三章 實驗流程與分析…………………………44
3.1 實驗材料…………………………44
3.1.1 製備CuGaS2漿料之化合物…………………………44
3.1.2 基材…………………………44
3.1.3 製備前驅層薄膜所需氣體…………………………44
3.2 製程設備…………………………44
3.2.1 超細粉末製造設備…………………………44
3.2.2 旋轉塗佈機…………………………45
3.2.3 快速退火系統 …………………………45
3.3 實驗流程…………………………46
3.3.1 基板前處理…………………………46
3.3.2 漿料製備…………………………46
3.3.3 快速退火處理 …………………………47
3.4 實驗分析設備…………………………48
3.4.1 掃瞄式電子顯微鏡（Scanning Electron Microscope，SEM）………48
3.4.2 能量散佈光譜儀（Energy Dispersive Spectrometer，EDS）………50
3.4.3 X光繞射儀（X-Ray diffraction，XRD……………50
3.4.4 UV-VIS（紫外光-可見光）光譜儀…………………………52
3.4.5 螢光激發光譜儀(Photoluminescence Excitation，PLE)………53
第四章 結果與討論…………………………64
4.1 顯微結構分析…………………………64
4.1.1 熱處理溫度對銅鎵二硫薄膜顯微結構之影響……………64
4.1.2 熱處理溫度對銅鎵二硫薄膜橫截面結構之影響……………65
4.2 CuGaS2薄膜成份分析…………………………66
4.3 結晶特性分析…………………………68
4.3.1 熱處理溫度對銅鎵二硫薄膜結晶特性之影響……………68
4.3.2 熱處理溫度對銅鎵二硫薄膜(204)特徵峰之影響……………70
4.3.3 貧銅與富銅對銅鎵二硫薄膜(204)特徵峰之影響……………71
4.4 CuGaS2光學特性分析…………………………72
4.4.1 (紫外光-可見光)光譜分析…………………………72
4.4.2 螢光激發光譜分析…………………………73
第五章 結論…………………………89
參考文獻…………………………91
Extended Abstract…………………………96
簡歷…………………………99

表目錄

表1.1 Ⅰ-Ⅲ-Ⅵ族化合物半導體能隙…………………………11

表3.1 Cu-poor球磨參數…………………………54
表3.2 Cu-rich 球磨參數…………………………54
表3.3 熱處理參數…………………………55
表3.4 各種X光源靶材之波長…………………………55

表4.1 Cu、Ga、S元素一覽表…………………………75
表4.2 Cu-poor之CuGaS2薄膜在不同熱處理溫度下之EDS分析………76
表4.3 Cu-rich之CuGaS2薄膜在不同熱處理溫度下之EDS分析………76


圖目錄

圖1.1 單晶、多晶、非晶示意圖…………………………12
圖1.2 非晶矽薄膜太陽能電池結構圖…………………………13
圖1.3 非晶矽/微晶矽堆疊薄膜太陽能電池結構圖……………14
圖1.4 碲化鎘薄膜太陽能電池結構圖…………………………15
圖1.5 CIGS薄膜太陽能電池結構圖…………………………16
圖1.6 黃銅礦(Chalcopyrite)結構圖…………………………17

圖2.1 太陽照射下的p-n接面示意圖（上圖）及能帶圖（下圖）………36
圖2.2 太陽能電池I-V特性曲線 …………………………37
圖2.3 太陽能電池之p-n接面等校電路圖…………………………38
圖2.4 各類太陽能電池吸收材料之各波長之吸收係數……………39
圖2.5 物理氣相沉積之蒸鍍法和濺鍍蒸鍍法(左圖)及硒化法(右圖)………40
圖2.6 Cu2Se-In2Se3 (CIS)合金相圖…………………………41
圖2.7 緩衝層能舒緩主吸收層與透明導電層之間的Band-Offset………42
圖2.8 NREL 三階段共蒸鍍製程 …………………………43
圖2.9 磨球與磨球之間的有效粉碎區…………………………43

圖 3.1 行星式離心球磨機Retsch PM-200 …………………………56
圖 3.2 氧化鋯球磨罐&氧化鋯磨球…………………………56
圖 3.3 旋轉塗佈機…………………………57
圖 3.4 紅外線快速退火爐…………………………57
圖 3.5 實驗流程圖…………………………58
圖 3.6 二階段軟烤示意圖…………………………59
圖 3.7 熱處理載台設計…………………………59
圖 3.8 掃描式電子顯微鏡暨能量散佈光譜儀……………60
圖 3.9 掃描式電子顯微鏡系統示意圖…………………………60
圖 3.10 X光繞射儀…………………………61
圖 3.11 (紫外光-可見光)光譜分析儀…………………………62
圖 3.12 (紫外光-可見光)光譜分析儀示意圖……………62
圖 3.13 螢光激發光譜儀…………………………63
圖 3.14 螢光激發光系統示意圖…………………………63

圖4.1 Cu-poor之CuGaS2薄膜在不同熱處理溫度下之顯微結構………77
圖4.2 Cu-rich之CuGaS2薄膜在不同熱處理溫度下之顯微結構………78
圖4.3 各種元素之飽和蒸汽壓與溫度關係圖……………79
圖4.4 Cu-poor之CuGaS2薄膜在不同熱處理溫度下之橫截面結構………80
圖4.5 Cu-rich之CuGaS2薄膜在不同熱處理溫度下之橫截面結構………81
圖4.6 (a) Cu-S、(b) Ga-S之二元相圖…………………………82
圖4.7 (a) Cu-poor、(b) Cu-rich之CuGaS2在不同熱處理溫度之XRD………83
圖4.8 Cu-poor之CuGaS2在不同熱處理溫度的特徵峰強度之XRD………84
圖4.9 Cu-rich之CuGaS2在不同熱處理溫度的特徵峰強度之XRD………84
圖4.10 Cu-poor之CuGaS2在不同熱處理溫度的(204)特徵峰之XRD………85
圖4.11 Cu-rich之CuGaS2在不同熱處理溫度的(204)特徵峰之XRD………85
圖4.12 Cu-poor&Cu-rich之CuGaS2在650℃的(204)特徵峰之XRD………86
圖4.13 Cu-poor&Cu-rich之CuGaS2薄膜在溫度650℃之UV圖譜………87
圖4.14 Cu-poor&Cu-rich之CuGaS2薄膜在溫度650℃之PLE圖譜………88

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