本研究提出了一種新穎的氯化銀薄膜製作方法，將氯化鈉溶液與固態硝酸銀溶液反應製得析出型氯化銀薄膜，且使用粉末熔融凝固的方法製得氯化銀平板，並探討不同燒結溫度及時間對兩者薄膜晶態之變化。析出型氯化銀薄膜的晶態，下表面型態為幅射狀之多孔棒狀結構，上表面型態為近等軸晶粒。析出型氯化銀薄膜在較高燒結溫度才有較顯著之界面擴散效應，低溫燒結以擴散控制成長，其界面控制活化能約50.2kJ/mol，擴散控制活化能約9.84kJ/mol。氯化銀平板經空冷後的晶態可區分為放射狀、羽毛狀、羽毛柱狀晶；爐冷則會形成晶粒大具羽毛狀的晶態，晶態主要受溫度梯度影響。氯化銀平板的燒結成長機制則是以擴散控制為主，擴散控制所需之活化能約4.2kJ/mol，界面控制活化能約12.6kJ/mol。在應用上，結合析出型氯化銀薄膜與氯化銀平板，製造具多孔性結構且具光回收之染料敏化太陽能電池(DSSC)電極，氯化銀平板對ITO玻璃的潤濕性與鍵結良好，但析出型氯化銀薄膜下表面的多孔性結構卻因熱量而成長，顆粒間彼此頸合融合導致孔隙數量減少。

This study proposes a novel method of fabricating silver chloride films by the precipitation of sodium chloride aqueous solution and solid-state silver nitrate aqueous solution .Bulk-type silver chloride film was obtained by melting and solidification of silver chloride powder. The effect of different sintering temperature and time to the morphology of both silver chloride films was discussed. The morphology of the precipitation-type AgCl bottom-surface is full of radial porous stick structure ,and the top-surface is composed of equiaxed grains. For precipitation-type AgCl films, the interface diffusion shows remarkable effect only at high sintering temperatures while diffusion-controlled growth is predominant at low sintering temperatures. The activation energy of interface-controlled growth of precipitation-type AgCl film is calculated to be approximately 50.2kJ/mol ,and 9.84 kJ/mol for diffusion controlled growth. The morphology of bulk-type AgCl after air-cooling can be identified as radial grains, feather-like grains and feather-like columnar grains. Large grains with feather-like morphology were formed under furnace-cooling. The morphology of Bulk-type AgCl is dominated greatly by temperature gradient. The growth mechanism of sintered bulk-type AgCl is mainly focused on diffusion-controlled growth, which has the activation energy of 4.2 kJ/mol, while the interface-controlled growth activation energy is about 12.6 kJ/mol. Precipitation-type and bulk-type AgCl films are combined to be manufactured as Dye-Sensitized Solar Cells electrodes, which have porous structures and light-recycling ability. Bulk-type AgCl and ITO glass perform extraordinary wettability and bonding. However, the porous structures grow due to heat and inter-particle necking occurs ,which decreases the quantity of voids.

總目錄
總目錄	III
圖目錄	VII
表目錄	XI
符號說明 XII
壹、導論	1
1-1前言	1
1-2文獻回顧	2
1-2.1結晶概論	2
1-2.2微溶物系晶體成核與成長	3
1-2.2.1 成核機制	3
1-2.2.2 均質成核	4
1-2.2.3 異質成核	5
1-2.2.4 二次成核	6
1-2.2.5成長機制	6
1-2.3成長動力學	7
1-2.3.1擴散控制成長	8
1-2.3.2界面控制成長	9
1-2.4燒結理論	10
1-2.4.1燒結原理與驅動力	10
1-2.4.2傳遞機構	11
1-2.4.3粗化與緻密化	12
1-2.4.4燒結活化能	12
1-2.5凝固結晶	13
1-2.6氯化銀特性與應用	15
1-2.7氯化銀薄膜製造方法	17
1-2.7.1蒸鍍法	17
1-2.7.2濺鍍法	17
1-2.7.3溶膠-凝膠法	18
1-2.7.4輥軋法	18
1-2.8染料敏化太陽能電池薄膜電極	19
1-3研究範疇	20
貳、實驗步驟	28
2-1實驗材料與設備	28
2-1.1實驗材料	28
2-1.2實驗設備	28
2-2實驗程序	29
2-2.1析出型氯化銀薄膜實驗	29
2-2.1.1析出型氯化銀薄膜的製作	29
2-2.1.2析出型氯化銀薄膜的燒結	31
2-2.2氯化銀平板實驗	31
2-2.2.1氯化銀粉末的製作	31
2-2.2.2氯化銀平板的製作	32
2-2.2.3氯化銀平板的燒結	32
2-2.3應用於染料敏化太陽能電池之氯化銀薄膜電極製作	33
参、結果與討論	34
3-1析出型氯化銀薄膜的製作	34
3-2析出型氯化銀薄膜的燒結	37
3-3析出型氯化銀薄膜之燒結活化能	40
3-4氯化銀平板的製作	42
3-5氯化銀平板的燒結	45
3-6氯化銀平板之燒結活化能	46
3-7氯化銀薄膜電極之顯微結構	46
肆、結論	85
伍、參考文獻	87
 
圖目錄
圖1-1. 結晶的準安定域	21
圖1-2. 核半徑r與自由能 的關係	21
圖1-3. 結晶表面的晶階與結點	22
圖1-4. 平板析出物的擴散控制成長 (a)示意圖; (b)組成對距離之變化	23
圖1-5. 平板析出物的界面控制成長 (a)初期; (b)後期	24
圖1-6. 燒結的傳遞機構	25
圖1-7. 液體與固體的自由能-溫度曲線	26
圖1-8. 凝固結晶的溫度-時間之冷卻曲線	26
圖1-9. AgCl/Ag-NP (NanoParticle)、AgCl與氮摻雜TiO2的UV/可見光的漫射-反射光譜	27
圖3-1. 析出型氯化銀薄膜之XRD分析(a)上表面；(b)下表面；(c)標準繞射圖譜	49
圖3-2. 析出型氯化銀薄膜之形成機制示意圖	50
圖3-3. 析出型氯化銀薄膜於不同浸泡時間之上表面形態SEM  照片 (a)10分鐘；(b)12小時；(c)24小時	51
圖3-4. 析出型氯化銀薄膜於不同浸泡時間之下表面形態SEM照片 (a)10分鐘；(b)12小時；(c)24小時	52
圖3-5. 析出型氯化銀薄膜於不同浸泡時間之剖斷面形態SEM照 片 (a)10分鐘；(b)12小時；(c)24小時	53
圖3-6. 析出型氯化銀薄膜於不同溫度燒結一天之上表面形態SEM照片 (a)25℃；(b)100℃；(c)200℃；(d)300℃；(e)400℃；(f)440℃	54
圖3-7. 析出型氯化銀薄膜未經燒結及經過100℃、200℃、300℃、400℃、440℃一天燒結後之晶粒尺寸	55
圖3-8. 析出型氯化銀薄膜於不同溫度燒結一天之下表面形態SEM照片 (a)25℃；(b)100℃；(c)200℃；(d)300℃；(e)400℃；(f)440℃	56
圖3-9. 析出型氯化銀薄膜於不同溫度燒結一天之剖斷面形態SEM照片 (a)25℃；(b)100℃；(c)200℃；(d)300℃；(e)400℃；(f)440℃	57
圖3-10. 析出型氯化銀薄膜於440℃燒結不同天數之上表面形態SEM照片 (a)1天；(b)2天；(c)3天；(d)4天；(e)5天；(f)6天；(g)7天；(h)8天	58
圖3-11. 析出型氯化銀薄膜於440℃、400℃、300℃、200℃燒結不同天數之晶粒尺寸	60
圖3-12. 析出型氯化銀薄膜於440℃燒結不同天數之下表面形態 SEM照片 (a)1天；(b)2天；(c)3天；(d)4天；(e)5天；(f)6天；(g)7天；(h)8天	61
圖3-13. 析出型氯化銀薄膜440℃燒結不同天數之剖面形態SEM照片 (a)1天；(b)2天；(c)3天；(d)4天；(e)5天；(f)6天；(g)7天；(h)8天	62
圖3-14. 析出型氯化銀薄膜進行燒結，晶粒尺寸增量對飽合尺寸增量之比值對時間之變化及曲線配合圖	63
圖3-15. 析出型氯化銀薄膜燒結晶粒成長之Arrhenius圖	65
圖3-16.  AgCl粉末之TEM照片	66
圖3-17.  AgCl粉末之XRD分析 (a)AgCl粉末；(b)標準繞射圖譜	67
圖3-18. 高溫爐空冷、爐冷降溫曲線	68
圖3-19. 氯化銀粉末加熱至500℃熔融後空冷之OM照片	69
圖3-20. 氯化銀粉末加熱至600℃熔融後空冷之OM照片	70
圖3-21. 氯化銀粉末加熱至700℃熔融後空冷之OM照片	71
圖3-22. 氯化銀粉末加熱至500℃熔融後爐冷之OM照片	72
圖3-23. 氯化銀粉末加熱至600℃熔融後爐冷之OM照片	73
圖3-24. 氯化銀粉末加熱至700℃熔融後爐冷之OM照片	74
圖3-25. 氯化銀平板於440℃、400℃、300℃、200℃燒結1~8天之晶粒尺寸	76
圖3-26. 氯化銀平板燒結，晶粒尺寸增量對飽合尺寸增量之比值對時間之變化及曲線配合圖	77
圖3-27. 氯化銀平板燒結晶粒成長之Arrhenius圖	79
圖3-28. 傳統以TiO2為電極之DSSC結構示意圖	80
圖3-29. 析出型氯化銀薄膜下表面棒狀立體多孔性結構 (a)上視; (b)側視	81
圖3-30. 以AgCl為電極之DSSC結構示意圖	82
圖3-31. 析出型氯化銀薄膜UV光照射24小時後之XRD分析      (a)析出型氯化銀薄膜UV光照射24小時；(b)銀標準繞射圖譜；(c)氯化銀標準繞射圖譜	83
圖3-32. 析出型氯化銀薄膜 /氯化銀平板接合界面之SEM照片	84

 
表目錄
表3-1. 析出型氯化銀薄膜未經燒結及經過100℃、200℃、300℃、400℃、440℃一天燒結後之晶粒尺寸	55
表3-2. 析出型氯化銀薄膜於440℃、400℃、300℃、200℃燒結不同天數之晶粒尺寸	59
表3-3. 析出型氯化銀薄膜燒結之CaseI擴散係數(D)及CaseII擴散速率(v)	64
表3-4. 析出型氯化銀薄膜燒結之擴散控制活化能(ED)及界面控制活化能(Ev)	65
表3-5. 氯化銀平板於440℃、400℃、300℃、200℃燒結不同天數之晶粒尺寸	75
表3-6. 氯化銀平板燒結之CaseI擴散係數(D)及CaseII擴散速率(v)	78
表3-7. 氯化銀平板燒結之擴散控制活化能(ED)及界面控制活化能(Ev)	79

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