臺灣博碩士論文加值系統

0.1~1.0% Mn 添加鈦酸鋇介電薄膜由磁控濺鍍法製備。

amorphous, as confirmed by XRD results, and started to crystallize at temperature of 600°C or above, depending the Mn content. The as-deposited films became generally refined as Mn content increased. Granular structures and clusters were seen in SEM micrographs of post-annealed films, and the clusters were larger and densed with increasing Mn contents. DSC results revealed that the activation energies for crystallization and cubic-to-hexagonal structure phase transformation are ~100 and ~500 kJ/mole, varying with the Mn content Effects of Mn have also been observed on film leakage current and dielectric constant.

Contents
Abstract……………………………………………………………………….. Ⅰ
Contents………………………………………………………………………. Ⅱ
List of Tables…………………………………………………………………. Ⅵ
List of Figures………………………………………………………………... Ⅶ
Chapter 1 Introduction……………………………………………………… 1
Chapter 2 Background……………………………………………..…….… 2
2-1 Crystal Structures…………………………………………………… 2
2-2-1 Crystal Structures of BaTiO3………………………………….. 2
2-1-2 Crystal Structures of Mn-doped BaTiO3…………………….. 3
2-2 Electrical Properties……..…..……………………………………... 9
2-2-1 Ferroelectricity…………………….…….…………………….. 10
2-2-2 Dielectric Properties…………………………….……………. 13
2-2-2-1 Dielectric Properties of BaTiO3………………………….. 13
2-2-2-2 Dielectric Properties of Mn-doped BaTiO3…………….. 17
2-2-3 Leakage Current………………………………………………. 17
2-2-4 Positive Temperature Coefficient of Resistance………….. 17
2-3 Recent Development of BaTiO3-base Thin Films………………. 26
2-3-1 Applications of BaTiO3 in DRAM……………………………. 26
2-3-2 Applications of BaTiO3 in MLCCs…………………………… 28
2-3-3 Application of BaTiO3 in Optical Waveguide Devices……. 30
2-4 Principle of PVD……………………………………………………. 30
2-4-1 Principle of Sputter Deposition……………………………… 31
2-4-2 Nucleation and Growth of Sputter-Deposited Films……… 34
Chapter 3 Experimental Procedure………………………………………. 37
3-1 Pre-Deposition Preparation……………………………………….. 37
3-1-1 Targets Preparation…………………………………………... 37
3-1-2 Substrates Preparation………………………………………. 37
3-2 Film Deposition…………………………………………………….. 42
3-3 Post-Deposition Heat Treatment………………………………… 45
3-4 Top Electrodes Preparation………………………………………. 45
3-5 Characterizations………………………………………………….. 45
3-5-1 Compositional Analyses……………………………………... 50
3-5-2 Crystal Structure Analyses………………………………….. 50
3-5-3 Microstructural Analyses…………………………………….. 50
3-5-4 Electrical Property Analyses………………………………… 50
Chapter 4 Results and Discussion………………………………………... 52
4-1 Characterizations of the Targets…………………………………. 52
4-1-1 Chemical Compositions……………………………………... 52
4-1-2 Crystal Structure……………………………………………… 52
4-1-3 Microsturcture…………………………………………………. 61
4-1-4 Physical Characterizations………………………………….. 65
4-2 Characterization of Films…………………………………………. 68
4-2-1 Chemical Compositions……………………………………… 68
4-2-2 Crystallography……………………………………………….. 68
4-2-3 Tetragonalities of Targets and Films……………………….. 80
4-2-4 Microstructures……………………………………………….. 85
4-2-5 Thermal Analyses…………………………………………….. 104
4-2-6 Deposition Rates……………………………………………… 122
4-2-6-1 Effect of Sputtering Time……………………………….. 122
4-2-6-2 Effect of Composition and Argon-Oxygen Atmosphere………………………………………………. 125
4-2-6-3 Effect of Substrate………………………………………. 131
4-2-7 Electrical Properties………………………………………….. 131
4-2-7-1 Leakage Current………………………………………… 132
4-2-7-2 Dielectric Constant……………………………………… 133
Chapter 5 Summary and Conclusions……………………………………. 139
Reference……………………………………………………………………. 141
Appendix……………………………………………………………………… 144

References
[1] von Hippel, A. R. In Dielectrics and Waves, New York, (1954)202.
[2] R.E. Jones, Jr., P. Zurcher, P. Chu, D.J. Taylor, Y.T. Lii, B. Jiang, P.D. Maniar, and S.J. Gillespie, Microelectronic Engineering, 29, (1995)3.
[3] N. Halder, D. Chattopadhyay, A. Das Sharma, D. Saha, A. Sen, H.S. Maiti, Materials Research Bulletin, 36, (2001) 905.
[4] Tamara Pencheva, Milen Nenkov, Vacuum , 58, (2000) 374.
[5] Holger Ihrig, J. Am. Ceram. Soc., 64, (1981)617.
[6] S. Urek and M. Drofenik, J. European Ceram. Soc., 19, (1999)931.
[7] T. Miki and A. Fujimoto, J. Appl. Phys., 83, (1998 ) 1592.
[8] H.T. Langhammer, T. Muller, A. Polity, K.-H. Felgner, H.-P. Abicht, Mater. Lett., 26, (1996) 205.
[9] H.T. Langhammer, T. Muller, K.-H. Felgner, H.-P. Abicht, Mater. Lett., 42, (2000) 21.
[10] H.T. Langhammer, T. Muller, K.-H. Felgner, H.-P. Abicht, J. Am. Ceram. Soc., 83, (2000) 605.
[11] Toshikatsr Miki, and Akira Fujimoto, J. Appl. Phys., 83, (1998)1592.
[12] B.Matthias, Science, 113, (1951)591.
[13] William D., Callister, Jr., Materials Science And Engineering , fifth edition, (1999).
[14] T.Yamamoto, K. Hayashi, Y. Ikuhara and T. Sakuma, Philosophical Magazine Letters, 79, (1999)327.
[15] S.M. Kornienko, I.P. Bykov, M.D. Glinchuk, and V.V. Laguta, Physics of the Solid State, 41, (1999)1688.
[16] Hiroshi Kishi, Noriyuki Kohzu, Yoshiaki Iguchi, Junichi Sugino, Makoto Kato, Hitoshi Ohsato, Takashi Okuda, J. Eruopean Ceram. Soc., 21, (2001)1643.
[17] S.G. Lee, Structure and Electric Properties of La-doped Barium Titanate Thin Films by Sputter Deposition, (2001).
[18] J.P. Chu, S.F. Wang, S.J. Lee, C.W. Chagn, J. Appl. Phys., 88, (2000)6086.
[19] R. Bö ttcher, C. Klimm, D. Michel, H.-C. Semmelhack, and G. Vo¨ lkel, PHYSICAL REVIEW B, 62, (2000)2085.
[20] R.S. Liu , C.H. Shen , J.G. Lin , J.M. Chen , R.G. Liu , C.Y. Huang, Journal of Inorganic Materials , (1999) 61.
[21] F.S. Shiau, T.T. Fang, C.J.M.S., 24, (1992)No.2.
[22] Seok Hyun Yoon, Hwan Kim, J. European Ceram. Soc., 22, (2002) 689 .
[23] Anthony R. West, Basic Solid State Chemistry, second edition, (1999).
[24] Tu Lee and Ilhan A. Aksay, Crystal Growth & Design, 0, (2001)1.
[25] Merz, W. J. Phys. Rev., 76, (1949)1221.
[26] Shirane, G., Jona, F., Pepinsky, R. Proc. IRE, 43, (1955)1738.
[27] Kay, H. F.,Vousden, P. Philos. Mag., 7, (1949) 1019.
[28] S.B. Desu, E.C. Subbarao,Ferroelectric , 37, (1981)665.
[29] Toshikatsu Miki, and Akira Fujimoto, J. Appl. Phys., 83 (3), (1998)1598.
[30] W. Heywang, Solid-State Electron., 3, (1961)51.
[31] W. Heywang, J. Am. Ceram. Soc., 17, (1964)484.
[32] W. Heywang, J. Mater. Sci., 6, (1971)1214.
[33] G. H. Jonker, Solid-State Electron., 7, (1964)895.
[34] M. Kuwabara, J. Am. Ceram. Soc., 64, (1981).
[35] G. V. Lewis, C. R. A. Catlow, and R. E. W. Casselton, J. Am. Ceram. Soc., 68, (1985)555.
[36] S. B. Desu and D. A. Payne, J. Am. Ceram. Soc., 73, (1990)3416.
[37] Sreenivas, K., Mansingh, A. and Sayer, M., J. Appl. Phys., 62, (1987)4475.
[38] Shintani, Y. and Tada, O., J. Appl. Phys., 41, (1970)2376.
[39] P.C. Fazan,V.K. Mathews, N. Sandler, G.Q. Lo, and D.L. Kwong, Intern. Electron Devices Meeting Techn. Digest, (1992)263.
[40] H. Watanabe, T. Tatsumi, S. Ohnishi, T. Hanada, I. Honma, and T. Kikkawa, Intern. Electron Devices Meeting Techn. Digest, (1992)259.
[41] S.C. Lee, Preparation and Characterization of Dielectric Barium Titanate films by Sputter Deposition, M.S. thesis, National Taiwan Ocean University, Keelung, (2000).
[42] Qi Li, Jianquan Qi, Yongli Wang, Zhilun Gui, Longtu Li, J. European Ceram. Soc., 21, (2001)2217.
[43] D.F.K. Hennings and B.S. Schreinemacher, J. European Ceram. Soc., 14, (1994) 463.
[44] H. Saito, H. Chazono, H. Kishi, and N. Yamaoka, Jan. J. Appl. Phys., 30, (1991)2307.
[45] J. M. Rigsbee, "Physical Vapor Deposition", in "Surface Modification Engineering", R. Kossowsky ed., CRC (1989)231.
[46] M. Ohring, "Materials Science of Thin Film", Academic Press, (1991).
[47] "Thin Film Processes", J. L. Vossen and W. Kern ed., Academic Press, California, (1978).
[48] Francois Batllo, Eric Duverger, Jean-Charles Jules, Jean-Claude Niepce, Bernard Jannot, Mario Maglione, Ferroelectrics, 109, (1990)113.
[49] K. Sreenivas, Abhai Mansingh, M. Sayer, J. Appl. Phys., 62, (1987)4475.
[50] C. A. T. Salama and E. Siciunas, Journal of Vacuum Science and Technology, 9, (1972)91.
[51] J. P. Chu and T. N. Lin, J. Appl. Phys., 85, (1999)6462.
[52] Tamara Pencheva, Milen Nenkov,Vacuum , 58, (1997) 43.
[53] Donald L. Smith, Thin-Film Deposition
[54] J. H. Kim, S. Hishita, Joural of Materials Science, 30, (1995)4645.
[55] M. T. Buscaglia, V. Buscaglia, M. Viviani, P. Nanni, M. Hanuskova, J. Eruopean Ceram. Soc., 20, (2000)1997.
[56] A. Ionue, C. Fan, A. Takiuchi, J. Non-crystalline Solids, (1999)724.
[57] C. Fan, C. Li, A.Inoue, J. Non-crystalline Solid, 270, (2000)28
[58] H.-Y. Tina et al., Materials Chemistry and Physics, 69, (2001)166.
[59] M. N. Wakamatsu, N. Takeuchi, G. C. Lai, S. Ishida, Yogyo Kyokaishi (Engl. Abstract), 95, (1987)1181.
[60] N. Takeuchi, S. Ishida, M. Wakamatsu, Kyoto Institute of Technology, 43, (1995)51.
[61] F. Ren, S. Ishida, S. Mineta, J. Ceram. Soc. Jpn., 102, (1994)106.
[62] H. E. Kissinger, Anal. Chem., 29, (1957)1702.