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研究生： 林志隆
Chih-lung Lin
論文名稱： 以微波水熱法合成新穎硒化銅銦鎵(CuIn1-xGaxSe2)材料應用於薄膜CIGS太陽能電池之研究
Microwave-assisted Hydrothermal Synthesis of Novel Copper Indium Gallium Selenide (CuIn1-xGaxSe2) Materials for Thin Film CIGS Solar Cells
指導教授： 蕭敬業
Ching-Yeh Shiau
黃炳照
Bing-Joe Hwang
口試委員: 邱秋燕
Yen-Chiou Chiou
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2009
畢業學年度： 97
語文別： 中文
論文頁數： 150
中文關鍵詞： 硒化銅銦鎵 、非晶相亞硒酸鹽前驅物 、黃銅礦結構 、微波促進合成 、水熱法 、電泳沉積 、硒化 、薄膜太陽能電池
外文關鍵詞： CuIn1-xGxSe2, Amorphous selenite precursors, Chalcopyrite structure, Microwave-assisted synthesis, Hydrothermal method, Electrophoresis deposition, Selenization, Thin film solar cells
相關次數： 點閱：370  下載：4 
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    • 本論文之研究方向主要分為四元CuIn1-xGaxSe2奈米材料之合成及電泳沉積製備CuIn1-xGaxSe2薄膜之兩個部分進行。首先，於材料合成之研究中，吾人成功建立以微波水熱法合成四元CuIn1-xGaxSe2奈米粒子，此合成法利用水為溶劑進行液相反應，除了解決一般溶熱法中有機溶劑之汙染外，並可於30分鐘之短時間內快速合成。而此法合成之CuIn1-xGaxSe2材料具有新穎的非晶性結構，不僅粒子尺寸十分均一，且可達所需之計量比例。此非晶之奈米粒子，於氫氣之氣氛下經熱處理還原及硒化後，即可轉變成純相之CuIn1-xGaxSe2黃銅礦結構。此研究結果顯示，所建立之合成方法不但可以大幅降低對環境之影響，亦對薄膜製備之均勻度有明顯之助益，具有相當的潛力應用於薄膜CIGS太陽能電池之吸收層材料。
    於製備CuIn1-xGaxSe2薄膜研究中，本研究藉由快速、均勻且可精準控制薄膜厚度之電泳沉積法製備CuIn1-xGaxSe2薄膜，並利用所合成之新穎材料作為電泳懸浮液之粒子。研究結果發現，此非結晶性之薄膜經由500 ℃~ 600 ℃之氫氣還原及550 ℃之硒化程序後，即可得到所需之黃銅礦結構，且無CuxSe、In2O3及Ga2O3等雜相產生。此外，藉由Ga於CuIn1-xGaxSe2 摻雜之比例提高，造成薄膜表面不緻密之孔洞可明顯的改善，顯示Ga元素的存在能有效提高薄膜之密度，此發現可作為改善CIGS薄膜製備之依據。
    另外，本研究建構一系列CuIn1-xGaxSe2之晶格模型，同時配合密度泛函理論(DFT)方法計算，以提供理論之XRD圖譜、電子能帶結構與電荷轉移，並分析解釋摻雜不同成分Ga進入CuInSe2晶格中，造成結構扭曲及能隙改變之原因。同時，藉由理論計算模擬與實驗值作一比較，其XRD之相關數據，結果為十分相似，表示利用DFT計算可得到合理的原子位置與結構。此模擬參數未來將可應用於不同摻雜元素取代CuInSe2之In元素，並作深入探討。

    The study is divided into two parts, including synthesis of CuIn1-xGaxSe2 nanomaterials and preparation of CuIn1-xGaxSe2 thin films. First, novel CuIn1-xGaxSe2 nanoparticles have been successfully prepared by the developed microwave-assisted hydrothermal method. The developed method avoids the use of the organic solvents in the frequently used solvothermal method. Further, uniform CuIn1-xGaxSe2 nanoparticles of exact stoichiometric ratio can be prepared within 30 mins, showing the high efficiency of the developed method. It should be noticed that the amorphous nature for the synthesized CuIn1-xGaxSe2 nanoparticles is shown. However, the chalcopyrite structure for the synthesized CuIn1-xGaxSe2 particles can be obtained after further reduction and selenization. Undoubtedly, the developed microwave-assisted hydrothermal method is environment-friendly and the synthesized CuIn1-xGaxSe2 is of great potential as an absorption layer of thin film CIGS solar cell.
    Secondly, the controllable thickness of the film fabricated by EPD technique was carried out with the synthesized CuIn1-xGaxSe2 precursors. With further reduction and selenization process the synthesized CuIn1-xGxSe2 showed only chalcopyrite structure without any impurities. Owing to the limited heating conditions by the melting temperature of the glass substrate (600℃) for longer time (10 hr), the porous nature of the deposited film needs further improvement. Surprisingly, the high porosity can be reduced by increasing Ga content in the CuIn1-xGaxSe2. The finding can be the guide for the future improvement.
    On the other hand, theoretical X-ray diffraction patterns, electronic band structure, and charge transfer among hetero-atoms have been achieved by model establishment accompanied with density functional theory (DFT) calculation on CuIn1-xGaxSe2. Further, the effect of Ga doping in CuIn1-xGaxSe2 to distortion of crystalline structure and change in the energy gap can be understood. The strategy could be further extended to the understanding of other elements (M) doping effect for CuIn1-xMx Se2.

    中文摘要..........................................................................................................I 英文摘要.......................................................................................................III 誌謝................................................................................................................V 目錄...............................................................................................................VI 圖目錄...........................................................................................................XI 表目錄....................................................................................................XXV 第一章 緒論...................................................1 1.1 前言....................................................................1 1.2 太陽能電池的發展簡介..........................................................................2 1.2.1 太陽能電池基本原理...................................................................2 1.2.2 太陽能電池材料及種類...............................................................4 1.2.2.1 晶圓型太陽能電池..........................................................5 1.2.2.2 薄膜型太陽能電池..........................................................7 1.3 研究動機與目的....................................................................................12 第二章 文獻回顧與理論基礎.....................................................................14 2.1 硒化銅銦鎵吸收層材料結構與組成....................................................14 2.2 硒化銅銦鎵吸收層薄膜製備技術........................................................17 2.2.1 共蒸鍍沉積硒化銅銦鎵吸收層.................................................18 2.2.2 二階段法(硒化法)製備硒化銅銦鎵薄膜..................................20 2.2.3 電鍍法沉積硒化銅銦鎵薄膜......................................................23 2.2.4 硒化銅銦鎵漿料塗佈技術..........................................................25 2.2.4.1 硒化銅銦鎵漿料配製.....................................................25 2.2.4.2 漿料塗佈製備硒化銅銦鎵薄膜.....................................28 2.3 電泳技術於太陽能電池上的應用........................................................32 2.3.1 電泳沉積之原理..........................................................................32 2.3.2 電泳沉積技術於太陽能電池之應用及發展.............................34 2.4 漿料製程之硒化銅銦鎵奈米粒子製備................................................38 2.4.1 固態法合成硒化銅銦鎵粉體....................................................38 2.4.2 單一來源熱裂解法合成硒化銅銦鎵粉體.................................39 2.4.3 水熱/溶熱法合成硒化銅銦鎵粉體.......................................41 2.5 微波輔助加熱促進硒化銅銦奈米粒子合成........................................48 2.5.1 微波合成之原理..........................................................................48 2.5.2 微波輔助加熱促進硒化銅銦鎵奈米粒子合成.........................49 第三章 實驗方法和儀器設備.....................................................................52 3.1 儀器設備................................................................................................52 3.2 實驗藥品................................................................................................54 3.3 實驗方法................................................................................................55 3.3.1 微波水熱法合成硒化銅銦鎵粒子..............................................55 3.3.2 電泳沉積製備硒化銅銦鎵薄膜..................................................57 3.4 材料特性分析與儀器原理....................................................................59 3.4.1 X光繞射(XRD)分析....................................................................59 3.4.2 掃描式電子顯微鏡(SEM)材料表面形態分析.......................60 3.4.3 能量分散光譜(EDX)元素組成分析..........................................61 3.4.4 感應耦合電漿原子發射光譜(ICP)元素組成分析....................62 3.4.5 穿透式電子顯微鏡(TEM)穿透形態分析..................................63 3.4.6 拉曼光譜(Raman spectra)鑑定...................................................64 3.4.7 X射線光電子能譜(XPS)之鑑定................................................65 第四章 結果與討論.....................................................................................67 4.1 微波水熱法合成硒化銅銦鎵粒子之特性分析....................................67 4.1.1 X光粉末繞射(XRD)晶體結構分析...........................................67 4.1.2 掃描式電子顯微鏡(SEM)表面形態分析..................................71 4.1.3 能量分散光譜(EDX)元素組成分析..........................................77 4.1.4 穿透式電子顯微鏡(TEM)穿透形態分析..................................83 4.1.5 X射線光電子能譜(XPS)之鑑定.................................................86 4.2 電泳沉積製備硒化銅銦鎵薄膜............................................................90 4.2.1 X光繞射(XRD)晶體結構分析...................................................90 4.2.1.1 還原程序及硒化程序對電泳薄膜晶體結構之影響.....90 4.2.1.2 鎵之組成變化對硒化銅銦鎵薄膜晶體結構之影響.....93 4.2.2 掃描式電子顯微鏡(SEM)表面形態分析.................................96 4.2.2.1電泳條件對薄膜厚度之分析...........................................96 4.2.2.2 還原及硒化程序之電泳薄膜表面形態分析.................99 4.2.3 能量分散光譜(EDX)元素組成分析........................................106 4.2.4 拉曼光譜(Raman spectra)之鑑定.............................................110 4.3 硒化銅銦鎵系統之理論計算模擬......................................................112 4.3.1 三元CuInSe2之XRD模擬與模型建構(Model construction)..113 4.3.2 四元CuInSe2之XRD模擬與模型建構(Model construction)..118 第五章 綜合討論.......................................................................................124 5.1 新穎硒化銅銦鎵材料性質之探討......................................................124 5.1.1 微波水熱法合成條件及結晶條件之探討...............................124 5.1.2 製備硒化銅銦鎵粒子之相關文獻比較. .................................127 5.2 鎵的組成變化對硒化銅銦鎵影響之探討..........................................129 5.2.1 表面型態之探討........................................................................129 5.2.2 晶體結構變化之探討................................................................130 5.3 電泳沉積硒化銅銦鎵薄膜之探討. ....................................................134 第六章 結論...............................................................................................135 第七章 未來方向.......................................................................................137 第八章 參考文獻.......................................................................................138 附錄.............................................................................................................147

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