臺灣博碩士論文加值系統

本研究是以溶凝膠法製備奈米晶型之氧化鋅膠體粉末與透明薄膜。起始材料分別為醋酸鋅及氯化鋅，且分別摻雜AlCl3或SiO2，並改變不同的溶液濃度，經由溶液的混合、水解、解膠、及縮聚合反應製備氧化鋅膠體粉末與透明膠體薄膜。
實驗發現，適量的水濃度、酸性電解質及摻雜Al或Si劑量，均可形成透明溶膠與凝膠，水量過多或過少及鹼性電解質均會使溶膠呈混濁析出。不同水濃度與摻雜Al或Si劑量，對膠體粉末及薄膜的熱性質、結晶性及分子結構無顯著影響，但會明顯影響粉末及薄膜的微結構。經熱處理200℃後，均開始產生氧化鋅結晶，薄膜均具有(002)面優先取向但粉末無此特性。
經熱處理200~800℃後，未摻雜的氧化鋅粉末，具有針狀及粒狀結構，煆燒至600℃後均為奈米晶型；摻雜Al 之氧化鋅粉末均為粒狀且有明顯細化，經煆燒至800℃後，仍呈奈米晶型。
經燒結500℃後，未摻雜的薄膜呈粒狀與長條狀結構，可見光穿逶率為65~83%，摻雜Al之薄膜均呈粒狀結構，平均晶粒大小為60~70nm，摻雜Al含量為0.5at% 薄膜具有最佳透光性，可見光透光率為80~86%，增加Al量會降低透光性，但添加Si含量對薄膜透光性無明顯改善效果。

In this study, nanocrystalline zinc oxide powders and transparent films are prepared by sol-gel process, using zinc acetate and zinc chloride as precursors, respectively. The influences of water content, dopant type and concentration on the characterizations of gel powders and gel films are also studied. The powders and films can be prepared via the procedures of mixing, hydrolysis, petization, and condensation reaction. Transparent sols and gels can be obtained from proper concentrations of water, acidic electrolyte, and doped Al or Si. Improper water content or basic electrolyte will result in cloudy sol and precipitation . The concentrations of water, doped Al or Si are not significant influence the thermal and crystalline behaviors as well as the molecular structures of powders and thin films. After heat-treatment at 200oC, the processed powder and films started to convert into ZnO phase. All the thin films have (002) plane preferred orientation, while powders lack such property.
After heat-treatment at 200~800oC, the undoped-ZnO powders have needle and granular structures with nanocrystal in size up to 600oC；the doped-ZnO powders all have granular strctures and smaller crystal sizes, moreover, maintain nanocrsystalline up to 800oC.
On firing at 500oC, the undoped-ZnO films possess granular and long-stripe microstructures with transmittance of 65~84% in visible light range. The visible transmittances of thin films decrease with increasing the content of doped-Al, but do not remarkable influenced by the doped treatment of Si.

中文摘要……………………………………………………………… i
英文摘要………………………………………………………………іі
誌謝……………………………………………………………………іv
總目錄………………………………………………………………… v
表目錄…………………………………………………………………іx
圖目錄………………………………………………………………… x

第一章 緒論……………………………………………………………1
1.1 前言 ………………………………………………………………1
1.2 氧化鋅之特性 ……………………………………………………2
1.3 氧化鋅粉末之特性 ………………………………………………2
1.4 氧化鋅薄膜之特性 ………………………………………………3
1.5 氧化鋅粉末與薄膜的製備方法 …………………………………3
1.5.1 沉澱法 …………………………………………………………4
1.5.2 水熱法 …………………………………………………………4
1.5.3 噴霧熱分解法 …………………………………………………4
1.5.4 真空蒸鍍法 ……………………………………………………5
第二章 文獻回顧………………………………………………………9
2.1 氧化鋅粉末之文獻探討 …………………………………………9
2.2 氧化鋅薄膜之文獻探討…………………………………………10
2.3 溶凝膠製程之介紹………………………………………………15
2.3.1 溶凝膠法之起源………………………………………………15
2.3.2 溶凝膠法之製程簡介…………………………………………15
2.3.3 溶凝膠法之優缺點……………………………………………17
2.4 實驗目的…………………………………………………………18
第三章 實驗方法與流程 ……………………………………………21
3.1 實驗方法…………………………………………………………21
3.2 實驗流程圖………………………………………………………24
3.3 結構分析…………………………………………………………27
3.3.1 熱分析(TG-DTA/DSC)…………………………………………27
3.3.2 X光繞射分析（XRD）…………………………………………27
3.3.3 霍式轉換紅外光光譜(FT-IR) ………………………………28
3.4 微結構分析………………………………………………………28
3.4.1場發射掃描式電子顯微鏡（FE-SEM）……………………… 28
3.5 特性分析…………………………………………………………29
3.5.1 比表面積測定儀(BET) ………………………………………29
3.6 光電分析…………………………………………………………30
3.6.1 紫外光-可見光-紅外光穿透光譜儀(UV-Vis-IR)………30
第四章 結果與討論 …………………………………………………37
4.1 製備氧化鋅奈米粉末……………………………………………37
4.1.1 溶凝膠反應……………………………………………………37
4.1.2 TG-DSC分析……………………………………………………40
4.1.3 XRD繞射分析 …………………………………………………50
4.1.4 FT-IR分析 ……………………………………………………56
4.1.5 FE-SEM分析……………………………………………………60
4.1.6 比表面積分析…………………………………………………70
4.2 製備氧化鋅透明薄膜……………………………………………75
4.2.1 溶凝膠反應……………………………………………………75
4.2.2 TG-DTA分析……………………………………………………78
4.2.3 XRD繞射分析 …………………………………………………80
4.2.4 FE-SEM分析……………………………………………………85
4.2.5 UV-Vis-IR分析 ………………………………………………93
4.3摻雜Si對氧化鋅薄膜性質之影響 ………………………………96
4.3.1 溶凝膠反應……………………………………………………96
4.3.2 TG-DTA分析……………………………………………………98
4.3.3 XRD繞射分析…………………………………………………101
4.3.4 FE-SEM分析 …………………………………………………104
4.3.5 UV-Vis-IR分析………………………………………………112
第五章 結論…………………………………………………………115
未來研究方向 ………………………………………………………118
參考文獻 ……………………………………………………………119
個人資料介紹 ………………………………………………………122

[1] T.Hattori. , Journal of Materials Science Letters, 2(1983) 503-504
[2] J. P. Chatelon, C. Terrier and J. A. Roger, Journal of Sol-Gel Science and
Technology, 10 (1997) 55-66.
[3] M. T. Tsai, H. C. Chang, P. J. Tsai, K.Y. Yeh, H. C. Tsai, Y. C. Lan,
2005, November, 2005 International Symposium on Nano Science and
Technology, Tainan, Taiwan, Paper # PC022 (2005-ISNST).
[4] L.C.Klein, Journal of Sol-Gel Science and Technology, Noyes Pub., New
Jersey, 1988
[5] M. T. Tsai, Materials Research Bulletin, 37 (2002) 2213-2226
[6] S. Major, A. Banerjee and K. L. Chopr, Thin Solid Films, 108(1983) 333-340
[7] H. L. Hartnagel, A. K. Jain and C. Jagadish, published by Institute of
Physics Publication, 1995, 17-21
[8] 楊明輝,“金屬氧化物透明導電材料的基本原理”, 工業材料雜誌, 179 (2001)p.134- p 144
[9] 廖世傑,“奈米氧化鋅粉體之新穎合成與應用技術”, 工研院材料所, p.1-pl4
[10] 鄭世裕,“無機奈米材料產業應用” , 工業材料雜誌, 190(2002) p.85-p.95
[11] B. Pal, M. Sharon, Materials Chemistry and Physics 76 (2002) 82-87.
[12] J. H. Park, Y. J. Choi, J. G. Park, Journal of the European Ceramic
Society, 25 (2005) 2037–2040
[13] 楊明輝, “透明導電膜材料與成膜技術的新發展”, 工業材料雜誌, 189(2002)
p.161-p.174
[14] E.M. Bachari, G. Baud, S. Ben Amor, M. Jacquet, Thin Solid Films, 348
(1999) 165-172
[15] D. L. Raimondi and E. Kay, Journal of Vacuum Science & Technology, 7
(1969) 96-98
[16] Y. Igasaki and H. Saito, Thin Solid Films, 199(1991) 223-230
[17] V. Fathollahi, M. Mohammadpour Amini, Materials Letters, 50(2001) 235–239
[18] J. Han, P.Q. Mantas, A.M.R. Senos, Journal of the European Ceramic
Society, 2(2001) 1883–1886
[19] W. S. Law, Journal of Electron Materials, 141(1987) 16-21
[20] O.Takai, M.Futsuhara, G. Shimizu, C.P. Lungu, J. Nozueb, Thin Solid
Films, 318 (1998) 117–119
[21] J. S. Kim, Thin Solid Films, 133(1992) 217-221
[22] S. N. Bai, J. S. Shieh, T. Y. Tseng, Materials Chemistry and Physics, 41
(1995) 104-109
[23] H. C. Chang, M. T. Tsai, 2006, Journal of the Chinese Vacuum Society, 19
(2006) (in press).
[24] A. Chittofrati and E. Matijevic, Colloids and Surface, 48(1990) 65-78.
[25] Y. Kavanagh, M.J. Alam, D.C. Cameron, Thin Solid Films, 447 (2004) 85–89
[26] S. Bandyopadhyay, G.K. Paul, R. Roy, S.K. Sen, S. Sen, Materials
Chemistry and Phys-ics, 74 (2002) 83–91
[27] J.L.Van Heerden R.Swanepeol, Thin solid films, 299(1997) 72-77
[28] J. Xu, E. S. O’Keefeb and C. C. Perry, Journal of Materials Chemistry,
14 (2004) 1744-1748
[29] D. Jezequel, Jean Guenot, Noureddine Jouini, and Fernand Fievet, Journal
of Materials Research, 10 (1995) 77-83
[30] J. Xu, E. S. O’Keefeb and C. C. Perry, Journal of Materials Chemistry,
14 (2004) 1744-1748
[31] 廖世傑 ,林秀芬 ,洪松慰 ,董志偉, “奈米粉體製造與應用”, 工業材料雜誌, 204
(2003) p.161-p.174
[32] H. T. Lu, M. Yokoyama, Journal of Crystal Growth, 260 (2004) 186–190
[33] H. Ma, J. S. Cho, C. H. Park, Surface and Coatings Technology, 153 (2002)
131–137
[34] V. Fathollahi, M. Mohammadpour Amini, Materials Letters, 50 (2001) 235–
239
[35] V.Musat, B.Teixeira, E.Fortunato, R.C.C.Monteiro, P.Vilarinhoc, Surface
and Coaings Technology, 180 (2004) 659–666
[36]Jiaping Han, P.Q. Mantas, A.M.R. Senos, Journal of the European Ceramic
Society, 21 (2001) 1883–1886
[37] G.K. Paul, S.K. Sen, Materials Letters, 57 (2002) 959–963
[38] J. H. Lee, B. O.k. Park, Thin Solid Films, 426 (2003) 94–99
[39] Y. Igasaki and H. Saito, Thin Solid Films, 199 (1991) 223-230
[40] K. H. Kim, K. C. Park and D. Y. Ma, Jounal of Applied Physical, 82 (1997)
7764.-7767
[41] G.K. Paul, S.K. Sen, Materials Letters, 57 (2002) 742–746
[42] Masashi Ohyama, Journal of the American Ceramic Society, 81 (1998) 1622– 1632
[43] N. Fujimura, T. Nishihara, S. Goto, J. Xu and T. Ito, Journal of Crystal
Growth, 130 (1993) 269-271
[44] M. T. Tsai, H. C. Chang, C. C. Liao, H. W. Liu, 2005, November,
Proceeding of the 2005 Annual Conference of the Chinese Society for
Materials Science, Taipei, Taiwan, Paper PB-052.
[45] J. J. Ebelmen, Ann., 57(1846) 331
[46] R. Roy, Journal of the American Ceramic Society, 39 (1956) 145
[47] K. S. Matediyasni, R. T. Doll, J. S. Smith, Journal of the American
Ceramic Society, 52 (1969) 513
[48] W.Tang, Thin Solid Films, 238 (1994) 83-87
[49] O. Yamamoto, T. Sasamoto and M. Inagaki, Journal of Materials Research, 7
(1992) 2488-2491.
[50] P. Layrolle, A. Ito, T. Tateishi, Journal of the American Ceramic
Society, 81(1998) 421-424
[51] Lopatin, C.M.; Pizziconi, V. Alford, T.L. Laursen, Thin Solid Films, 326
(1998) 227-232
[52] M. T. Tsai, Journal of the European Ceramic Society, 22 (2002)1073-1083
[53] H. C. Chang, C. C. Liao, M. T. Tsai, 2005, Chemical Monthly, 23 (2005) 57-
63.
[54] M. T. Tsai, P. J. Tsai, H. C. Chang, 2005, November, 2005 Electronics
Devices and Ma-terials Symposia, Kaohsiung, Taiwan, Paper PC-16, 2005.
[55] S. Fujihara, C. Sasaki, T. Kimura, Journal of the European Ceramic
Society, 21 (2001) 2109–2112
[56] B. Jirhennsons et al, Colloid Chemistry, Mc.Millan Co. New York (1962)
[57] 蔡木村, “以化學方法合成透光性MgO及SiO2陶瓷粉末之研究” , 國科會研究報告,
1996年, p.11
[58] T.C Hang, Y.T. Wang, Y.S. Hong, Y.S. Chen, J.C. Yang, Polymer Degradation
and Stability, 69 (2000) 317-320
[59] 陳永志, 陳姿秀, 陳致源, “溶膠-凝膠法之研究與技術發展近況(上)”, 工業材料
雜誌, 206 (2004) 169-177
[60] J. H. Lee, K. H. Ko, B. O.k. Park, Journal of Crystal Growth, 247 (2003)
119–125
[61] A. K., T. Misono, Y. Abe, Journal of Non-Crystalline Solids, 243 (1999)
168-174
[62] K.S.Mazdiyasni, Journal of the American Ceramic Society, 48(1965) 372
[63] D.W. Johnson, American Ceramic Society Bulletin, 66 (1983) 688-693
[64] W. Zhang, W. Liu, C. Wang, Journal of the European Ceramic Society, 22
(2002) 2869–2876
[65] 盧裕豐 , “場發射掃描式電子顯微鏡(FE-SEM)研討會”, 12/02/2005
[66] 林智仁 ,羅聖全 , “場發射穿透式電子顯徽鏡簡介”, 工業材料雜誌, 201(2003)
90 -98
[67] 楊家銘 ,“奈米孔洞材料之物理吸脫附分析” , 科儀新知, 26 (2005) 32-38
[68] D.B.Akolekar, G. Foran, S. K. Bhargava, Journal of Synchrotorn
Radlation,11(2004) 284-290
[69] D. Bao, H. Gu, and A. Kuang, Thin Solid Films, 312(1998) 37-39
[70] K.Nakamoto, “Infrared and Raman Spectra of Inorganic and Coordination
Comounds”, 4thed. Wiely, New York, 1986