此研究採用靜電輔助氣相沉積法(EAVD)以四氯化錫(SnCl4)及DBTDC (C12H24O4Sn)為溶液先驅物去沉積二氧化錫薄膜。適當的沉積鍍膜參數確認可以得到多孔與緻密的薄膜。沉積後經過600°C兩小時煅燒後的薄膜可以得到結晶性良好的金紅石氧化錫結構。
電性的量測結果顯示，大部分由乙醇當溶劑的溶液先驅物所得到的多孔薄膜內部並不連續；而由卡畢醇與乙醇之混合溶劑所得到之不多孔的薄膜有較穩定的電性量測所得到的阻抗值。電性的量測結果顯示，由70%乙醇-30%卡畢純的溶劑混合之溶液所得的薄膜，對100ppm之CO氣體的最高敏感度為2.55。另外從含有DBTDC之溶液先驅物所得到之薄膜試片可得到更高的氣體偵測敏感度6.55。

Electrostatic Assisted Vapor Deposition method was adopted to deposit SnO2 thin films in this work using either SnCl4 or DBTDC (C12H24O4Sn) as precursors. Appropriate deposition parameters were identified for deposition of porous and dense films . A post-deposition calcination of 600°C/2h yielded well crystalline rutile phase. Electrical resistance measurement indicated that the most porous films ,derived from the precursor solution of ethanol solvent, were not continuous. Instead, films derived from precursor solution of mixed ethanol-carbitol solvent were less porous allowing stable resistance values to be measured. A detection sensitivity of 2.55 for 100ppm CO gas was obtained from films derived from a 30% ethanol-70% carbitol solution. A higher sensitivity of 6.55 was obtained from films derived from solutions containing Di-n-butyltin diacetate (DBTDC) as precursor.

目錄
Abstract…………………………………………………………….…………. i
中文摘要……………………………………………………………..………. ii
目錄…………………………………………………………………..………. iii
圖目錄………………………………………………………………..………. v
表目錄………………………………………………………………..………. xi

第一章 前言……………………………………………………………….... 1
1-1 二氧化錫薄膜的性質與應用…………………………………............. 1
1-2 二氧化錫薄膜的製備方式……………………………………………. 2

第二章 文獻回顧…………………………………………………............... 5
2-1 SnO2之結構與簡介…………………………………………….…….. 5
2-1.1 SnO2之摻雜……………………………………………….……. 7
2-2 EAVD之鍍膜方法與原理……………………………………….……. 8
2-2.1形成cone-jet mode之研究……………………………………… 11
2-2.2 Cone-jet的形成理論……………………………………………. 14
2-2.3霧滴尺寸之估算……………………………………………........ 16
2-2.4影響jet之參數…………………………………………………... 19
2-2.5鍍膜形貌之研究……………………………………………........ 21
2-3 二氧化錫氣體偵測器的導電原理……………………………............. 24
2-4 氣體吸附機制…………………………………………………............. 27

第三章 實驗方法及步驟……………………………………...………….... 31
3-1 溶液先驅物之準備………………………………………………........ 32
3-1.1鍍膜溶液SnCl4之調配……………………………….………..
3-1.2摻雜溶液SbCl3之調配…………………………………….......
3-1.3 TGA (Thermogravimetric Analyzer) 量測…………….….......... 32
32
33
3-2 基材之準備………………………………………………………......... 33
3-3 EAVD鍍膜……………………………………………………….......... 34
3-4 鍍膜參數……………………………………………………...……….. 36
3-5 分析儀器…………………………………………………………......... 38
3-5.1截面(cross section)觀察試片製作………………………………
3-5.2表面觀察試片之製作……………………………………………
3-5.3電性量測試片之準備…………………………………………… 39
42
42
3-6 氣體偵測系統的建立與偵測軟體之使用……………………………. 44

第四章 實驗結果..…………..………………………………………………. 46
4-1 TGA分析……………………………………………………………… 46
4-2 XRD分析結果與討論……………………………………………....... 47
4-3 SEM表面形貌觀察結果與討論…………………………………....... 54
4-3.1溫度系列………………………………………………………...
4-3.2時間系列………………………………………………………...
4-3.3流率系列………………………………………………………...
4-3.4溶劑系列…………………………………………………….......
4-3.5觀察粗糙度影響之SEM結果………………………………….. 54
59
62
66
72
4-3.6以DBTDC先驅物鍍膜之溫度系列SEM結果……………….. 76
4-4 SEM截面觀察結果…………………………………………………… 82
4-5 氣體偵測結果………………………………………………………… 89
4-5.1 T系列試片…………………………………………………….
4-5.2 S系列試片…………………………………………………….
4-5.3 t系列試片……………………………………………………..
4-5.4 DBTDC之溫度系列試片…………………………………….. 89
92
94
95

第五章 討論…………………………………………………………………. 97
5-1 溫度系列之討論……………….……………………………………… 97
5-2 時間系列之討論……………….……………………………………… 99
5-3 流率系列之討論……………….……………………………………… 100
5-4 溶劑系列之討論……………….……………………………………… 101
5-5 DBTDC之溫度系列之討論…...……………………………………… 102
5-6 試片粗糙度的影響.…………………………………………………… 103
5-7 溶液的沾溼性(wetting)探討……..…………………………………… 104
5-8 霧滴尺寸之估算方法.………………………………………………… 107

第六章 結論…………………………………………………………………. 108
第七章 參考文獻……………………………………………………………. 109

附錄A 霧滴尺寸計算之程式……………………………………………… 112
附錄B GPES軟體操作步驟…………………………………….…………. 113

1. Z. M. Jarzebski and J. P. Marton, J. Electrochem. Soc.- Rew, 123(7)(1976)199C
2. E. Aperathitis, et al., Materials and Solar Cells, 45(1997)161
3. G.H. Heilmier, Sci. Am., 222(4)(1970)100
4. K.H. Choi, J.Y. Kim, Y.S. Lee, H.J. Kim, Thin Solid Films, 341 (1999)152
5. H. DE WAAL and F. SIMONIS, Thin Solid Films,77(1981)253.
6. C.Klein and C.S. HurlBut, Proc 1993”Manual of Mineralogy ”p383.
7. G. Sberveglieri , Sensors and Actuators , B 23 (1995) 103.
8.台灣環保產業雙月刊/第12期 攜帶式氣體分析儀與偵測器市場
9. A. Smith, J.M. Laurent, D.S. Smith and J.P. Bonnet, Thin Solid Films,315(1998)17
10. Y.Kobayashi, M.Okamoto and A.Tomita, J. Mater. Sci., 31(1996)6125
11. D.J.Yoo, J. Tamaki,S.J. Park,N. Miura and N. Yamazoe, J.Am.Ceram.Soc.,79(8)(1996)2001
12. A. Smith, J.M. Laurent, D.S. Smith and J.P. Bonnet, Thin Solid Films,266(1995)20
13. G. Sanon, R. Rup and A. Mansingh, Thin Solid Films, 190(1990)287
14. D. Das and R. Banerjee, Thin Solid Films,147(1987)321
15. J.L. Huang, D.W. Kuo, B.Y. Shew, Surface and Coatings Technology,79(1996)263
16. H. Gourari, M. Lumbreras, R. Van Landschoot, J. Schoonman,Sensors and Actuators, B 47(1998)189
17. H. Gourari, M. Lumbreras, R. Van Landschoot, J. Schoonman,Sensors and Actuators, B 58(1999)365
18. D. Zaouk, Y. Zaatar, A. Khoury, C. Llinares, J.-P. Charles, J.Bechara, Microelectronic Engineering, 51-52(2000)627
19. El Hadj Algaphe Diagne, M. Lumbreras, Sensors and Actuators B, 78(2001)98
20. W. H. Baur, Acta Cryst, 9 (1956)515
21. 李尚謙，碩士論文，以超音波物化法製備之銻及鉭摻雜氧化錫薄
膜之光電特性，國立中山大學材料科學研究所(2002)
22. J. DUTTA, J. PERRIN, et al., J.Mater. Sci.,30(1995)53
23. T.D.Senguttuvan, L.K.Malhotra, Thin Solid Films, 289(1996)22
24. H.DE WAAL AND F.SIMONIS, Thin Solid Films, 77(1981)253
25. H.Yang, S.Han,et al., Mater. Chem. Phys., 56(1998)153
26. C. H. Chen, M. H.J. Emond, E. M. Kelder, B. Meester,J.Schoonman,
J. Aerosol Sci., 30(1999)959
27. W.Balachandran et al.,Journal of Electrosatics ,50(2001)249
28. Chunhua Chen, Erik M. Lelder, et al., J. Mater. Chem., 6(5)(1996)765
29. CHEN,C. H.,Kelder,e.m. and Schoonman, J. Eur. Ceram.
Soc.,J.(1997c)
30. Cloupeau M., Prunet-Foch, J. Aerosol Sci. 25(1994)1021
31. KEQI TANG AND ALESSANDRO GOMEZ, J. Colloid. Interface
Sci, 184(1996)500.
32. Ian G. Harpur, Adrian G. Bailey and Adel H. Hashish, J. Aerosol Sci.
Vol.27, No. 7(1996)987
33. Bailey,Electostatic spraying of liquids,John Wiley and Sons,New
York,1988
34. L.Rayleigh, Philos.Mag., 1882, 5, 184
35. G.I. Taylor, Proc.R.Soc.London, A, 1964, 280, 383
36. J. Zeleny, Phys. Rev. 10(1917)
37. B. Vonnegut, R.L. Neubaruer, J. Colloid Sci., 7(1952)616.
38. A.M. Gana-Calvo, J. Davila, A. Barrero, J. Aerosol Sci. 28 (1997)249.
39. A. Neukermans, J. Appl. Phys. 44(1973) 4769
40. A.G. Bailey, W. Balachandran, J. Electrostatics 10 (1981) 99.
41. M. Cloupeau, B. Prunet-Foch, J. Electrostatics 22 (1989) 135.
42. C. H. Chen, E. M. Kelder, J. Schoomman, : J. Mater. Sci.
31(1996)5437
43. J. Watson, K. Ihokura and G. S V Coles, Meas. Sci.
Technol.,4(1993)711
44. S.M. Sze, Semiconductor Sensors, John Wiley and Sons,(1994)388
45. J. Ding, T.J. McAvoy, R.E. Cavicchi, S. Semancik, Sensors and Actuators B,77(2001)597
46. N. Barsan, U. Weimar, Journal of Electroceramics,7(2001)143
47. Hisahito Ogawa, Masahiro Nishikawa, and Atsushi Abe, J. Appl.
Phys., 53(6),(1982)4448
48.許慶雄，以超音波霧化製程製備之SnO2薄膜性質，國立中山大學
材料科學與工程研究所碩士論文，(2001)。