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論文名稱 Title |
以離子束濺鍍製備奈米氧化鋯薄膜及其相變化之研究 The Preparation and Phase Transformation of Nanometer Zirconia Thin Film by Ion Beam Sputtering Method |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
87 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2006-06-08 |
繳交日期 Date of Submission |
2006-06-30 |
關鍵字 Keywords |
氧化鋯、介面、離子束濺鍍、擇優取向、聚合 ion beam sputtering, zirconia, preferred orientation, interface, nanocrystal, coalescence |
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統計 Statistics |
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中文摘要 |
本文使用金屬鋯為靶材,NaCl (001)單晶為基材,以離子束濺鍍製備奈米鋯薄膜和氧化鋯薄膜,經由解析穿透式電子顯微鏡,觀察這些薄膜的相變化、形狀、顆粒大小分佈和合併生長的行為。 第一部分以離子束濺鍍法生成純鋯薄膜,再進行不同溫度之後續大氣熱處理,經由擇區繞射的鑑定,可知薄膜經大氣熱處理後發生相變化,隨著熱處理溫度的升高而生成奈米級α-Zr+ZrO、α-Zr+ZrO+c-ZrO2、c-ZrO2、c-+t-ZrO2、t-ZrO2以及t-+m-ZrO2等混合相,並具有些微之擇優取向。而濺鍍於玻璃片上之鍍層,當熱處理溫度為300 ℃與350 ℃之間,玻璃基材上之薄膜顏色由黑色不透光轉變為乳白色透光。 第二部份以不同的基材溫度來成長奈米鋯薄膜,隨著基材溫度的升高生成quasiamorphous、 α-Zr、 α-Zr+ZrO 以及α-Zr+ZrO+c-ZrO2奈米薄膜。選擇基材溫度為400℃,氧氣的流量分別通以1~20sccm,結果不論氧流量多寡都以c-+t-ZrO2出現,並且皆有良好的擇優取向,在濺鍍所得之氧化鋯高溫相,以小晶粒、氧空缺及體積制約效應等解釋之。 第三部份以第二部份反應式濺鍍所得之結果做進一步分析,氧化鋯晶粒受到NaCl(001)單晶基材的影響,進行小顆粒之布朗運動而轉動聚合,使少部份的晶粒擇優取向為[001]Z//[001]N, (100)Z//(1 0)N (group A),大部份為[011]Z//[001]N, (100)Z//(100)N (group B1) or (100)Z//(010)N (group B2)。且隨著通氧量的增加,氧化鋯晶粒的擇優取向更趨明顯,擇優取向主導因素以庫倫作用力解釋之。同一group的晶粒擇可以旋轉而調整接觸面,進而聚合成單一晶粒,反之(不同group)則形成高角度晶界。 第四部份不同group之間有特殊的介面,group A 與group B之間的介面為{220}A/{200}B 和 {200}A/{111}B,另外group B1與group B2的介面為{220}B1/{200}B2。這些特殊介面的形成,以晶格misfit來討論。 |
Abstract |
Nanocrystalline α-Zr condensates deposited by ion beam sputtering on the NaCl (100) surfaces and then annealed at 100 ℃ to 750 ℃ in air. The phases present were identified by transmission electron microscopy to be nanometer-size α-Zr+ZrO、α-Zr+ZrO+c-ZrO2、c-ZrO2、c-+t-ZrO2、t-ZrO2、and t-+m-ZrO2 phase assemblages with increasing annealing temperature. The zirconia showed strong {100} preferred orientation due to parallel epitaxy with NaCl (100) when annealed between 150 ℃ and 500 ℃ in air. The c- and t-zirconia condensates also showed (111)-specific coalescence among themselves. The c- and/or t-ZrO2 formation can be accounted for by the small grain size, the presence of low-valence Zr cation and the lateral constraint of the neighboring grains. (Part 1) Nanocrystalline α-Zr condensates were deposited on the NaCl (100) plane at 25 to 450 ℃ by radio frequency ion beam sputtering from a pure 99.9% Zr disk. The nano condensates were identified by transmission electron microscopy to be quasiamorphous, α-Zr, α-Zr+ZrO and α-Zr+ZrO+c-ZrO2 phase assemblages with increasing substrate temperature. At 400 ℃ and under 1-20 sccm oxygen, c- and t-ZrO2 nanocondensates were assembled on NaCl (100) as monolayer nanocrystalline material and showed strong preferred orientation. The c- and/or t-ZrO2 were retained by small grain size, low-valence Zr cation and 2-D matrix constraint of the film. (Part 2) Nanosized c- and t-ZrO2 were formed as monolayer nanocrystalline film on NaCl (100) plane by radio frequency ion beam sputtering. The microstructure and the epitaxy relationship with the NaCl (100) plane were studied by a high resolution transmission electron microscope. The epitaxy orientation was found to be [001]Z//[001]N, [100]Z//[1 0]N (group A), and [011]Z//[001]N, [100]Z//[100]N (group B) between zirconia (Z) and NaCl (N). Group B has two variants and is the dominant type. The possible causes for the epitaxy relationship are discussed. Crystallites within the same group can merge by rotation and coalesce into a single crystal, whereas crystallites in different groups can form high-angle grain boundaries. (Part 3) Special interfaces were formed for the c- and/or t-ZrO2 (Z) nano-crystals when deposited on the NaCl (N) (100) cleavage plane by ion beam sputtering to follow the epitaxy relationships of [001]Z//[001]N, (100)Z//(1 0)N (group A); and [011]Z//[001]N, (100)Z//(100)N (group B1) or (100)Z//(010)N (group B2). The nanoparticles in group A and B were impinged and coalesced to form {220}A/{200}B and {200}A/{111}B interfaces; with anchored dislocation whereas those in group B1 and B2 form {220}B1/{200}B2 interface. The {220}A/{200}B interface is found to be of especially low energy due to good match O2– lattice sites, and smoothly joints {200} and {220} planes across the interfaces without mismatch strain and dislocations. The special interfaces may shed light on the epitaxial mechanism of nanocrystalline materials in general. (Part 4) |
目次 Table of Contents |
論文提要(中) .Ⅰ Abstract Ⅲ Contents Ⅴ List of Figure Ⅷ Part 1 Annealing induced oxidation and transformation of Zr thin film prepared by ion beam sputtering deposition 1.Introduction 1 2. Experimental 2 3. Results 3 3.1. Phase identity 3.2. Coalescence 3.3. Translucency of the thin film on glass substrate 4. Discussion 5 4.1. Zirconia phase specification 4.2. Energetics 5. Cnclusions 10 Figures 11 Part 2 Zirconium and zirconia thin films prepared on NaCl by ion beam deposition 1. Introduction 22 2. Experimental 23 3. Results 24 3.1. Phase identities 3.2. Lattice image of the condensates in coalescence 3.3. Preferred orientation of Zr and ZrO2 coating on glass substrate 3.4. Color of zirconia coating 4. Discussion 27 4.1. Condensation and oxidation of Zr film 4.2. Stabilization of c- and t-ZrO2 4.3. Preferred orientation 4.4. Brownian rotation of condensates 5. Conclusions .32 Figures 33 Part 3 The oriented growth of zirconia thin films on NaCl (001) surface 1. Introduction 44 2. Experimental 45 3. Results 46 3.1 SAED pattern 3.2 High resolution image 3.3 Lattice image of the condensates in coalescence 4. Discussion 49 4.1 Orientation relationship 4.2 Rotation and coalescence 4.3 Stabilization of c- and t-ZrO2 5. Conclusions 54 Figures 55 Part 4 Special interfaces of ZrO2 nano-crystals constrained by NaCl (001) plane: implication for epitaxial nanocrystalline materials 1. Introduction. 67 2. Experimental 68 3. Results 69 3.1 A/B interface 3.2 B1/B2 interface 4. Discussion 70 4.1 {220}/{200} Interface 4.2 {200}/{111} interface 5. Conclusions 74 Figures 75 Reference 83 |
參考文獻 References |
Bansal G.K., Heuer A.H., J. Am. Ceram. Soc. 58 (1975) 235. Chen I.M., Yeh S.W., Chiou S.Y., Gan D., Shen P., Thin Solid Films, 491 (2005) 339. Chen I.W., Chiao Y.H., in: Heuer A.H., Hobbs L.W. (Eds.), Science and Technology of Zirconia in Advances in Ceramics, Vol. 12, American Ceramic Society, Columbus, OH, 1984, p.33. Chen I.W., Chiao Y.H., Acta Metall. 31 (1983) 1627. Chiao Y.H., Chen I.W., Acta Metall. Mater. 38 (1990) 1163. Christensen A. and Carter E.A, Phys. Rev. B 58 (12) (1998) 8050. Claussen N., in: Claussen N., Rühle M., Heuer A.H. (Eds.), Science and Technology of Zirconia, II, Advances in Ceramics, Vol. 12, The American Ceramic Society, Columbus, Ohio, 1984, 325. Egami B. and Ogura A., Apply. Phys. Lett 47 (1985) 1059. El-Shanshoury I.A., Rudenko V.A., Ibrahim I.A., J. Am. Ceram. Soc. 53 (1970) 264. Fabris S., Paxton A. T., Finnis M. W., Acta Mater. 50 (2002) 5171. Friedlander S.K., Jang H.D., Ryu K.H., Apply. Phys. Lett. 72 (1998) 173. Garvie R.C., Hannink R.H.J., Pascoe R.T., Nature 258 (1975) 703. Garvie R.C., J. Phys. Chem. 69 (1965) 1239. Givargizov E.I., Oriented crystallization on amorphous substrate, Plenum Press, New York, 1991. Green D.J., Hannink R.H.J., Swain M.V., Transformation toughening of ceramics, CRC Press, Inc. 1989, pp. 1-232. Guinebretiere R., Soulestin B., Dauger A., Thin Solid Films, 319 (1998) 197. Gupta T.K., Bechtold J.H., Kuznicki R.C., Cadoff L.H., Rossing B.R., J. Mater. Sci. 12 (1977) 2421. Hansen K.H., Ferrero S., Henry C.R., Applied Surface Science 226 (2004) 167. Harada T., Ohkoshi H., Journal of Crystal Growth 173 (1997) 109 Harding J.H. Stoneham A.M., Venables J.A., Physical Review B, 57 (11) (1998) 6715. Henry C.R., Meunier M., Mater. Sci. Eng. A217 (73) (1990) 239. Henley S.J., Ashfold M.N.R., Cherns D., Thin Solid Films, 422 (2002) 67 Hwang S.L., Chen I.W., J. Am. Ceram. Soc. 73 (1990) 3269. James M.A., HIbma T., Surface Science, 433-435 (1999) 718. Kuo L.Y., Shen P., Surface Science, 373 (1997) L350-L356. Kuo L.Y., Shen P., Mater. Science and Eng. (A). 277 (2000) 258. Kuo L.Y., Shen P., Mater. Sci. Eng (A). 276 (2000) 99. Kado T., Thin Solid Films, 459 (2004) 187. Kato M., Jpn. J. Apply. Phys. Part 1, 15 (1976) 757. Kern R., Masson A., Métois J.J., Surface Sci. 27 (1971) 483. Lee W.H., Shen P., J. Crystal Growth 205 (1999) 169. Lucchese R.R., Marlow W.H., in: P.J. Reynolds (ed.) On clusters and clustering - from atoms to fractals, North-Holland, Amsterdam, 1993, 143. Masson A., Métois J.J., Kern R., Surface Science 27 (1971) 463. Masek K., Matolin V., Thin Solid Films 286 (1996) 330. Masek K., Moroz V., Nemsak S., Matolin V., Journal of Electron Spectroscopy and Phenomena, 137-140 (2004) 113. Métois J.J., Gauch M., Masson A., Kern R., Surface Sci. 30 (1972) 43. Métois J.J., Surface Science 36 (1973) 269. Nilsen O., Foss S., Fjellvag H., Kjekshus A., Thin Solid Films, 468 (2004) 65. Okmura Y., Miyazaki T., Taniuchi Y., Sasaki Y.C., Thin Solid Films 471 (2005) 91. Padture N. P., Gell M. and Jordon E. H., Acta Mater. 49 (2001) 2551. Padture N. P., Gell M. and Jordon E. H., Science 296 (2002) 280. Penn R.L., Banfield J.F., Science 281 (1998) 969. Penn R.L., Banfield J.F., Am. Mineral. 83 (1998) 1077. Rata A.D., Chezan A.R., Presura C., Hibma T., Surface Science, 532-535 (2003) 341. Reniers F., Delplancke M.P., Asskali A., Rooryck V., Sinay O. V., Applied Surface Science, 92 (1996) 35. Rühle M., Bischoff E., Claussen N., in: Aaronson H.I., Laughlin D.E., Sekerka R.F., Wayman C.M. (Eds.), Solid-Solid Phase Transformations, Metallurgical Society of AIME, warrendale, PA, 1982, p. 1563, and references cited therein. Ruh R., Garrett H.J., J. Am. Ceram. Soc. 50 (1967) 257. Sears G. W. and Hudson J.B, J. Chem. Phys. 39 (1963) 2380. Shannon R. D., Acta Cryst. A32 (1976) 751. Shen P., Lee W.H., Nano Lett. 1(12) (2001) 707. Shibata N., Yamamoto T., Ikuhara Y. and Sakuma T., “Structure of [110] tilt grain boundaries in zirconia bicrystals,” J Electron Microsc (Tokyo). 50(6) 2001, 429-433. Shibata N., Oba F., Yamamoto T., Ikuhara Y., “Systematic study of grain boundary atomistic structures and related properties in cubic zirconia bicrystals,” Metallkunde 02/2005, 177-185. Teufer G., Acta Crystall. 15 (1962) 1187. Thomas J.M. and Walker P.L, J. Chem. Phys. 41 (1964) 587. Venables J.A., Harding J.H., Journal of Crystal Growth, 211 (2000) 27. Walton D., J. Chem. Phys. 37 (1962) 2182. Williams D.B., Practical Analytical Electron Microscopy in Materials Science, (Mahwah: Philips Electronic Instruments Inc., 1984). Yamada Y., Kasukabe Y., Yoshida K., Japanese Journal of Applied Physics, 29 (4) (1990) 706. Yeh S.W., Huang H.L., Gan D., Shen P., “The oriented growth of zirconia thin films on NaCl (001) surface,” J. Cryst. Growth, 289 (2006) 690 Zanghi J.C., Métois J.J., Kern R., Surface Sci. 52 (1975) 556. |
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