臺灣博碩士論文加值系統

本研究以化學水浴沉積法製備ZnS緩衝層薄膜，應用於CIGS太陽電池上。研究中採用封閉式CBD製程方法改善以開放式製程中易受到濕度影響造成薄膜披覆不均，並比較CdS及ZnS對CIGS太陽電池效率影響。研究中利用掃描式電子顯微鏡分析其ZnS表面形貌，搭配XPS測量成份影響，透過X光繞射儀進行薄膜結晶性分析，並藉由UV量測其光學穿透度特性。在研究結果得知，以密閉式化學水浴沉積法在不同大氣溼度下所製備出ZnS薄膜，其薄膜並不會受到環境溼度變化而有所影響，從XPS量測其薄膜在不同濕度下其O所佔比率約26 %，而S/Zn比約為0.82，表面粗糙度約4.5 nm，而其結構為閃鋅礦結構。若以密閉式化學水浴沉積法製程中以硫酸鋅( ZnSO4 ) 0.1M、硫脲(SC(NH2)2) 0.6 M、聯氨(N2H4) 10cc、溶液溫度為80℃及pH為9.7時沉積25 min可製備出良好披覆性之ZnS薄膜，其平均光學穿透度在可見光( 380~800nm )可達約77%，光學能隙約3.8eV，而將其ZnS薄膜參數應用於CIGS太陽電池緩衝層，其可得到0.56 % 之光電轉換效率。

In this research were prepared ZnS buffer layer thin films by
chemical bath deposition, and used in CIGS solar cells. The research used
Hermetic CBD process to improve the open process is vulnerable to
humidity caused by the uneven films coated, and compare the impact of
CdS and ZnS on the CIGS solar cell efficiency. In this research using
scanning electron microscopy analysis of ZnS surface morphology,
analysis component of film by XPS, films structural analysis by X-ray
diffraction, and films optical transmittances by spectroscopy (UV-VIS).
The results of the research, Hermetic CBD process under different
atmospheric humidity prepared ZnS film, the films is not easy to be
affected by environmental humidity changes, films at different humidities
O measured from the XPS volume percentage of about 26%, while the
S/Zn ratio of about 0.82, the surface roughness of about 4.5 nm, and films
structure for the zinc blende structure. The Hermetic CBD process zinc
sulfate ( ZnSO4 ) 0.1M. thiourea (SC(NH2)2) 0.6 M. hydrazine (N2H4)
10cc. the solution temperature at 80℃ and pH 9.7 deposited at 25 min
can prepared better ZnS films, the average optical transmittance in the
visible (380 to 800nm) approximately 77%, the optical bandgap of 3.8eV,
and used in CIGS solar cells buffer layer, available the photoelectric
conversion efficiency of 0.56%.

目次

中文摘要 I
英文摘要 II
謝誌 III
目次 IV
表次 VI
圖次 VII
第一章 緒 論 1
1-1 研究目的 1
1-2 名詞解釋 2
第二章 理論分析與文獻回顧 3
2-1 太陽電池基本原理 3
2-2 CIGS太陽電池 7
2-3 緩衝層製備方法 21
2-4 化學水浴沉積法製備ZnS薄膜 25
2-5 ZnS結構與性質 28
第三章 研究方法 30
3-1 實驗流程 30
3-2 實驗材料與試片準備 32
3-3 實驗參數及步驟 34
3-4 薄膜分析 38
3-4-1 薄膜表面及截面形貌量測 38
3-4-2 薄膜表面粗糙度量測 39
3-4-3 薄膜沉積率量測 40
3-4-4 薄膜結構分析 42
3-4-5 薄膜成分分析 43
3-4-6 薄膜光學性質分析 44
第四章 結果與討論 45
4-1 環境溼度對不同CBD製程影響 45
4-1-1 形貌分析 45
4-1-2 成分分析 52
4-1-3 結構分析 57
4-1-4 光學性質分析 59
4-2 參數設計 61
4-2-1 pH值控制 61
4-2-2 硫酸鋅濃度調變 65
4-2-3 硫脲濃度調變 68
4-2-4 錯合物添加 71
4-3 不同氣體對CBD製程之影響 76
4-4 薄膜披覆於CIGS元件 81
第五章 結論與未來研究 86
5-1 結論 86
5-2 未來研究 87
參考文獻 88



表次
表2-1 CIGS薄膜沉積於不同基板文獻回顧 9
表2-2 Mo電極文獻回顧 10
表2-3 吸收層晶格常數及能係大小 12
表2-4 不同製程方法製備CIGS吸收層文獻回顧 13
表2-5 不同材料及方法製備緩衝層之元件效率 17
表2-6 緩衝層不同材料晶格常數及能係大小 18
表2-7 緩衝層文獻回顧 18
表2-8 CIGS ZnO/TCO文獻回顧 19
表2-9 以CBD製備ZnS薄膜文獻回顧 25
表3-1 蘇打玻璃成分 32
表3-2 參數設定 37
表4-1 不同製程在不同濕度下之O及S/Zn之比值 53
表4-2 製程中通入不同氣體之O及S/Zn比值 77
表4-3 ZnS及CdS沉積於CIGS元件參數 82
表4-4 ZnS薄膜披覆於CIGS太陽電池之效率量測 82



圖 次
圖2-1 太陽能電池的工作原理 4
圖2-2 電壓與電流之關係圖 6
圖2-3 CIGS太陽電池結構圖 7
圖2-4 材料光吸收係數 12
圖2-5 CIS/CdS 能係不連續結構 15
圖2-6 各種製作薄膜太陽電池緩衝層之製作方法 16
圖2-7 ZnS不同製程之轉換效率 21
圖2-8 ZnS不同晶態(a)纖鋅礦(b)閃鋅礦 29
圖3-1 實驗流程圖 31
圖3-2 實驗藥品 33
圖3-3 化學水浴沉積法示意圖 35
圖3-4 玻璃基板清洗流程 36
圖3-5 熱場發射掃描式電子顯微鏡 38
圖3-6 表面粗糙度儀 39
圖3-7 薄膜測厚儀 40
圖3-8 橢圓偏光儀 41
圖3-9 X-ray繞射儀 42
圖3-10 化學分析電子能譜儀 43
圖3-11 紫外光光譜分析儀 44
圖4-1 開放式CBD製程不同環境溼度下ZnS薄膜表面形貌分析，平均溼(a)60%(b)70%(c)80% 47
圖4-2 密閉式CBD製程不同環境溼度下ZnS薄膜表面形貌分析，平均溼度(a)60% (b)70%(c)80% 48
圖4-3 開放式CBD製程不同環境溼度下ZnS薄膜粗糙度，平均溼度(a)60% (b)70%(c)80% 50
圖4-4 密閉式CBD製程不同環境溼度下ZnS薄膜粗糙度，平均溼度(a)60% (b)70%(c)80% 51
圖4-5 CBD製程不同環境溼度下ZnS薄膜之全譜線圖(a)開放式(b)密閉式 54
圖4-6 CBD製程不同環境溼度下ZnS薄膜之O、Zn及S含量(a)開放式(b)密閉式 55
圖4-7 CBD製程不同環境溼度下ZnS薄膜Zn2p3細掃分析(a)開方式(b)密閉式 56
圖4-8 CBD製程不同溼度下ZnS薄膜之繞射圖(a)開放式(b)密閉式 58
圖4-9 CBD製程不同環境溼度下ZnS薄膜光學穿透光譜(a)開放式(b)密閉式 60
圖4-10 密閉式CBD製程中不同pH值之薄膜表面形貌分析(a)pH9.3(b)pH9.5 (c)pH9.7(d)pH9.9 63
圖4-11 密閉式CBD製程中不同pH值之薄膜光學穿透光譜 64
圖4-12 密閉式CBD製程中不同ZnSO4濃度之薄膜表面形貌分析(a)0.067M (b)0.1M(c)0.2M 66
圖4-13 密閉式CBD製程中不同ZnSO4濃度之薄膜光學穿透光譜 67
圖4-14 密閉式CBD製程中不同SC(NH2)2濃度之薄膜表面形貌分析(a)0.3M(b)0.6M(c)0.9M 69
圖4-15 密閉式CBD製程中不同SC(NH2)2濃度之薄膜光學穿透光譜 70
圖4-16 密閉式CBD製程中不同N2H4添加量之薄膜表面形貌分析(a)0cc(b)5 cc(c)10cc(d)15cc 72
圖4-17 密閉式CBD製程不同N2H4濃度之薄膜光學穿透光譜 73
圖4-18 最佳薄膜能隙值 75
圖4-19 製程中通入氣體之薄膜表面形貌分析(a)Without gas(b)Ar (c)Ar+H2(＞2.93%) 78
圖4-20 CBD製程中通入不同氣體之ZnS薄膜Zn2p3細掃分析 79
圖4-21 製程中通入氣體之薄膜光學穿透光譜 80
圖4-22 CdS及ZnS薄膜沉積於CIGS基板前後之表面形貌分析(a)未披覆(b)ZnS披 覆於CIGS基板(c)CdS披覆於CIGS基板 83
圖4-23 CdS及ZnS薄膜沉積於CIGS基板前後之剖面圖(a)未披覆(b)ZnS披覆於CIGS基板(c)CdS披覆於CIGS基板 84
圖4-24 ZnS薄膜沉積於CIGS太陽電池I - V曲線 85

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