臺灣博碩士論文加值系統

本研究選用氯化銅(Copper(II) chloride, CuCl2)、氯化鋅(Zinc(II) chloride, ZnCl2)、五水合氯化錫(Stannic(IV) Chloride, SnCl4．5H2O)與硫代乙烯胺(Thioacetamide, TAA)為前驅鹽，並以去離子水與乙醇之混和溶液作為溶劑，成功合成出Cu2ZnSnS4(CZTS)粉體。吾人藉由改變CZTS前驅物溶液之反應溫度發現，於65 oC反應1小時，並於氬氣的氣氛煅燒550 ¬oC後，可獲得純相之CZTS粉體；於35-55 oC的反應溫度下，會有過量的六角柱狀結構之Cu3(TAA)3Cl3中間相，導致CZTS前驅物在高溫煅燒後會有Cu2S之不純相產生。利用濾紙過濾移出六角柱狀構之中間相，獲得殘留之球狀沉澱物，於氬氣氣氛煅燒至450 oC後，合成出Cu2SnS3(CTS)粉體，並非吾人所預期之CZTS粉體，推論Zn是以離子態Zn2+之形式存在於溶液中，故欲獲得CZTS粉體，必須將含有Zn2+之溶液與沉澱物一同煅燒。藉由改變煅燒溫度發現，當煅燒溫度達210 oC時，開始形成CZTS之結晶結構，提升煅燒溫度至250 oC時，僅顯現屬於CZTS主要晶面(112)、(200)、(220)及(312)之繞射峰，且並無其他不純物之結晶相。為了討論合成CZTS之反應機構，吾人分別將氯化銅、氯化鋅、氯化錫、氯化銅＋氯化鋅、氯化銅＋氯化錫與TAA混合後，於65 oC反應1小時，並選取190 oC及250 oC進行煅燒，利用XRD晶相繞射分析發現，當煅燒溫度升高時，(1) Cu原子由2價Cu2+還原成1價Cu+，並與S2-鍵結形成Cu2S；(2) (NH4)2ZnCl4 → ZnS；(3) (NH4)2SnCl6 → SnS2，而Cu2S會先與SnS2反應形成CTS之結晶結構後，再與ZnS反應合成CZTS粉體。

Cu2ZnSnS4 (CZTS) powders have been synthesized from aqueous solutions consisting of copper (II) chloride, zinc (II) chloride, stannic (IV) chloride, and thioacetamide (TAA) dissolved in mixtures of deionized water and ethanol. The CZTS powders were obtained when the precursor solutions were held isothermally at 65 oC followed by annealing at 550 oC in Ar atmosphere. When the reaction temperature was held at 35 to 55 oC, a pronounced formation of intermediate Cu3(TAA)3Cl3 prisms resulted which produced Cu2S at elevated temperatures as an impurity. In addition, rounded particles were obtained from the CZTS precursor solutions by filtering removal of the Cu3(TAA)3Cl3 prisms. Since Zn was present as Zn2+ ions in the reaction solution, Cu2SnS3 (CTS) resulted rather than the formation of CZTS when the rounded particles were annealed at 450 ¬oC. Therefore, a successful synthesis of the CZTS powders requires annealing of the solution containing Zn2+ and the precipitate in the same pot. From thermal analyses, crystalline CZTS powders began to form as the annealing temperature was raised above 210 oC. XRD pattern revealed that the CZTS diffraction peaks appeared when the annealing temperature was raised to 250 oC and no other phases were observed. We have also conducted separate experiments involving CuCl2, ZnCl2, SnCl4, CuCl2+ZnCl2, CuCl2+SnCl4 mixture with the TAA respectively and reacted isothermally at 65 oC for 1 h. After the reaction, the solutions were annealed at 190 oC and 250 oC, respectively. When the annealing temperature was increased, following reaction steps resulted: (1) Cu2+ ions were firstly reduced to Cu+ which facilitated Cu2S formation；(2) (NH4)2ZnCl4 → ZnS；(3) (NH4)2SnCl6 → SnS2. The Cu2S reacted with SnS2 to form CTS first, and then CTS reacted with ZnS to form the CZTS powders.

第一章 緒論 1
1-1 前言 1
1-2 研究動機 2
第二章 文獻回顧 3
2-1 太陽能電池發電原理 3
2-2 Cu2ZnSnS4太陽能材料 5
2-3 Cu2ZnSnS4晶體結構 5
2-4 Cu2ZnSnS4太陽能電池效率演進 7
2-5 真空製程合成CZTS 8
2-6 非真空製程合成CZTS 13
第三章 實驗流程與分析儀器介紹 26
3-1 實驗藥品與製程設備 26
3-1-1 實驗藥品 26
3-1-2 製程設備 26
3-2 合成CZTS粉體之實驗流程 27
3-2-1反應溫度對合成CZTS粉體之影響 27
3-2-2 分離六角柱狀結構之中間相與球狀顆粒 28
3-2-3 鍛燒溫度對合成CZTS粉體之影響 29
3-2-4 TAA與Cu、Zn及Sn合成二元與三元硫化物 30
3-3 分析儀器與樣品製備 33
第四章 結果與討論 34
4-1 反應溫度對合成CZTS粉體之影響 34
4-1-1 XRD晶相繞射分析 34
4-1-2 不純相Cu2S的產生 34
4-1-3 CZTS粉體之HR-TEM顯微結構觀察及其SAD與EDS分析 39
4-2 球狀沉澱物 40
4-2-1 XRD晶相繞射分析 40
4-2-2 HR-TEM之EDS成分分析與顯微結構觀察 41
4-3 燒結溫度對合成CZTS粉體之影響 43
4-3-1 XRD晶相繞射分析 43
4-3-2 合成CZTS粉體之反應機制 44
4-3-3 TAA與Cu、Zn及Sn合成二元與三元硫化物 46
第五章 結論 52
參考文獻 54

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