臺灣博碩士論文加值系統

本研究主要是探討摻雜銻之二氧化錫溶膠在水熱法製程中水熱溫度、持溫時間、鹽類效應、起始溶膠濃度等製程參數與晶粒成長的關係。以四氯化錫-乙醇-水的方式及三氯化銻溶於醇類加入二氧化錫溶膠的方式製備摻雜銻之二氧化錫溶膠後，在260℃，持溫一小時的水熱法處理之下，可以得到平均晶粒大小為7.55nm且分布均一的二氧化錫溶膠，鍍成薄膜後電阻率值為3.87ohm-cm。在260℃的水熱處理之下，晶粒在持溫一小時內成長迅速，一小時以後晶粒成長趨緩；在同樣持溫時間條件下，水熱溫度在230℃至260℃間晶粒有明顯的快速增長；在不同起始溶膠濃度作水熱處理之下，結果發現隨著起始溶膠濃度的增大，晶粒分布愈不集中；而含有鹽類之溶膠在260℃，持溫一小時的水熱處理後，粒子會聚集而形成凝膠；以溶膠及凝膠兩種不同形式予以水熱處理，結果以溶膠形式之結晶度較佳。

The object of this thesis is to systematically discuss the relation between Sb/SnO2 crystal growth and hydrothermal process variables, which include hydrothermal treatment temperature, treatment duration time, salt effect, concentration of original sol.
The aqueous Sb/SnO2 sol was prepared by ethanol-water-stannic chloride, and then mixed SnO2 sol with methyl alcohol which contained antimony chloride. Under 260℃and 1 hour duration of hydrothermal treatment, well-distributed crystals of 7.55nm size were formed and the resistivity value of the sol coated on a substrate in the form of film is 3.87ohm-cm.
In the aspect of researching the relation between crystal growth and hydrothermal treatment temperature, crystals grew rapidly between 230℃to 260℃under the same duration time. Furthermore, in 260℃but different duration time treatment conditions, crystals grew expeditiously in 1 hour but tardily in longer than 1 hour duration.
As the concentration of original sol raised, the distribution of crystal size showed a wider orientation after hydrothermal treatment. In the salt effect discussion, stable sol containing different salt all agglomerated after 260℃1 hour hydrothermal treatment. Between sol-type and gel-type hydrothermal process, the results of which revealed that the crystallite of sol-type was higher.

第一章　文獻回顧1
1.1二氧化錫之應用1
1.2 SnO2的晶格構造與基本物性5
1.3 溶膠-凝膠（sol-gel）法7
1.4 SnCl4和SbCl3的水解縮合反應與摻雜方法10
1.5 DLVO理論簡述13
1.6水熱法簡介17
1.7研究目的20
第二章 實驗22
2.1 實驗引言22
2.2 實驗藥品23
2.3 製備Sb/SnO2溶膠24
2.4 不同製程參數之水熱法處理與薄膜之製備30
2.5 樣品特性分析35
第三章 結果與討論38
3.1 水熱溫度對晶粒的影響38
3.2 持溫時間對晶粒的影響49
3-3 加入鹽類對晶粒的影響.59
3-4 起始溶膠濃度對晶粒的影響62
3-5 溶膠-凝膠對晶粒的影響67
3.6 水熱法與固相鍛燒法所鍍薄膜之性質比較72
第四章 結論82
第五章 參考資料84

1. R. S. Hiratsuka, S. H. Pulcinelli, and C. V. Santilli, Journal of Non-Crystalline Solids, 121, 76(1990).
2. H. Ogawa, A. Abe, M. Nishikawa, and S. Hayakawa, Journal of Electrochemistry Society- Solid State Science Technology, 128, 2020(1981).
3. N. J. Arfsten, R. Kaufmann, and H. Dislich, Processing International Conference on Ultrastructure Processing of Ceramics Glass and Composites, 189(1983).
4. Z. M. Jarzebski and J. P. Marton, Journal of Electrochemistry Society-Reviewed News, 123, 199(1976).
5. Y. S. He, J. C. Campbell, and R. C. Murphy, Journal of Materials Research, 8, 3131(1993).
6. T. A. Kuku, Thin Solid Films, 142, 241(1986).
7. N. S. Murty and S. R. Jawatekar, Thin Solid Film, 108, 277(1983).
8. E. Shanthi, V. Dutta, A. Banerjee, and K. L. Chopra, Journal of Applicational Physica, 51, 6243(1980).
9. G. Behr, G. Krabbes, J. Werner, P. Dordor, and J. P. Doumerc, Physica Status Solidi (a), 118, K91(1990).
10. P. C. Hollamby, P. S. Aldridge, Gmoretti, and R. G. Egdell, Surface Science, 280, 393(1993).
11. J. M. Herrmann, J. L. Portefaix, M. Forissier, F. Fiqueros, and P. Pichart, Journal of Chemistry Society, Faraday Transition 1, 1346(1979).
12. S. M. Jarzebski and J. P. Marton, Journal of Electrochemistry Society, 123, 199(1976).
13. P. A. Cox, R. G. Egdell, A. F. Orchard, C. Harding, W. R. Patterson, and P. J. Tavener, Solid State Communication, 44, 837(1982).
14. P. A. Cox, R. G. Egdell, C. Harding, W. R. Patterson, and P. J. Tavener, Surface Science, 123, 179(1982).
15. R. G. Egdell, W. R. Flavell and P. J. Tavener, Journal of Solid State Chemistry, 51, 345(1984).
16. H. Chang, C. H. Pitt, and G. B. Alexander, Material Science and Engineering, B8, 99(1991).
17. A. Verma, A. Roy, and T. R. Anantharaman, The International Journal of Powder Metallurgy, 27, 51(1991).
18. H. H. Hausner, Handbook of Powder Metallurgy, Chemical Publishing, New York, 432(1973).
19. M. Ponisatowski, E. D. Schultz, and A. Wirth, Processing 8th International Conference on Electrical Contact Phenomena, Tokyo, 359(1976).
20. H. Shiomi, M. Sasaki, M. Nakamura, and Y. Matsumura, Journal of Material Science: Material in Electronics, 8, 179 (1997).
21. J. Henry and J. Livingstone, Physica Status Solidi (a), 156, K9 (1996).
22. J. Henry and J. Livingstone, Physica Status Solidi (a), 148, K51 (1995).
23. A. Geoffroy, G. Campet , J. Portier, M. Bourrel , and J. Salardenne, Material Science and Engineering , 8, 141 (1991).
24. K. Hematsu, N. Mizatani, and M. Kato, Journal of Material Science, 22, 915(1987).
25. T. Kimura, S. Inada, and T.Yamaguchi, Journal of Material Science, 24, 220 (1989).
26. M. Yoshizmi and K, Nakabayashi, Plastics Engineering, March, 915(1987).
27. S. S. Park, H. Zheng, and J. D. Mackenzie, Material of Letter, 17, 346(1993).
28. P. Bonzi, L. E. Depero, F. Parmigiani, C. Perego, G. Sberveglieri, and G. Quattroni, Journal of Material Research, 9, 1250(1994).
29. J. Zhang, B. K. Miremadi, and K. Colbow, Journal of Material Science Letter, 13, 1048(1994).
30. R. W. G. Wyckoff, Crystal Structures, Interscience, New York (1951).
31. L. C. Klein and G. J. Garvey, Journal of Non-crystalline Solids, 8(1982) 97.
32. E. A. Gulliver, J. W. Garvey, T. A. Wark, M. J. Hampden-Smith and A. Datye, Journal of American Ceramics Society, 74, 1091(1991).
33. S.S. Park, H.Zheng and J.D. Mackenzie, Material Letters, 17, 346(1993).
34. A. Maddalena, R. Dal Maschio, S. Dire and A. Raccanelli, Journal of Non-crystalline Solids, 121, 365(1990).
35. T. M. Tillotson, L. W. Hrubesh and I. M. Thomas, Materials Research Society, 121, 685(1988).
36. M.K. Paria and H.S. Maiti, Journal of Material Science, 17, 3275(1982).
37. J. Livage, Journal of Solid State Chemistry, 64, 322(1986).
38. R.S. Hiratsuka, S. H. Pulcinelli and C.V. Santilli, Journal of Non-crystalline Solids, 121, 76(1990).
39. J. F. Goodman and S. J. Gregg, Journal of Chemistry Society, 237, 1162(1960).
40. Y. Kobayashi, M. Okamoto and A. Tomita, Journal of Material Science, 31, 6125(1996).
41. R. T. Presecatan, S. H. Pulcinelli and C. V. Santilli, Journal of Non-crystalline Solids, 147, 340 (1992).
42. J. Zarzycki, M. Prassas and J. Phalippou, Journal of Material Science, 17, 3371(1982).
43. N.L. Wu, L.F. Wu, Y.C. Yang, and S.J. Huang, Journal of Material Research, 11, 813(1996).
44. J.G. Giuntini, W. Gramier, J.V. Zanchetta and A. Taha, Journal of Material Science Letters, 9, 1383(1990).
45. C.J.R. Gonzalez-Oliver and I. Kato, Journal of Non-crystalline Solids, 82, 400(1986).
46. T.M. Racheva, I.D. Stambolova and T. Donchev, Journal of Material Science, 29, 281(1994).
47. B. Orel, U. Lavrencic-Stangar, Z. Crnjak-Orel, P. Bukovec and M. Kosec, Journal of Non-crystalline Solids, 167, 272 (1994).
48. 王世源，"二氧化錫膠體製程之研究"，國立台灣大學化學工程研究所博士論文(1999)。
49. J. Livage, M. Henry and C. Sanchez, Solid State Chemistry, 18, 259(1988).
50. J. Hunter, Zeta-Potential in Colloidal Science- Properties and Applications, Academic Press, London, 1981.
51. C.J. Brinker, G.W. Scherer, Sol-Gel Science, Academic Press, New York, 1990.
52. 賴元正，"水熱環境下製備氧化鋅陶瓷粉體及變阻器應用之研究"，國立台灣大學化學工程研究所碩士論文(1998)。
53. H. Nishikura, S. Yamamoto, and Y. Terao, U. S. Patent, 4775412(1988).
54. 呂維明，戴怡德，粉粒體粒徑量測技術，高立圖書有限公司(1998)。
55. 顏月珠，統計學，三民書局(1994)。
56. I. Hease, L. Yi, E. M. Nicht, H. Xiaoxian, and G. Jinkun, Ceramics International, 18, 343(1992).