臺灣博碩士論文加值系統

本文主要是在研究半導體薄膜材料CuIn0.7Ga0.3Se2的合成並使用了溶劑熱迴流法來製備四元CuIn0.7Ga0.3Se2奈米油墨，其優點在於此為簡單、便捷、低成本的非真空技術。本實驗採用純粉末的銅(Cu)銦(In)鎵(Ga)硒(Se)作為原料，莫爾數比依序為1：0.7：0.3：2 並一起添加到新型有機溶劑D400（聚醚胺）中在200oC到250oC 溫度下 加熱3至20小時後加以討論。首先我們觀察到在不同的反應條件下有明顯的相變化，然後透過檢測進一步的了解了Cu、In、Ga、Se在D400（聚醚胺）內的反應機制並推測出本實驗中CuIn0.7Ga0.3Se2 的反應途徑和Ga的擴散及影響，發現Ga是合成出CuIn0.7Ga0.3Se2 的關鍵，也合成出了純相CuIn0.7Ga0.3Se2。
藉著前面部分的探討，我們客觀的認為在我們的實驗環境下相對於元素銦(In)，元素鎵(Ga)更難以加入反應形成CuIn0.7Ga0.3Se2。理由在於兩者在活性上的差異以及兩者在元素週期表上的同III族關係，這意味著它們具有相似的化學性質並導致在反應順序上互相的競爭，因此，我們嘗試先合成出CuGaSe2來使Ga先加入反應。但在已知的一般溶劑熱法上很難在200OC附近形成較純的CuGaSe2，最後我們成功合成出純相的CuGaSe2並以後續的檢測結果猜測了其在本實驗中的反應途徑；然後再將同為純相的CuGaSe2及CuInSe2以3：7的莫爾數比例混合來進行後續的硒化退火處理來形成CuIn0.7Ga0.3Se2改善其結晶性並觀測其表徵等特性。

In this paper, we are mainly studying the synthesis of semiconductor material thin film CuIn0.7Ga0.3Se2. The quaternary phase CuIn0.7Ga0.3Se2 nano-ink was prepared by Solvothermal Refluxing Method with a simple, convenient and low-cost non-vacuum technology. Use elemental powder of copper (Cu), indium (In) , gallium (Ga) and selenium (Se) powder as material with stoichiometric ratio of 1 : 0.7 : 0.3 : 2 to add into the novel organic solvent D400 (polyetheramine) And then heats at 200-250℃ for 3-20 hours to discuss. First of all, we observe the phase change at different time, and then we know the reaction mechanism of Cu, In, Ga, Se and D400 (polyetheramine) by measurement further to deduce the reaction pathway of CuIn0.7Ga0.3Se2 and the effect of Ga at this experiment. We find Ga is the key to synthsis CuIn0.7Ga0.3Se2 and successfully synthesize pure phase CuIn0.7Ga0.3Se2.
We think Ga is more difficult than In to join the reaction of synthesizing CuIn0.7Ga0.3Se2 because the activity difference and both of them are III at Periodic Table of Elements. It means they have similar chemical properties lead to competition. So we try to form CuGaSe2 to make Ga join the reaction first. But it is hard to synthsis a pure CuGaSe2 with Solvothermal process and low reaction temperature. We do our best to synthsis a pure CuGaSe2 and discuss his reaction¬ way. And then we mixture the pure CuGaSe2 and CuInSe2 with a 3: 7 ratio to selenized at 600~675OC to synthsis CuIn0.7Ga0.3Se2, improve its crystallinity and observe the characteristics.

中 文 摘 要 ............................................................................................................ i
Abstract ........................................................................................................................ ii
致 謝 ...................................................................................................................... iii
Contents ....................................................................................................................... iv
List of Tables ............................................................................................................... vi
List of Figures ............................................................................................................ vii
Chapter 1 Introduction ............................................................................................... 1
1-1 Background ......................................................................................................... 1
1-2 Cu-III-VI Group Semiconductor material………………………………………1
1-3 Solar Cell……… …………………………………………………………….....2
1-4 Literature review of Cu-III-Se ............................................................................ 4
1-4-1 Non-vacuum technology ............................................................................ 4
1-4-1-1 Solvotherml method ......................................................................... 4
1-4-1-2 Colloidal method .............................................................................. 5
1-4-2 Vacuum techology ..................................................................................... 5
1-4-2-1 Sputtering ......................................................................................... 5
1-5 Motivation ........................................................................................................... 6
1-6 The structure of this paper ................................................................................... 6
Chapter 2 Preparation and Characterization of Cu-III-Se Thin Films ............... 10
2-1 Material and solvent .......................................................................................... 10
2-1-1 Material source......................................................................................... 10
2-1-2 Solvent source .......................................................................................... 10
2-2 Characteristics and comparison of solvents ...................................................... 10
2-3 Preparation of Cu-III-Se thin films ................................................................... 11
2-4 Fabrication of Cu-III-Se thin films use precursor inks by a two-step process .. 11
2-4-1 Preparation of CuIn0.7Ga0.3Se2 precursor films……………………….....11
2-4-2 Selenization of CuIn0.7Ga0.3Se2 thin films ................................................ 12
2-5 Thin Film analysis characterization technologies ............................................. 12
2-5-1 X-Ray Diffraction (XRD) ...................................................................... 12
2-5-2 High-Resolution Thermal Field Emission Scanning Electron Microscopy (FE-SEM) and Energy Dispersive Spectroscopy (EDS) ... 13

2-5-3 High-Resolution Transmission Electron Microscopy (HR-TEM) ......... 14
2-5-4 UV/VIS/NIR Spectrophotometer ........................................................... 15
Chapter 3 The Effect in CIGS Synthesis by Non-vacuum Solvothermal Processed…………………….…………………………………….……..24
3-1 Abstract ............................................................................................................. 24
3-2 Introduction ....................................................................................................... 25
3-3 Experiment ........................................................................................................ 26
3-4 Results and Discussion ...................................................................................... 26
3-5 Summary ........................................................................................................... 29
Chapter 4 Synthesis CuGaSe2/CuInSe2 hybrid ink and selenized to form CuIn0.7Ga0.3Se2 thin film………………………………….………………38
4-1 Abstract ............................................................................................................. 38
4-2 Introduction ....................................................................................................... 48
4-3 Experiment ........................................................................................................ 39
4-4 Results and Discussion ...................................................................................... 40
4-5 Summary ........................................................................................................... 44
Chapter 5 Conclusions and Future work ................................................................ 56
5-1 Conclusions ....................................................................................................... 56
5-2 Future work ....................................................................................................... 56
References................................................................................................................... 59

Chapter 1
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Chapter 2
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Chapter 3
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Chapter 4
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[16]Ye Lian, Jinqiu Zhang, Xiaochuan Ma, Peixia Yang, Maozhong An, " Synthesizing three-dimensional ordered macroporous CuInxGa1−xSe2 thin films by template-assisted electrodeposition from modified ionic liquid ", Ceramics International Vol. 44, issue. 2, pp. 2599-2602, 2018.

Chapter 5
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