本研究已提出一新穎之氯化銀薄膜製造方法，將硝酸銀水溶液相變化成固態後，滴入氯化鈉水溶液，藉由析出反應製得氯化銀薄膜。並探討在暗室及UV曝照環境下對AgCl薄膜的晶體形態影響。暗室環境之AgCl薄膜晶態，上表面形態為接近等軸狀晶體；下表面型態為微小顆粒以異質孕核於薄膜下表面的硝酸根晶體及以優選方向成長成棒狀結構。UV曝照環境之AgCl薄膜晶態，上表面形態為AgCl晶體以銀原子簇為異質成核點成長成展弦比較大之長軸晶態，其中銀原子簇來自於UV光照射AgCl晶體後產生的光分解所致。

This research has brought a new method to fabricating silver chloride films. The silver nitrate solution phase-changed into solid phase and the sodium chloride solution were infused, and then the silver chloride film was produced by precipitation reaction. And the research is a study of the effects on the crystalline morphology of AgCl film which grew in the UV-exposed environment and in the darkness, respectively. The crystalline morphology of AgCl film upper-surface which grew in the darkness is close to equiaxed crystals. The crystalline morphology of AgCl film under-surface is small particles which heterogeneously nucleated on the nitrate crystals under the surface of the film and to be in accordance with the preferred orientation into the stick-like structure. As the crystalline AgCl film grew in the UV-exposed environment, the AgCl crystal became a long axis crystal due to the silver clusters as heterogeneous nucleation site. And the crystal is identified with a higher aspect ratio. The silver clusters were derived from AgCl crystal photodecomposition which was caused by UV rays irradiation.

總目錄
總目錄	I
圖目錄	IV
符號說明	VII
壹、導論	1
1-1 前言	1
1-2文獻回顧	3
1-2-1 氯化銀簡介	3
1-2-2 溶解度	3
1-2-3 過飽和度	5
1-2-4 成核現象	8
1-2-4-1 均質成核	9
1-2-4-2異質成核	12
1-2-4-3二次成核	15
1-2-5 晶體成長	18
1-2-6 雜質對結晶的影響	21
1-3.研究動機與論文架構	23
1-3-1研究動機與目的	23
1-3-2論文架構	24
貳、實驗步驟	28
2-1. 實驗裝置	28
2-1-1 實驗藥品與材料	28
2-1-2 實驗設備及分析儀器	28
2-2 實驗步驟	29
2-2-1氯化銀薄膜之製備	29
2-2-1-1暗室析出氯化銀薄膜Type I與UV曝光氯化銀薄膜之製備	29
2-2-1-2 暗室析出氯化銀薄膜Type II	31
2-2-1-3暗室析出氯化銀薄膜Type I添加HNO3之實驗	32
2-2-2氯化銀薄膜顯微結構及性質分析	33
2-2-2-1顯微結構觀察	33
2-2-2-2 X-光繞射分析(XRD)	33
參、結果與討論	35
3-1暗室析出AgCl薄膜	35
3-1-1暗室析出AgCl薄膜之上表面形態	35
3-1-2暗室析出AgCl薄膜下表面形態	38
3-2  UV曝光析出AgCl薄膜	41
3-2-1 UV曝光析出AgCl薄膜上表面形態	41
3-2-2 UV曝光析出AgCl薄膜下表面形態	44
肆、結論	69
伍、參考文獻	71

圖目錄
Fig.1-1溶解度曲線-超溶解度曲線示意圖	25
Fig.1-2晶體粒徑與自由能之關係示意圖	25
Fig.1-3於外來粒子表面進行異質成核反應	26
Fig.1-4群聚體孕核成穩定晶核	26
Fig.1-5吸收層內的成核現象示意圖	27
Fig.1-6溶液中結晶的驅動力	27
Fig.3-1暗室析出AgCl薄膜上表面形態；反應時間(a)1分鐘；(b) 5分鐘之SEM圖片	46
Fig.3-2 暗室析出AgCl薄膜剖面形態；反應時間(a)1分鐘；(b)5分鐘；(c)10分鐘之SEM圖片	47
Fig.3-3暗室析出AgCl薄膜上表面形態；反應時間(a)10分鐘；(b)20分鐘；(c)30分鐘之SEM圖片	48
Fig.3-4 暗室析出AgCl薄膜剖面形態；反應時間(a)20分鐘；(b)30分鐘之SEM圖片	49
Fig.3-5暗室析出AgCl薄膜上表面形態；反應時間(a)1小時；(b)8小時；(c)16小時之SEM圖片	50
Fig.3-6 暗室析出AgCl薄膜剖面形態；反應時間(a)1小時；(b)4小時；(c)12小時；(d)20小時之SEM圖片	51
Fig.3-7暗室析出AgCl薄膜反應時間24小時之上表面形態SEM照片	52
Fig.3-8暗室析出AgCl薄膜下表面形態；反應時間(a)1分鐘；(b)5分鐘之SEM圖片	53
Fig.3-9暗室析出AgCl薄膜下表面形態；反應時間(a)10分鐘；(b)20分鐘；(c)30分鐘之SEM圖片	54
Fig.3-10(a)暗室析出AgCl薄膜TypeII； (b)(c) 暗室析出AgCl薄膜TypeI添加HNO3上表面形態SEM圖片	55
Fig.3-11暗室析出AgCl薄膜下表面形態；反應時間(a)1小時；(b)8小時；(c)20小時之SEM圖片	56
Fig.3-12 UV曝光AgCl薄膜反應時間1分鐘上表面形態；放大倍率(a)2000；(b)1200之SEM圖片	57
Fig.3-13 UV曝光AgCl薄膜反應時間3分鐘上表面形態；放大倍率(a)2000；(b)1200；(c)500之SEM圖片	58
Fig.3-14 UV曝照氯化銀薄膜之XRD分析(a)UV曝照氯化銀薄膜 (b)銀標準繞射圖譜 (c)氯化銀標準繞射圖譜	59
Fig.3-15 UV曝光反應時間1分鐘氯化銀薄膜之EPMA mapping分析	60
Fig.3-16 UV曝光反應時間24小時氯化銀薄膜之EPMA mapping分析	61
Fig.3-17 UV曝光AgCl薄膜上表面形態；反應時間(a)7分鐘；(b)10分鐘；(c)20分鐘之SEM圖片	62
Fig.3-18 UV曝光AgCl薄膜上表面形態；反應時間(a)1小時；(b)8小時之SEM圖片	63
Fig.3-19 UV曝光AgCl薄膜剖面形態；反應時間(a)30分鐘；(b)1小時；(c)4小時；(d)12小時；(e)16小時；(f)24小時之SEM圖片	64
Fig.3-20 UV曝光AgCl薄膜上表面形態；反應時間(a)12小時；(b)20小時；(c)24小時之SEM圖片	65
Fig.3-21 UV曝光AgCl薄膜下表面形態；反應時間(a)1分鐘；(b)10分鐘；(c)20分鐘之SEM圖片	66
Fig.3-22 UV曝光AgCl薄膜下表面形態；反應時間(a)1小時；(b)8小時；(c)20小時之SEM圖片	67
Fig.3-23 UV曝光AgCl薄膜下表面形態；反應時間(a)8小時；(b)20小時；(c)24小時之SEM圖片	68

伍、參考文獻
1.	Chi-Kit Siu, Brigitte S. Fox-Beyer, Martin K. Beyer, and Vladimir E. Bondybey, “Ab Initio Molecular Dynamics Studies of Ionic Dissolution and Precipitation of Sodium Chloride and Silver Chloride in Water Clusters, NaCl(H2O)n and AgCl(H2O)n, n = 6, 10, and 14”, Chem. Eur. J 12(2006), pp.6382 – 6392.
2.	簡文鎮,「以凝聚理論探討碳酸鈣之成核引發時間」,國立台灣大學化學工程研究所博士論文(2001)pp.28-46.
3.	Söhnel O. and J. Garside, Precipitation: Basic Principles and Industrial Applications, Butterworth-Heinemann, Oxford. (1992).
4.	Nielsen, A. E. “Electrolyte Crystal Growth Mechanisms”, J. Cryst. Growth, 67, 2(1984a) pp.289-310.
5.	Nielsen, A. E. and J. M. Toft, “Electrolyte Crystal Growth Kinetics”, J. Cryst. Growth, 67, 2 (1984b) pp.278-288.
6.	King, M. and A. Mersmann, “On Supersaturation during Mass Crystallization from Solution”, Chem. Eng. Technol., 13, 1(1990) pp.50-62.
7.	Dirksen, J. A. and T. A. Ring, “Fundamentals of Crystallization: Kinetic Effects on Particle Size Distributions and Morphology”, Chem. Eng. Sci., 46, 10, (1991) pp.2389-2427.
8.	石政怡,「次成核的機構和其在結晶程序上之應用」,國立台灣大學化學工程研究所博士論文(1995)pp.6-11.
9.	Myerson, A. S., Handbook of Industrial Crystallization, Butterworth-Heinemann, (1992).
10.	Mullin, J. W., Crystallization, 3rd, Butterworth-Heinemann, Oxford, (1993).
11.	Mullin, J. W. and M. M. Osman, “Nucleation and Precipitation of Nickel Ammonium Sulphate Crystals from Aqueous Solution”, Kristall and Technik, 8, 4 (1973) pp.471-481.
12.	Nývlt, J., O. Söhnel, M. Matuchova and M. Broul, The Kinetics of Industrial Crystallization, Elsevier, Amsterdam, (1985).
13.	Walton,A. G., “Nucleation in Liquids and Solutions”, in Nucleation, A. C. Zettlemoyer, ed., Dekker, NY, (1969).
14.	Nomura, T., M. Alonso, Y. Kousaka and K. Tanaka, “A Model for Simultaneous Homogeneous and Heterogeneous Nucleation”, J. Colloid Interface Sci., 203, 1 (1998).pp.170-178.
15.	Kousaka, Y., T. Nomura, S. Hasebe, K. Tanaka and M. Alonso, “A Model of Liquid-phase Homogeneous Nucleation in a System Containing Seed Particles”, KONA, 17, (1999) pp.190-196.
16.	Grünewald, T, L. Dahne and C. A. Helm, “Supersaturation and Crystal Nucleation in Confined Geometries “J. Phys. Chem. B, 102, 25 (1998) pp 4988–4993.
17.	Derjaguin, B. V. and L. D. Landau “ Theory of stability of strongly Charged lyophobic sols and of the adhesion of strongly charged particles In solutions of electrolytes”, Acta Physicochimca URSS, 43, 1-4, (1941) pp.733-762
18.	Verwey, E. J. W. and J. Th. G. Overbeek ,Theory of the stability of lyophobic colloids, Elsevier, Amsterdam. (1948).
19.	Wonczak, S. and R. Strey, “Confirmation of Classical Nucleation Theory by Monte Carlo Simulations in the 3-Dimensional Ising Model at Low Temperature”, J. Chem. Phys., 113, 5 (2000).pp.1976-1980.
20.	N. H. Fletcher, “Size effect in heterogeneous nucleation,” J. Chem. Phys., 29(1958).pp.572-576.
21.	Liu, X. Y., “A New Kinetic Model for Three-Dimensional Heterogeneous Nucleation”, J. Chem. Phys., 111, 4(1999) pp.1628-1635.
22.	Clontz, N. A. and W. L. McCabe, “Contact Nucleation of Magnesium Sulfate Heptahydrate”, AIChE Symp. Ser., 110, 67 (1971).pp.6
23.	Johnson, R. T., R. W. Rousseau and W. L. McCabe, “Factors Affecting Contact Nucleation”, AIChE Symp. Ser., 68,121 (1972).pp.31.
24.	Strickland-Constable, R. F., “Kinetics and Mechanism of Crystallization’’ Academic Press, New York, (1968) pp.112.
25.	Sung, C. Y., J. Estrin and G. R. Youngquist, “Secondary Nucleation of MgSO4 by Fluid Shear”, AIChE J, 19, 5(1973).pp.957-962
26.	Denk, E. G. and G. D. Botsaris, “Fundamental Studies in Secondary Nucleation from Solution”, J. Cryst. Growth, 13/14, (1972).pp.493-499
27.	Garabedian, H. and R. F. Strick-Constable, “Collision Breeding of Crystal Nuclei: Sodium Chlorate”, J. Cryst. Growth, 13/14, (1972).pp. 506-509.
28.	Youngquist, G. R. and A. D. Randolph, “Secondary Nucleation in a Class II System: Ammonium Sulfate-Water”, AIChE J., 18, 2 (1972).pp.421-429
29.	J. W. Gibbs: The Scientific Papers of J. Willard Gibbs, Vol.1: Thermodynamics, Dover Publications, New York, (1961).
30.	Noyes, A. A. and Whitney, W. R.,”The rate of solution of solid substances in their own solutions”, J. Amer. Chem. Soc., 19, 3, （1897）. pp. 930-934.
31.	Frank, F.C.”On the equations of motion of crystal dislocations”, Proceedings of the Physical Society. Section A 62, 2, (1949) pp. 131-134.
32.	Gilmer, G.H., Bennema, P., “Simulation of crystal growth with surface diffusion” Journal of Applied Physics 43, 4 (1972) pp. 1347-1360.
33.	Garside, J. “The concept of effectiveness factors in crystal growth.” Chem. Eng. Sci., 26, (1971) pp.1425-1431.
34.	Senol, D. and Myerson, A.S., “Effect of Impurities on Occlusion During Crystallization from Solution.” AIChE, vol. 78, 215, (1982). pp. 37-41.
35.	Cooke, E. G.,” The effect of additives on the crystal form of sodium chloride.” In: J. L. RAU (Editor), Proceedings of the Second Symposium on Salt, 2. Northern Ohio Geol. SOC., Cleveland, Ohio, (1966).pp. 259-268.
36.	Harano, Y.and Yamamato, H."Impurity Effect of some Amino Acids on Formation and Growth of L-Glutamic Acid Nuclei by Secondary Nucleation in Agitated Solution", Journal of Chemical Engineering of Japan, 14 , 1(1981).pp.59-64.
37.	Falini, G., M. Gazzano, A. Ripamonti, “Crystallization of Calcium Carbonate in Presence of Magnesium and Polyelectrolytes”, J. Crystal Growth, 137, 3-4 (1994).pp.577-584.
38.	Söhnel O. and J. W. Mullin, “Precipitation of Calcium Carbonate”, J. Cryst. Growth, 60, 2 (1982).pp.239-250
39.	Van der Leeden, M.C., Van Rosmalen, G.M.“Aspects of additives in precipitation processes: Performance of polycarboxylates in gypsum growth prevention “Desalination, 66, (1987) pp.185-200.
40.	Buckley, H.E.”Habit modification in crystals as a result of the introduction of impurities during growth” Discussions of the Faraday Society 5, (1949) pp. 243-254.
41.	陳寶祺,「微溶物系之沉澱與結晶」, 國立台灣大學化學工程研究所博士論文,(1992)pp.26.
42.	Balluffi, Allen and Carter ,Kinetics Of Materials 1Ed (2005)