臺灣博碩士論文加值系統

硒化銅銦(CuInSe2，CIS)系列化合物為目前較具潛力之薄膜太陽能電池材料，其直接能隙非常接近太陽能光的波長範圍，且耐光裂化性質佳，實驗室中轉化效率已達17.6%。而目前硒化銅銦(CuInSe2)薄膜太陽能電池生產的方式仍以真空製程為主，例如蒸鍍法(Evaporation)與濺鍍法(Sputtering)，不但操作成本昂貴，且不利於大面積生產。本研究則嘗試以非真空製程進行硒化銅銦(CuInSe2)與相關化合物的合成包含以熱分解法合成硒化亞銅(Cu2Se)與硒化銦(In2Se3)，以及利用固態反應以硒化銦(In2Se3)與硒化亞銅(Cu2Se)為原料合成硒化銅銦(CuInSe2)，觀察製程中的變化，並探討其反應的機制。
製備硒化亞銅(Cu2Se)時，主要探討不同的配位溶劑添加量，及起始原料預先溶解與否等參數，推測油胺(Oleylamine)之使用量較多時，可將多數的銅離子還原成Cu+，故較不易產生Cu3Se2之中間相，且當Se粉體未事先溶解時，反應系統中會同時不斷地出現成核與成長之反應，使得產物顆粒較大。若將CuCl事先溶解於油胺溶液，而Se粉體事先溶解於十八烯溶液(1-Octadecene)中(Process A)，於250℃恆溫進行3小時反應便可成功獲得約20 nm左右之硒化亞銅(Cu2Se)奈米顆粒。
製備硒化銦(In2Se3)時，主要以調整不同之反應溫度與反應時間為實驗的參數，由XRD分析結果可發現當反應溫度為210℃，而反應時間低於3小時，或反應時間為1小時，反應溫度低於230℃時，容易出現閃鋅礦(Sphalerite)結構之產物，而提高反應時間至3小時或溫度至230℃以上後則會逐步轉換為纖鋅礦(Wurzite)結構之γ-In2Se3，且產物顆粒大小亦逐漸變大。推測纖鋅礦(Wurzite)結構硒化銦(γ-In2Se3)粉體之生成機制應有二種：分別為表面成核反應與界面成核反應。利用熱分解法於反應條件250℃、1小時下進行反應可成功獲得顆粒大小約為1~2 μm左右之γ-In2Se3。
利用熱分解法所產出之硒化銦(γ-In2Se3)與硒化亞銅(Cu2-xSe)為起始原料，以固態反應法合成硒化銅銦(CuInSe2)時，發現隨著反應時間逐漸延長，γ-In2Se3之繞射峰逐漸地消失，而CuInSe2之繞射峰則逐漸地增強。此外，當溫度升高時，可發現γ-In2Se3繞射峰的消失速率或CuInSe2繞射峰的增強速率明顯地提升。進一步分析其反應動力學之行為時，得到硒化銦(γ-In2Se3)消失之活化能約為122.5 kJ/mol，此數值與前人文獻中CuInSe2的生成活化能相近，而反應級數n大約= 0.5，且由TEM發現熱處理後之粉體多為接近與反應物Cu2-xSe顆粒大小相近之奈米粒子，因此本研究合成CuInSe2之反應機制推測為In3+離子擴散主導之一維擴散控制。

Copper indium diselenide (CuInSe2, CIS) and related materials are the promising candidates for photovoltaic applications due to their effectively light-absorbing property in thin-film solar cells. However, the widespread utilization of CIS based solar cells has been hindered by the high cost associated with vacuumed processes such as evaporation or sputtering.
In this study, the synthesis of Cu2Se, In2Se3 nano-particles using thermal decomposition method and CuInSe2 by solid state reaction method were investigated. For the synthesis of Cu2Se, the quantity of chelating solvent and pre-dissolving Se powder or not are the main variables. The results showed that the more oleylamine added, the fewer Cu3Se2 produced because oleylamine is a good reductant. Moreover, as Se powder was not pre-dissolved, the Cu2Se particle will grow rapidly. The Cu2-xSe nanoparticles ( about 20 nm) was obtained at 250oC for 3 h by thermal decomposition method as Se powder was pre-dissolved.
In the case of synthesizing In2Se3, the reaction time and temperature are the main variables. The results showed that as the reaction time was not long enough or temperature was not high enough, the intermediate phase, sphalerite, would be observed. The sphalerite structure would transform intoγ-In2Se3 (Wurzite structure) as the reaction time was prolonged or the temperature was raised. The particles ( about 1~2 μm) with singleγ-In2Se3 (Wurzite structure) phase can be obtained at 250oC for 1 h by thermal decomposition method.
Then formation activation energy formation of CuInSe2 powders using as-prepared Cu2-xSe andγ-In2Se3 as the raw materials via solid state reaction is about 122.5 kJ/mol and the reaction constant is about 0.5. Moreover, the particle size of the obtained CuInSe2 powders is closed to that of Cu2-xSe, suggesting that the mechanism of the formation of CuInSe2 by solid state reaction method may be one-dimensional diffusion of In3+ ions towardγ-In2Se3.

目錄
摘要 I
AbstractIII
致謝 IV
目錄 VI
表目錄 VIII
圖目錄 IX
附錄 XI

第一章 緒論1
1-1 前言1
1-2 研究目的2
第二章 前人研究與理論基礎5
2-1 硒化銅銦(CuInSe2，CIS)5
2-1-1硒化銅銦(CuInSe2，CIS)之簡介5
2-1-2 晶體結構6
2-1-3 合成方法6
2-2 硒化亞銅(Cu2Se)11
2-2-1硒化亞銅(Cu2Se)之簡介11
2-2-2 晶體結構11
2-2-3 合成方法12
2-3 硒化銦(In2Se3)17
2-3-1 硒化銦(In2Se3)之簡介17
2-3-2 晶體結構17
2-3-3 合成方法18
2-4 熱分解法(Thermal decomposition method)24
2-4-1 配位化合物 (Coordination compounds)24
2-4-2 成核及成長(Nucleation and growth)24
2-4-3 熱分解法(Thermal decomposition method)24
2-5 固態反應(Solid state reaction)28
2-5-1固態反應(Solid state reaction)之簡介28
2-5-2 物質擴散的方式29
2-5-3 反應動力學29
第三章 實驗方法與步驟31
3-1實驗藥品31
3-2 實驗流程31
3-2-1 Cu2Se之製備流程31
3-2-2 In2Se3之製備流程36
3-2-3 CuInSe2之製備流程38
3-3 分析與量測40
3-3-1 結晶相鑑定與粒徑分析(X-ray Diffraction)40
3-3-2 成份/組成分析40
3-3-3 微結構分析41
3-3-4 化學分析電子能譜儀(Electron Spectroscopy for Chemical Analysis)41
3-3-5 微差掃描卡計/微分熱重分析(DSC/DTG)41
第四章 結果與討論42
4-1 硒化亞銅(Cu2Se)42
4-1-1 Cu2Se反應機制探討42
4-1-2 油胺用量及未預先溶解Se對反應之影響47
4-2 In2Se3反應機制探討53
4-3 CuInSe2之動力學與反應機制探討60
第五章 結論71
參考文獻73
附錄80

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