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姓名	王宣文(Hsuan-Wen Wang)  查詢紙本館藏	畢業系所	光電科學與工程學系
論文名稱	以濺鍍法製作矽異質接面太陽能電池之研究:矽薄膜特性對元件效率的影響 (Research of High Efficiency Silicon Heterojunction Solar Cell Fabricated by Sputtering:Impact of Silicon Thin Film Properties on Device Performance)
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摘要(中)	濺鍍為一種廣泛應用於薄膜成長，且具有許多優點的技術。然而對於矽薄膜的成長而言，濺鍍製程中的離子轟擊效應會使薄膜產生微孔洞，造成電性上的缺陷。因此濺鍍所製作的薄膜易形成矽氫多鍵結構與不易摻雜的特性。所以使用濺鍍法製作太陽能電池的難度較高，未能普及。 本研究使用磁控濺鍍來成長含氫矽薄膜並應用此方法製作矽異質接面太陽能電池。研究發現對基板施加正偏壓下，可有效使矽氫多鍵轉變為矽氫單鍵之穩定型態，且可藉由調變濺鍍功率與氣壓等參數來提升薄膜的摻雜效率。此外再以提升摻雜的P型矽薄膜成長於N型矽晶片表面來製作異質接面太陽能電池。於選擇適當的薄膜製程條件下，可在平面型(未表面粗糙化)的矽晶片獲得10%轉換效率之異質接面太陽能電池。
摘要(英)	Sputtering is a popular technique with many advantages for thin film deposition. However, as for the preparation of hydrogenated silicon thin film, ion bombardment accompanies during sputtering may generate microstructures (voids, columnar structures) within the film, which leads to unfavorable silicon dihydride bodings and electrical defects. Therefore, hydrogenated silicon films fabricated by sputtering are hard to be doped. Those inferior properties made sputtering become non-popular in the fabrication of silicon thin film cells. In this research, we improved the qualities of hydrogenated silicon thin films and investigated electrical and optical properties with respect to deposition parameters. Our results indicated that applying positive bias voltage on the substrate provokes silicon monohydride formation, which is a rather stable bonding configuration as compared to silicon dihydride. Besides, the difficulties of doping can be reduced by refining fabrication parameters such as sputtering power and gas pressure. Futhermore, amorphous P-type / crystalline N-type silicon heterojunction solar cell using non-texture wafer surface has also been demonstrated. Proto-type solar cells with 1cm × 1cm area and 10% conversion efficiency were realized by choosing the appropriate sputtering parameters.
關鍵字(中)	★ 異質接面太陽能電池 ★ 矽薄膜 ★ 磁控濺鍍	關鍵字(英)	★ heterojuction solar cell ★ silicon thin film ★ magnetron sputtering
論文目次	目錄 第一章 緒論 1 1.1 研究背景 1 1.2 研究動機 2 1.3 研究規劃 3 1.4 本論文章節編排 3 第二章 文獻回顧 5 第三章 理論基礎與基本特性介紹 10 3.1電漿與濺鍍原理 10 3.2 太陽能電池工作原理 13 3.3 矽異質接面太陽能電池 16 3.4 非晶矽薄膜的缺陷鈍化與摻雜 17 3.5本質矽與摻雜矽之指標介紹 18 第四章 研究方法與分析工具 20 4.1 矽氫鍵結分析及光學相關特性 20 4.1.1 矽氫鍵結分析 20 4.1.2 薄膜光學特性分析 23 4.2 薄膜電特性與摻雜程度所需之量測 26 4.2.1 導電率 26 4.2.2 四點探針 28 4.2.3 霍爾效應量測儀 29 4.2.4 薄膜活化能 30 4.3 結晶特性分析 32 4.3.1 X光繞射儀(X-ray diffractometer) 32 4.3.2 拉曼光譜儀(Raman spectroscopy) 33 第五章 濺鍍參數影響矽薄膜特性及摻雜效率之實驗結果與分析 35 5.1 矽薄膜本質層之矽氫鍵結分析 35 5.1.1實驗設備與參數介紹 35 5.1.2比較製程參數對膜內氫含量之影響 36 5.1.3比較製程參數對微結構因子R*之影響 39 5.1.4比較製程參數對導電率之影響 42 5.1.5本節結論 43 5.2 改善摻雜效率 43 5.2.1實驗設備與參數介紹 44 5.2.2 P型含氫非晶矽(a-Si:H)薄膜之製作參數說明 45 5.2.3 P型過渡/微晶態含氫矽薄膜之製作參數說明 53 第六章 矽異質接面電池元件製作 62 6.1異質接面電池演進與背景介紹 62 6.2元件製作流程圖介紹與說明 62 6.3量測元件額外特性所需儀器與其原理 64 6.3.1載子生命量測儀(lifetime tester) 64 6.3.2量子效率(Quantum efficiency)量測系統 65 6.4 矽晶片表面清洗與處理實驗結果 65 6.5 背部電極試驗結果 67 6.6 用於元件製作之透明導電膜製程參數與特性 68 第七章 P型矽薄膜製作矽異質接面電池元件之結果與分析 71 7.1非晶P層之矽異質接面電池 71 7.1.1無AZO層之元件特性分析 72 7.1.3非晶元件結論 77 7.2微晶P型異質接面電池 78 7.2.1無AZO層之不同P層厚度元件特性分析 78 7.2.2含AZO層之不同P層厚度元件特性分析 79 7.2.3微晶元件結論 80 7.3後退火處理對元件之影響 81 7.4本章結論 83 第八章 元件優化 84 8.1 兩種不同特性的P型矽薄膜製程參數與薄膜特性 84 8.2 兩種不同特性之P層製作異質接面電池之分析 85 8.2.1微晶態P型矽薄膜所製作之元件特性分析 85 8.2.2過渡態P型矽薄膜所製作之元件特性分析 86 8.2.3綜合分析與討論 87 第九章 結論 90 參考文獻 94 圖目錄 圖1-1本論文之架構示意圖 4 圖3-1 電漿系統於不同電壓與電流狀態下之放電情形 11 圖3-2 射頻濺鍍系統與匹配網路示意圖 12 圖3-3 具有磁鐵之陰極結構示意圖 13 圖3-4 矽晶太陽能電池(同質接面)能帶結構圖 14 圖3-5 太陽能電池發電機制解說與等效電路圖 14 圖3-6 太陽能電池未照光與照光之I-V曲線變化 16 圖3-7 異質接面能帶示意圖 (a)接合前 (b)接合後 17 圖3-8 異質接面太陽能電池結構示意圖 17 圖3-9 矽晶圓與非晶矽薄膜之結構示意圖 18 圖4-1 FTIR光譜儀結構示意圖 21 圖4-2 矽氫鍵結種類與對應之波數 22 圖4-3由穿透光譜利用包絡法計算光學常數說明 24 圖4-4 Urbach tail擬合示意圖 26 圖4-5 薄膜樣品蒸鍍平行電極示意圖 27 圖4-6 暗導電率量測樣品所放置之小真空盒 28 圖4-7 霍爾效應量測原理示意圖 30 圖4-8 霍爾效應量測裝置示意圖 30 圖4-9 能帶與活化能關係示意圖 31 圖4-10 溫控器裝置圖 32 圖4-11晶體繞射X光時，布拉格方程式之幾何關係 33 圖4-12 XRD量測示意圖 33 圖5-1製程腔體示意圖 36 圖5-2不同的氫氣與氬氣分壓與偏壓下薄膜的640cm-1吸收峰量測與擬合結果 37 圖5-3在不同偏壓下薄膜的含氫量關係圖 39 圖5-4不同的氫氣與氬氣分壓與偏壓下薄膜的2000~2100cm-1吸收峰量測與擬合結果 41 圖5-5在不同偏壓下薄膜的微結構因子關係圖 42 圖5-6 不同偏壓下薄膜的暗導電率與光敏度關係圖 43 圖5-7 硼顆粒放置示意圖 44 圖5-8製程腔體示意圖 45 圖5-9 P型a-Si:H薄膜未經過退火(a)與400℃RTA後(b)之I-V量測曲線 46 圖5-10 P型a-Si:H薄膜鍍在矽晶片之表面照片。 (a)製程溫度250℃ (b)製程溫度300℃ 47 圖5-11 比較不同濺鍍功率之P型a-Si:H薄膜經由400℃ RTA前後之I-V曲線。 左上圖：200W，右上圖：150W，左下圖：100W 48 圖5-12 P型a-Si:H薄膜鍍在矽晶片之表面照片。(a)功率150W 溫度300℃ (b)功率100W溫度300℃ 49 圖 5-13 不同功率樣品RTA前後之吸收係數變化 49 圖5-14 P型a-Si:H薄膜缺陷密度與摻雜濃度、Urbach tail值之關係 51 圖5-15 不同濺鍍功率的P型a-Si:H薄膜之原子比例分析結果 (a)100W，(b)150W，(c)200W 52 圖5-16 製鍍過渡/微晶態硼顆粒放置示意圖 54 圖5-17 P型過渡/微晶態矽薄膜之I-V量測曲線 54 圖5-18功率150W與100W樣品於不同Ar/H2比例與閥門開口大小之吸收係數 57 圖5-19四個具摻雜效果的過渡/微晶態薄膜之拉曼光譜圖 58 圖5-20 (a)不同濺鍍參數之P型過渡/微晶態薄膜之SIMS量測結果，150W系列 60 圖5-20 (b)不同濺鍍參數之P型過渡/微晶態薄膜之SIMS量測結果，100W系列 61 圖6-1 矽異質接面電池製作流程圖 63 圖6-2 元件面積定義示意圖 64 圖6-3 Sinton WCT-120載子壽命量測儀 65 圖6-4 比較不同的矽晶片清洗法與氧化層去除法對於矽晶片有效載子生命之影響 66 圖6-5 鍍鎳於矽晶片經不同退火溫度之平行電極I-V曲線 67 圖6-6 (a)鎳化矽經過高溫退火後之XRD繞射圖 (b)比較500nm Ni與20nm Ni/500nm Ag之平行電極I-V量測結果 68 圖6-7 元件用AZO穿透反射與吸收光譜 69 圖7-1 非晶P層異質接面電池製作流程圖 72 圖7-2 縮小元件面積下，比較P層有無RTA處理之I-V與EQE比較 74 圖7-3 比較P層有無RTA處理之I-V與EQE比較 76 圖7-4 (a)含AZO之元件於RTA前後之反射光譜。(b)元件於RTA後表面霧化現象 76 圖7-5 (a)~(d)以掃描式電子顯微鏡觀察退火後元件表面形貌 77 圖7-6比較無AZO不同厚度之微晶P層元件的I-V與EQE 79 圖7-7比較含AZO不同厚度之微晶P層元件的I-V與EQE 80 圖7-8 不同後退火溫度之元件I-V曲線與EQE 83 圖8-1兩種不同結構之P層矽異質接面元件之I-V與EQE比較 88 圖8-2 比較20nm之過渡態與微晶態P型薄膜之吸收率 88 表目錄 表3-2 符合元件品質之摻雜非晶矽薄膜特性整理 19 表4-1 不同矽氫振動模式之常數A之數值 23 表5-1 比較不同製程溫度與氣體比例之P型a-Si:H薄膜導電率 46 表5-2 比較不同濺鍍功率之P型a-Si:H薄膜導電率 49 表5-3 RTA前後P型a-Si:H薄膜光學能隙數值 50 表5-4 RTA前後P型 a-Si:H Urbach tail數值 51 表5-5 閥門半開刻度對總壓以及PH2/PAr之影響 54 表5-6 不同濺鍍參數之P型過渡/微晶態薄膜導電率值 56 表5-7 不同濺鍍參數之P型過渡/微晶態薄膜光學能隙值 57 表5-8 不同濺鍍參數之P型過渡/微晶態薄膜結晶比率值 58 表5-9 不同濺鍍參數之P型過渡/微晶態薄膜Urbach energy值 59 表5-10不同濺鍍參數之P型過渡/微晶態薄膜活化能與電洞濃度 60 表7-1 最佳特性之非晶與微晶態P型矽薄膜製程參數整理 71 表7-2 最佳導電特性之非晶與微晶態P型矽薄膜數值整理 71 表7-3 無AZO層之元件，比較有無RTA以活化P層摻雜對於元件效率之影響 74 表7-4 含AZO層之元件，是否經過400℃ RTA活化P層摻雜對於元件效率之影響 76 表7-5 無AZO不同過渡/微晶態P型矽薄膜厚度之元件效率 79 表7-6 含AZO不同過渡/微晶態P型矽薄膜厚度之元件效率 80 表7-7不同的後退火溫度對元件特性之影響 82 表8-1 過渡態與微晶態P型矽薄膜之製程參數 85 表8-2 過渡態與微晶態P型矽薄膜之特性 85 表8-3 不同退火溫度對微晶態P型矽薄膜元件之影響 86 表8-4 不同退火溫度對過渡態P型矽薄膜元件之影響 86
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指導教授	李正中、陳昇暉 (Cheng-Chung Lee、Sheng-Hui Chen)	審核日期	2012-7-2
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