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研究生： 張善淵
Shan-yuan Chang
論文名稱： 使用電子迴旋共振化學氣相沉積製備異質接面太陽能電池表面鈍化氫化非晶矽薄膜之製程參數研究
Surface passivation layer of α-Si:H thin films from process parameters study in HIT solar cell was prepared by ECR-CVD
指導教授： 利定東
Ting-tung Li
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 能源工程研究所
Graduate Institute of Energy Engineering
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 108
中文關鍵詞： 氫化非晶矽 、表面鈍化 、光放射光譜儀 、電子迴旋共振 、化學氣相沉積 、載子生命週期
外文關鍵詞： hydrogenated amorphous silicon, surface passivation, Optical Emission Spectroscopy(OES), Electron Cyclotron Resonance(ECR), Chemical Vapor Deposition(CVD), carrier lifetime
相關次數： 點閱：15  下載：0 
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    • 本研究使用電子迴旋共振化學氣相沉積製備異質接面太陽能電池表面鈍化氫化非晶矽薄膜之製程參數，調變的參數為微波功率、壓力、磁場共振位置、溫度及氫稀釋濃度比。製程過程中輔以光放射光譜儀(OES)監測電漿物種變化，並搭配FTIR、拉曼光譜儀、橢圓偏光儀來探討薄膜的結構特性，最後以Photoconductance lifetime tester判斷鈍化效益的好壞。
    經由實驗可得，考慮到電子密度及電子溫度的影響因此製程壓力選用5mtorr最為恰當；至於功率可選用低功率500W；溫度方面，製程溫度以300℃為佳；綜合以上參數，可於磁場組態40/12/22、氫稀釋比0.2、厚度20nm下獲得品質穩定的非晶矽鈍化薄膜。經過退火270 ˚C-120s後數載子生命週(Lifetime)從523.79μsec提升至1.18msec；Implied Voc從626.48mV提升至657.48mV；R*從0.2下降到0.18；氫含量32.7%降至31.6%。

    Surface passivation layer of hydrogenated amorphous silicon thin films (α-Si:H) in heterojunction with intrinsic thin layer (HIT) solar cell was prepared by Electron Cyclotron Resonance Chemical Vapor Deposition (ECR-CVD). The process parameters effects on films of surface passivation were investigated. In this study, the Optical Emission Spectroscopy (OES) has been used as a tool for analyzing the plasma spectrum and tried to find out the relationship to the deposition properties under varying process settings such as microwave power, pressure, magnetic field resonance position, temperature, and dilution ratio. The thin film properties were analyzed by Fourier transform infrared spectroscopy, Raman spectroscopy, and Ellipsometry. The surface passivation quality was determined by photo-conductance lifetime tester.
    The result showed that the stable and high quality of passivated amorphous silicon thin films could be obtained under the parameters of including thickness of 20nm, dilution ratio of 0.2, microwave power of 500W, substrate temperature of 300℃, pressure of 5mTorr and magnetic field configuration are of 40A, 12A and 22A which represents main coil, inner coil and outer coil current respectively.
    The thin film properties could be optimized after annealing process under the temperature 270 ˚C for 120sec. The lifetime of passivated amorphous silicon thin films increased from 523.79μsec to 1.18msec, the implied Voc increased from 626.48mV to 657.48mV, the microstructure parameter (R*) decreased from 0.2 to 0.18, and the hydrogen content (CH) decreased from 32.7% to 31.6%.

    目錄 第一章 緒論 1 1-1 前言 1 1-2 研究目的及方法 5 第二章 文獻整理及原理介紹 8 2-1太陽電池簡介 8 2-2矽晶片復合機制與光導量測之介紹 12 2-2-1輻射復合 (RADIATIVE RECOMBINATION) 13 2.2-2 歐傑復合 (AUGER RECOMBINATION) 14 2.2-3 夏克禮－里德－霍 (SHOCKLEY-READ-HALL)復合 16 2.2-4 表面復合 (SURFACE RECOMBINATION) 17 2.2-5 光導量測之介紹 17 2-3 薄膜沉積 20 2-3-1 薄膜沉積原理 20 2-3-2 化學氣相沉積 (CVD) 23 2-4 矽薄膜介紹 29 2-5 應用於單晶矽太陽能電池之矽晶圓上的表面鈍化 33 2-6 光放射光譜儀用於矽薄膜製程之研究 38 第三章 實驗方法與設備 41 3-1 實驗方法 41 3-2 實驗步驟 42 3-3 實驗設備及原理 43 3-3-1 電子迴旋共振氣相沉積系統(ELECTRON CYCLOTRON RESONANCE CHEMICAL VAPOR DEPOSITION , ECR-CVD) 43 3-3-2 光放射光譜儀OES 46 3-3-3 傅氏轉換紅外線光譜儀FTIR 49 3-3-4 橢圓偏光儀 (ELLIPOSMETER) 51 3-3-5 拉曼光譜儀(RAMAN SPECTROSCOPY) 52 3-3-6快速退火爐(ARTS-RTA) 53 3-3-7光電導生命週期量測儀(PHOTOCONDUCTANCE LIFETIME TESTER) 54 第四章 結果與討論 57 4-1微波功率對電漿與薄膜特性之影響 57 4-2工作壓力對電漿與薄膜特性之影響 65 4-3 磁場共振位置對電漿與薄膜特性之影響 73 4-4 溫度對電漿與薄膜特性之影響 79 4-5 氫稀釋濃度對電漿與薄膜特性之影響 84 4-6 熱退火處理對非晶矽薄膜特性之影響 91 第五章 結論 98 參考文獻 101   表目錄 表1-1 ECR與RF電漿源之差異 7 表2-1 SIH4初級反應式 23 表2-2 SIH4反應式[25] 25 表2-3 製作之A-SIH薄膜所具備各項數值特性 32 表3-1 矽氫鍵結對照表 50 表4-1 不同功率之參數設定 60 表4-2 不同工作壓力之參數設定 68 表4-3不同共振位置之參數設定 74 表4-4 不同溫度之參數設定 80 表4-5 不同氫稀釋濃度之參數設定 86   圖目錄 圖1-1、太陽能電池分類 4 圖2-1太陽電池電路模型 10 圖2-2 太陽電池I-V 曲線 11 圖2-3 導電帶中歐傑復合 圖2-4 價電帶中歐傑復合 14 圖2-5 N-SI 與P-SI 在不同參雜濃度下之載子生命週期[13] 15 圖2-6 薄膜沉積示意圖[20] 22 圖2-7 薄膜生長過程[22] 22 圖2-8 SIH4 經一次電子所需不同能量產生之物種[23] 24 圖2-9 個物種於電漿中存在之密度[24] 24 圖2-10 SIH3生長非晶矽薄膜示意圖[29] 31 圖2-11傳統太陽能電池結構與SANYO的H.I.T 結構太陽電池差異圖[32] 36 圖2-22(A)相同製程條件下使用A-SI與碘化學鈍化對於少數載流子LIFETIME的影響(B)HIT SOLAR CELL 以 A-SI鈍化後之少數載流子LIFETIME與開路電壓之關聯[33] 36 圖2-23單晶矽與P LAYER 間的I LAYER 的結晶化[34] 36 圖2-24界面I LAYER 結晶化對太陽能電池轉化效率的影響[34] 37 圖2-25不同氫稀釋率之生命週期、氫含量、結晶率之關係[37] 37 圖3-1 實驗流程圖 41 圖3-2 ECR-CVD 設備示意圖 45 圖3-3 ECR-CVD 主磁場示意圖 45 圖3-4 光放射光譜儀裝置圖 48 圖3-5 傅氏轉換紅外線光譜儀裝置圖 50 圖3-6 拉曼光譜以高斯分佈擬合出三種波型 52 圖3-7快速退火爐裝置圖 53 圖3-8 SintonWCT-120.…………………………………………………………………………………..56 圖3-9 WCT-120脈衝光源 56 圖3-10WCT-120濾片 56 圖3-11WCT-120量測底座……………………………………………………..……………………..56 圖4-1不同厚度之LIFETIME變化 61 圖4-2不同功率之光譜強度變化 61 圖4-3不同功率之物種相對於AR濃度變化 62 圖4-4不同功率之電子溫度光譜比值變化 62 圖4-5不同功率沉積矽薄膜之虛部介電函數的ΕI 63 圖4-6不同功率沉積矽薄膜之光吸收係數 63 圖4-7不同功率沉積矽薄膜之拉曼光譜圖 64 圖4-8不同功率下沉積矽薄膜之LIFETIME與IMPLIED VOC變化 64 圖4-9不同功率下薄膜氫含量與微結構參數之變化 65 圖4-10 不同工作壓力之物種之光譜強度變化 68 圖4-11不同工作壓力之物種相對於AR濃度比值變化 69 圖4-12不同工作壓力之電子溫度光譜比值變化 69 圖4-13不同工作壓力沉積矽薄膜之虛部介電函數的ΕI 70 圖4-14不同工作壓力沉積矽薄膜之光吸收係數 70 圖4-15不同工作壓力沉積矽薄膜之拉曼光譜圖 71 圖4-16不同壓力下沉積矽薄膜之LIFETIME與IMPLIED VOC變化 71 圖4-17不同工作壓力下薄膜氫含量與微結構參數之關係 72 圖4-18 ECR-CVD 主磁場示意圖 74 圖4-19不同共振位置之物種之光譜強度變化 75 圖4-20不同共振位置之物種相對於AR濃度比值變化 75 圖4-21不同共振位置之電子溫度光譜比值變化 76 圖4-22不同共振位置沉積矽薄膜之虛部介電函數的ΕI 76 圖4-23不同共振位置沉積矽薄膜之光吸收係數 77 圖4-24不同共振位置沉積矽薄膜之拉曼光譜圖 77 圖4-25不同共振位置下沉積矽薄膜之LIFETIME與IMPLIED VOC變化 78 圖4-26不同共振位置下薄膜氫含量與微結構參數之關係 78 圖4-27不同溫度之物種之光譜強度變化 80 圖4-28不同溫度之物種相對於AR濃度比值變化 81 圖4-29不同溫度沉積矽薄膜之虛部介電函數的ΕI 81 圖4-30不同溫度沉積矽薄膜之光吸收係數 82 圖4-31不同溫度沉積矽薄膜之拉曼光譜 82 圖4-32不同溫度下沉積矽薄膜之LIFETIME與IMPLIED VOC變化 83 圖4-33不同溫度之薄膜氫含量與微結構參數之關係 83 圖4-34不同氫稀釋濃度之光譜強度變化 86 圖4-35 不同氫稀釋濃度之物種相對於AR濃度變化 87 圖4-36不同氫稀釋濃度之電子溫度變化 87 圖4-37不同氫稀釋比沉積矽薄膜之虛部介電函數的ΕI 88 圖4-38 不同氫稀釋濃度下之拉曼圖譜 88 圖4-39 不同氫稀釋濃度下之HΑ*/SIH* 89 圖4-40不同氫稀釋比下沉積矽薄膜之LIFETIME與IMPLIED VOC變化 89 圖4-41不同氫稀釋比之薄膜氫含量與微結構參數之LIFETIME變化 90 圖4-42在不同退火溫度下各微波功率之LIFETIME變化 94 圖4-43在不同退火溫度下各工作壓力之LIFETIME變化 94 圖4-44在不同退火溫度下各共振位置之LIFETIME變化 95 圖4-45在不同退火溫度下各基材溫度之LIFETIME變化 95 圖4-46在不同退火溫度下各氫稀釋比之LIFETIME變化 96 圖4-47經過退火270 ˚C-120S後LIFETIME與IMPLIED VOC之改善 97 圖4-48經過退火270 ˚C-120S後R*與CH之改善 97

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