臺灣博碩士論文加值系統

本研究主要採用化學水浴沉積法(Chemical Bath Deposition,CBD)及濺鍍法(Sputtering)兩種製程方法製備CuInSe2(CIS)太陽能電池之硫化鋅緩衝層薄膜，CBD則分為(1)靜泡溶液反應成膜及(2)攪拌溶液反應成膜兩種成長方式。實驗前兩製程於各別進行前製分析後，先分別於鈉鈣玻璃基板進行硫化鋅薄膜的成長，經分析取得最佳製程參數再鍍製於CIS/Mo/Soda-lime進行堆疊，並藉由四點探針電性分析下量測其p-n二極體特性曲線，以便研判各製程下最佳參數之薄膜是否具備優良的二極體特性以利作為CIS太陽能電池元件之緩衝層。
經實驗分析後發現濺鍍法於製程壓力2.5mtorr、射頻濺鍍功率400W較易於控制薄膜之成膜速率且於兩製程法中能具較均勻緻密及較佳結晶性的薄膜品質。而對於CBD兩成長方式試劑添加濃度則採用前製實驗所獲得理想參數，分別為硫酸鋅0.08mol/L、硫脲0.24mol/L、氨水2mol/L、聯氨1.5mol/L、檸檬酸鈉0.03mol/L。經分析比較後發現，靜泡溶液反應成膜(90℃、30min)薄膜表面品質雖能有優於攪拌溶液反應成膜(80℃、30min)的表現，但於結晶性及成膜速率則較不及攪拌溶液反應成膜的結果，且在光學特性分析上則顯示攪拌溶液反應成膜於兩製程法中能具較佳的表現。經分別與CIS/Mo/Soda-lime堆疊後，電性分析量測下發現，各製程法皆能有效形成p-n接面，其中以攪拌溶液反應成膜(80℃、30min)可得較佳結果，故能確定化學水浴沉積法攪拌溶液反應成膜為較佳的成長CuInSe2太陽能電池硫化鋅緩衝層的製程方法，同時從結果中也顯示化學水浴沉積法在去除攪拌的成膜影響因子之靜泡溶液反應成膜於太陽能電池緩衝層應用也具有其可行性。

This study used chemical bath deposition (CBD) and sputtering two process prepared zinc sulfide buffer layer of a CuInSe2 (CIS) solar cells. CBD process is divided into two methods: (1) static solution reaction film; (2) stirring-mix solution reaction film. Two process completed the individual system analysis the experiment, the ZnS films are firstly grown on soda-lime glass substrate, then the optimal process parameters can be obtained by analysis, then they can be stacked and coated in CIS / Mo / Soda-lime. Then they are measured by four-point probe electrical analysis to obtain p-n diode characteristic curve. So that best parameters of the film in the process can be judged whether they have an excellent diodecharacteristics of buffer layer for CIS solar cells.
After experimental analysis, it can be found that the sputtering process pressure with 2.5 mtorr and the RF sputtering power with 400W are easier to control film growth rate with a more uniform and compact crystallinity film quality at the two process methods. As referring previous experiments for CBD methods, the desired parameters with 0.08 mol/L zinc sulfate, 0.24 mol/L thiourea, 2 mol/L ammonia, 1.5 mol/L hydrazine and 0.03 mol/L citric acid sodium, are adopted for the growth mode of reagent concentration. It is found by analyses that film quality performance of static bubble reaction film with (90 ° C, 30min) is better than stirring the solution reaction film with (80 ° C, 30min), but its crystalline film growth rate is worse than that of stirring-mix solution reaction film, and stirring-mix solution reaction film is also with better performance at optical properties analysis. Through the electrical analysis measurement after stack CIS / Mo / Soda-lime, it can be found that all process method can effectively form a p-n junction, among them, stirring-mix solution reaction film with (80 ° C, 30min) can get better results. Thus, it can determine that the CBD with stirring the solution reaction film can obtain the better ZnS buffer layer of CuInSe2 solar cell. From the results also proved that the CBD with static solution reaction film has its feasibility to obtain ZnS buffer layer of CuInSe2 solar cell.

摘要 ....................................................i
Abstract ..............................................iii
致謝 ....................................................v
目錄 ...................................................vi
表目錄 ..................................................x
圖目錄 .................................................xi
第一章 緒論 .............................................1
1.1 前言 ...............................................1
1.2 太陽能電池之種類與發展 .............................2
1.2.1 矽晶太陽能電池(Silicon Crystalline Solar Cell) ...3
1.2.2 化合物太陽能電池(Compound Solar Cell) ............4
1.2.3 有機太陽能電池(Organic Solar Cells) ..............5
1.3 太陽能電池原理特性介紹 .............................6
1.3.1 太陽幅射光譜 .....................................6
1.3.2 P-N接面二極體及I-V特性曲線 .......................8
1.3.3 太陽能電池發電原理 ..............................12
1.3.4 太陽能電池等效電路與效能參數 ....................14
1.4 研究動機 ..........................................18
第二章 背景理論 ........................................20
2.1 CuInSe2薄膜太陽能電池之介紹 .......................20
2.1.1 CuInSe2薄膜太陽能電池之研究背景 .................20
2.1.2 CuInSe2薄膜太陽能電池材料特性 ...................21
2.1.3 CuInSe2薄膜太陽能電池結構分析 ...................24
2.2 緩衝層介紹 ........................................28
2.2.1 緩衝層簡介 .......................................28
2.2.2 緩衝層之文獻回顧 .................................29
2.3 硫化鋅(Zinc Sulfide)特性與結構 ....................33
2.4 薄膜製備技術 ......................................35
2.5 濺鍍法 ............................................38
2.5.1 真空濺鍍原理介紹 ................................38
2.5.2 射頻濺鍍法(RF Sputtering) .......................40
2.6 化學水浴沉積法(Chemical Bath Deposition,CBD) ......42
2.6.1 化學水浴沉積法介紹 ..............................42
2.6.2 化學水浴沉積法優缺 ..............................43
第三章 實驗方法與儀器介紹 ..............................45
3.1 實驗流程與步驟 ....................................45
3.1.1 實驗材料 ........................................46
3.1.2 玻璃基板清洗流程 ................................47
3.2 濺鍍法薄膜製備實驗 ................................50
3.3 化學水浴沉積法薄膜製備實驗 ........................54
3.3.1 化學水浴沉積法之ZnS化學反應機制 .................60
3.4 儀器設備介紹 ......................................62
3.4.1 表面輪廓儀(α-Step) .............................62
3.4.2 X光繞射儀(X-Ray Diffraction) ....................63
3.4.3 掃描式電子顯微鏡(SEM) ...........................66
3.4.4 X射線能量散佈分析儀(EDS) ........................68
3.4.5 紫外光/可見光光譜儀(UV-VIS Spectrophotometer) ...69
3.4.6 霍爾量測儀(Hall-Measurement) ....................70
3.4.7 四點探針(Four-Point Probe) ......................72
第四章 結果與討論 ......................................74
4.1 熱退火處理參數設置實驗分析 ........................74
4.2 濺鍍法實驗分析 ....................................77
4.3 化學水浴沉積法實驗前製分析 ........................81
4.4 化學水浴沉積法/濺鍍法製備ZnS薄膜分析 ..............94
4.4.1 薄膜厚度與表面粗糙度分析 ........................94
4.4.2 X光繞射儀分析 ..................................103
4.4.3 表面微結構分析 .................................107
4.4.4 透光率及能隙分析 ...............................114
4.4.5 p-n 二極體特性分析 .............................118
第五章 結論與未來展望 .................................121
5.1 結論 .............................................121
5.2 未來展望與建議 ...................................124
參考文獻 ..............................................126
自傳 ..................................................129

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