MOD法制备YBCO薄膜及工艺研究
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摘要
YBCO高温超导薄膜在军事、医学及电子等众多领域有非常广阔的应用前景，目前制备这种薄膜的主要方法有磁控溅射、激光脉冲沉积等。本论文旨在采用无氟MOD法制得具有钙钛矿结构的致密YBCO薄膜。以无机盐为初始原料研究了溶胶形成过程中的化学反应及成膜机理，探讨了LaALO_3基板上薄膜沉积技术等。进一步用X射线衍射仪和扫描电镜研究了薄膜结构、结晶情况和表面形貌，分析了衬底对YBCO薄膜制备的影响、以及不同热处理条件对薄膜结晶结构、形貌及性能的影响。研究结果如下：
(1)采用钇、钡、铜的无机盐Y_2O_3，BaCO_3，CuO作出发原料，络合剂采用聚乙烯醇缩丁醛树脂的丙酸溶液，可以制得成膜质量好的稳定溶胶。
(2)为探索采用MOD方法在LaAlO_3(001)单晶基片上制备性能良好的YBCO超导薄膜的最佳热处理条件，我们在分解热处理条件相同的情况下改变成相、渗氧热处理的温度，确定了薄膜制备的最佳热处理工艺。
(3)XRD测试表明由溶胶制成的YBCO薄膜形成了比较完全的YBa_2Cu_3O_(7-φ)超导相，分析表明YBCO具有良好c轴取向，同时杂相较少。
(4)SEM测试分析YBCO薄膜具有较好的表面形貌，但样品转变温度(Tc)较低。
YBCO high temperature superconductor film holds great promise for applications in military affairs, iatrology, electronic and so on. Presently the main methods of preparing YBCO films have magnetron sputtering and laser deposition. In this paper the dense YBCO films with perovskite structure were expected to be prepared by metal organic deposition (MOD) process. The confecting methods of sot were discussed using inorganic salt as precursors, and the FT IR was adopted to analyse the chemical reaction and film forming mechanism of stable sol. The techniques of preparing film buffer layers on LaALO_3 were studied. The SEM, TEM and XRD were adopted to study the crystal structure of films. The influences of substrate and heat treatment condition on the crystal structure and performance of the YBCO films were discussed. The results are listed as follows:
(1)The inorganic formate of Y, Ba and Cu was used as precursors, for example, Y_2O_3, BaCO_3 and CuO, and PVB of Propionate as complexed agents. The stable fluorine-free YBCO sol can be obtained.
(2)In order to search after the best temperature in which YBCO superconductor film can be prepared on the single crystal of LaAlO_3 by MOD method. We change the high temperature of heat treatment in the condition of the same decomposed temperature.
(3)The XRD testing show that the film of YBCO superconducting structure had been prepared. And it was indicated that YBCO is tropism of C axes. Few A axes tropism exist.
(4) The SEM testing show that the film of YBCO surface is very good, but the Tc is low.
(1)采用钇、钡、铜的无机盐Y_2O_3，BaCO_3，CuO作出发原料，络合剂采用聚乙烯醇缩丁醛树脂的丙酸溶液，可以制得成膜质量好的稳定溶胶。
(2)为探索采用MOD方法在LaAlO_3(001)单晶基片上制备性能良好的YBCO超导薄膜的最佳热处理条件，我们在分解热处理条件相同的情况下改变成相、渗氧热处理的温度，确定了薄膜制备的最佳热处理工艺。
(3)XRD测试表明由溶胶制成的YBCO薄膜形成了比较完全的YBa_2Cu_3O_(7-φ)超导相，分析表明YBCO具有良好c轴取向，同时杂相较少。
(4)SEM测试分析YBCO薄膜具有较好的表面形貌，但样品转变温度(Tc)较低。
YBCO high temperature superconductor film holds great promise for applications in military affairs, iatrology, electronic and so on. Presently the main methods of preparing YBCO films have magnetron sputtering and laser deposition. In this paper the dense YBCO films with perovskite structure were expected to be prepared by metal organic deposition (MOD) process. The confecting methods of sot were discussed using inorganic salt as precursors, and the FT IR was adopted to analyse the chemical reaction and film forming mechanism of stable sol. The techniques of preparing film buffer layers on LaALO_3 were studied. The SEM, TEM and XRD were adopted to study the crystal structure of films. The influences of substrate and heat treatment condition on the crystal structure and performance of the YBCO films were discussed. The results are listed as follows:
(1)The inorganic formate of Y, Ba and Cu was used as precursors, for example, Y_2O_3, BaCO_3 and CuO, and PVB of Propionate as complexed agents. The stable fluorine-free YBCO sol can be obtained.
(2)In order to search after the best temperature in which YBCO superconductor film can be prepared on the single crystal of LaAlO_3 by MOD method. We change the high temperature of heat treatment in the condition of the same decomposed temperature.
(3)The XRD testing show that the film of YBCO superconducting structure had been prepared. And it was indicated that YBCO is tropism of C axes. Few A axes tropism exist.
(4) The SEM testing show that the film of YBCO surface is very good, but the Tc is low.
引文
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[2] 张裕恒．超导物理．中国科技大学出版社，1997．
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[8] Putilin S.N.,Antipov E.V.,Chmaissem O.,et al., Nature 1993,362,226
[9] Wagener J.L.,Radaelli P.G.,Hinks D.G., et al.,Physica C 210, 1993, 447.
[10] Bertinotti A.,Viallet V., Colson D, et al., physica C 268, 1996, 257.
[11] Schilling A., Cantoni M., Guo J.D.,et al., Nature 363, 1993, 56.
[12] Sheng Z.Z., Hermann A. M., Ali A. E., et al., Phys. Rev. Lett. 60, 1988, 937.
[13] Sheng Z.Z., Hermann A.M., Nature 332,1988, 55.
[14] Subramanian M. A., Calabrese J.C., Toradi C.C., et al., Nature 332, 1988, 420.
[15] Torardi C.C., Subramanian M. A., Clabrese J.C., et al., Science 240,1988, 631.
[16] 梁敬魁．中国科学，A32，1989，32．
[17] Parkin S.S.P., Lee V.Y., Nazzal A.L., et al., Phys. Rev. lett. 61, 1988,750.
[18] Nakajima S., Kikuchi M., SyonoY., et al., Physica C 158, 1989, 471.
[19] Michel C., Hervieu M., Borel M.M., et al., Z. Phys. B 68, 1987, 421.
[20] Tarascon J.M., Mckinnon W.R., Barboux P., et al., Phys. Rev. B 38, 1988, 8885.
[21] Torardi C.C., Subramanian M.A., Calabrese J.C., et al., Phys. Rev. B38, 1988, 225.
[22] Subramanian M. A., Torardi C.C., Calabrese J.C., et al., Science 239, 1988, 1015.
[23] Maeda H., Tanaka Y., Fukutomi M., et al., Jpn. J. Appl. Phys. L. 27, 1988, 209.
[24] Bordet P., capponi J.J., Chaillout C., et al., Physica C 189, 1988, 156,
[25] 张其瑞．高温超导电性．杭州：浙江大学出版社，1992
[26] 李国桢、曹光丽等．高温超导薄膜的研制．红外技术．第11卷 第5期．1989：25-29
[27] Clandio Zuccaro, Michael winter, Norbert Klein, etal.,J. Appl. Phy. 82(11),l December 1997,5695
[28] K.A.Muller, W. Berlinger, etal.,Phys. Rev. Lett., 21(1968)814
[29] 徐如人、庞文琴等．无机合成与制备化学．北京：高等教育出版社，2001：560-570
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[31] J.Ramtrez-Castellanos, M. Yalllet-Regi,J.M.Gonzalez-Calbet, Solid State Ionics 172, 2004, 539.
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[34] Lee Hee, Gyoun C. G., et al., International Workshop on processing& Application of Superconductors, Gatlinburg Tennessee, USA, 2002.
[35] S.B. Abolmaali, J.B. Talbot, Journal of Electrochemiacial Society 140, 1993, 443.
[36] I. Van Driessche, B. Schoofs, E. Bruneel, et al., Journal of the European Ceramic Societu 24, 2004, 1823.
[37] N. El Hhokh, R. Papirnik, L. G. Huabert, et al., Journal of Materials Science Letters 8, 1989, 762.
[38] P. Catania, N. Hovnanian, L. Cot, et al., Mat. Res. Bull. 25, 1990,631.
[39] M. W. Rupich, Y. P. Liu, Ibechem, et al., Applied Physics Letters 60, 1992, 1384.
[40] 金曾孙．薄膜制备技术及其应用．出版日期：1989年12月第1版
[41] Takeshi Araki, Izumi Hirabayashi, Supercond. Sci. Technol. 16, 2003,71.
[42] Katsumi Suzuki, Takeshi Araki, Takaharu Konno, et al., Physica C 372-376, 2002, 623.
[43] Takeshi Araki, Toshiharu Niwa, Yutaka Yamada, et at., Journal of Applied Physics 92, 2002, 3318.
[44] K. Yamagiwa, J. Shibata, T. Hirayama, et al., PhysicaC 309, 1998, 231.
[45] K. Yamagiwa, I. Hirabayashi, Physica C 304, 1998, 12.
[46] G. Riss, B. Schlobach, K. Fisher, et at., Journal of the European Ceramic Society 19, 1999,125.
[47] (美)J．M．波特K．N．杜J．W．迈耶．薄膜的相互扩散和反应．出版日期：1983年11月第1版
[48] (日)麻莳立男．薄膜技术基础．出版日期：1988年03月第1版
[49] 杨邦朝．薄膜物理与技术．出版日期：1994年01月第1版
[50] 顾培夫．薄膜技术．出版日期：1990年11月第1版
[51] (日)金原粲．薄膜．出版日期：1988年04月第1版
[52] 薛增泉．薄膜物理．出版日期：1991年09月第1版
[53] 唐伟忠．薄膜材料制备原理、技术及应用．出版日期：1998年05月第1版
[54] 《化学工程手册》编辑委员会．薄膜过程．出版日期：1989年10月第1版
[55] 姚连增．晶体生长基础．出版日期：1995年12月第1版
[56] 张克从．晶体生长科学与技术 (上、下册)．出版日期：1997年07月第2版
[57] Y.-A. Jeea,*,M. li,B. Mab, V.A. Maroni, B.L. Fisher, U. Balachandran, Physica C 356 (2001) 297-303
[58] J H Sul, P P Joshi,V Chintamaneni and S M Mukhopadhyay, Supercond. Sci. Technol. 18 (2005) 1496-1501
[59] N.J. Lee a,*, T. Doi a, Y. nakuraku a, N. Kashima b, S. Nagaya b, Physica C 412- 414 (2004) 900-904
[60] G. Sipos, B. Utz, W. Schmidt, H.-W. Neumueller, P. Mueller, Physica C 341- 348 (2000) 1457.
[61] Y. Yamamoto a,*, M.Mukaida a,b, A. Ichinose b,c, K. Matsumoto b,d,Y. Yoshida a,e, S. Horii b,f, A. Saito a, S. Ohshima a, Physica C 412-414 (2004) 1316-1320
[62] Parmigiani F, Chiarello G, Ripamonti N, Goretzki H and Roll U, Phys. Rev. B 36 (1987) 7148
[63] Gupta A, Jagannathan R, Cooper E I, Giess E A, Landman J I and Hussey B W, Appl. Phys. Lett. 52 (1988)2077
[64] H. Yamasaki, Y. Nakagawa, K. Develos-Bagarinao, M. Murugesan, H. Obara, and Y. Mawatari, APPLIED PHYSICS LETTERS 86, 192507 (2005)
[65] Katsumi Suzuki *, Takeshi Araki, Takaharu Konno, Takeo Suzuki, Izumi Hirabayashi, Youichi Enomoto, Physica C 372- 376 (2002) 623-625
[66] Mcintyre P.C., Cima M.J., Ng M.F., J. Appl. Phys. 68, 1990, 84183.
[67] Araki T., Yamagiwa K., Suzuki K., et al., Supercond. Sci. Technol. 14, 2001, 21.
[68] Shi D.L., Y.L. Xu, Lian L.M.,et al., Superconductor Science &Technology 15, 2002,660.
[69] Shi D.L., Y.L. Xu, S.X. wang, et al., Physica C 371, 2002,97.
[70] Peir Yung Chu, Relva C.,Buchanan, et al., J. Mater. Res. 8, 1993,2134.
[71] Gupta A. , Jagannathan R., Cooper E.I., et al., Appl. Phys. Lett. 52, 1998, 2077.
[2] 张裕恒．超导物理．中国科技大学出版社，1997．
[3] Wu M.K., Ashburn J.R., Tirng C.J., et al., Phys. Rev. Lett., 58, 1987, 908.
[4] Zhao Z.X., Chen I., Yang Q., et al., Chin Sci Bull, 32, 1987, 661.
[5] Scott B.A., Suard E.Y., Tsuei C. C., et al., Physica 230, 1944239.
[6] Lourero S.M., Antipov E.V., Alexandre E. T., et al., Physica C 235, 1994, 905.
[7] Paranthaman M., Chakournakos B.C., J. Solid State Chem. 122, 1996, 221.
[8] Putilin S.N.,Antipov E.V.,Chmaissem O.,et al., Nature 1993,362,226
[9] Wagener J.L.,Radaelli P.G.,Hinks D.G., et al.,Physica C 210, 1993, 447.
[10] Bertinotti A.,Viallet V., Colson D, et al., physica C 268, 1996, 257.
[11] Schilling A., Cantoni M., Guo J.D.,et al., Nature 363, 1993, 56.
[12] Sheng Z.Z., Hermann A. M., Ali A. E., et al., Phys. Rev. Lett. 60, 1988, 937.
[13] Sheng Z.Z., Hermann A.M., Nature 332,1988, 55.
[14] Subramanian M. A., Calabrese J.C., Toradi C.C., et al., Nature 332, 1988, 420.
[15] Torardi C.C., Subramanian M. A., Clabrese J.C., et al., Science 240,1988, 631.
[16] 梁敬魁．中国科学，A32，1989，32．
[17] Parkin S.S.P., Lee V.Y., Nazzal A.L., et al., Phys. Rev. lett. 61, 1988,750.
[18] Nakajima S., Kikuchi M., SyonoY., et al., Physica C 158, 1989, 471.
[19] Michel C., Hervieu M., Borel M.M., et al., Z. Phys. B 68, 1987, 421.
[20] Tarascon J.M., Mckinnon W.R., Barboux P., et al., Phys. Rev. B 38, 1988, 8885.
[21] Torardi C.C., Subramanian M.A., Calabrese J.C., et al., Phys. Rev. B38, 1988, 225.
[22] Subramanian M. A., Torardi C.C., Calabrese J.C., et al., Science 239, 1988, 1015.
[23] Maeda H., Tanaka Y., Fukutomi M., et al., Jpn. J. Appl. Phys. L. 27, 1988, 209.
[24] Bordet P., capponi J.J., Chaillout C., et al., Physica C 189, 1988, 156,
[25] 张其瑞．高温超导电性．杭州：浙江大学出版社，1992
[26] 李国桢、曹光丽等．高温超导薄膜的研制．红外技术．第11卷 第5期．1989：25-29
[27] Clandio Zuccaro, Michael winter, Norbert Klein, etal.,J. Appl. Phy. 82(11),l December 1997,5695
[28] K.A.Muller, W. Berlinger, etal.,Phys. Rev. Lett., 21(1968)814
[29] 徐如人、庞文琴等．无机合成与制备化学．北京：高等教育出版社，2001：560-570
[30] T.Maeda, S.B. Kim, T. Suga, et al., IEEE Transaction on Applied Superconductivity 11, 2001, 2897.
[31] J.Ramtrez-Castellanos, M. Yalllet-Regi,J.M.Gonzalez-Calbet, Solid State Ionics 172, 2004, 539.
[32] R.H. Hammond, Proceedings of the 8th Intennational Symposium on Superconductvity, Iss 95.
[33] Yoshifumi Kumagai, utaka Yoshida, Morihiro Iwata, et al, Physica C 304, 1998,35.
[34] Lee Hee, Gyoun C. G., et al., International Workshop on processing& Application of Superconductors, Gatlinburg Tennessee, USA, 2002.
[35] S.B. Abolmaali, J.B. Talbot, Journal of Electrochemiacial Society 140, 1993, 443.
[36] I. Van Driessche, B. Schoofs, E. Bruneel, et al., Journal of the European Ceramic Societu 24, 2004, 1823.
[37] N. El Hhokh, R. Papirnik, L. G. Huabert, et al., Journal of Materials Science Letters 8, 1989, 762.
[38] P. Catania, N. Hovnanian, L. Cot, et al., Mat. Res. Bull. 25, 1990,631.
[39] M. W. Rupich, Y. P. Liu, Ibechem, et al., Applied Physics Letters 60, 1992, 1384.
[40] 金曾孙．薄膜制备技术及其应用．出版日期：1989年12月第1版
[41] Takeshi Araki, Izumi Hirabayashi, Supercond. Sci. Technol. 16, 2003,71.
[42] Katsumi Suzuki, Takeshi Araki, Takaharu Konno, et al., Physica C 372-376, 2002, 623.
[43] Takeshi Araki, Toshiharu Niwa, Yutaka Yamada, et at., Journal of Applied Physics 92, 2002, 3318.
[44] K. Yamagiwa, J. Shibata, T. Hirayama, et al., PhysicaC 309, 1998, 231.
[45] K. Yamagiwa, I. Hirabayashi, Physica C 304, 1998, 12.
[46] G. Riss, B. Schlobach, K. Fisher, et at., Journal of the European Ceramic Society 19, 1999,125.
[47] (美)J．M．波特K．N．杜J．W．迈耶．薄膜的相互扩散和反应．出版日期：1983年11月第1版
[48] (日)麻莳立男．薄膜技术基础．出版日期：1988年03月第1版
[49] 杨邦朝．薄膜物理与技术．出版日期：1994年01月第1版
[50] 顾培夫．薄膜技术．出版日期：1990年11月第1版
[51] (日)金原粲．薄膜．出版日期：1988年04月第1版
[52] 薛增泉．薄膜物理．出版日期：1991年09月第1版
[53] 唐伟忠．薄膜材料制备原理、技术及应用．出版日期：1998年05月第1版
[54] 《化学工程手册》编辑委员会．薄膜过程．出版日期：1989年10月第1版
[55] 姚连增．晶体生长基础．出版日期：1995年12月第1版
[56] 张克从．晶体生长科学与技术 (上、下册)．出版日期：1997年07月第2版
[57] Y.-A. Jeea,*,M. li,B. Mab, V.A. Maroni, B.L. Fisher, U. Balachandran, Physica C 356 (2001) 297-303
[58] J H Sul, P P Joshi,V Chintamaneni and S M Mukhopadhyay, Supercond. Sci. Technol. 18 (2005) 1496-1501
[59] N.J. Lee a,*, T. Doi a, Y. nakuraku a, N. Kashima b, S. Nagaya b, Physica C 412- 414 (2004) 900-904
[60] G. Sipos, B. Utz, W. Schmidt, H.-W. Neumueller, P. Mueller, Physica C 341- 348 (2000) 1457.
[61] Y. Yamamoto a,*, M.Mukaida a,b, A. Ichinose b,c, K. Matsumoto b,d,Y. Yoshida a,e, S. Horii b,f, A. Saito a, S. Ohshima a, Physica C 412-414 (2004) 1316-1320
[62] Parmigiani F, Chiarello G, Ripamonti N, Goretzki H and Roll U, Phys. Rev. B 36 (1987) 7148
[63] Gupta A, Jagannathan R, Cooper E I, Giess E A, Landman J I and Hussey B W, Appl. Phys. Lett. 52 (1988)2077
[64] H. Yamasaki, Y. Nakagawa, K. Develos-Bagarinao, M. Murugesan, H. Obara, and Y. Mawatari, APPLIED PHYSICS LETTERS 86, 192507 (2005)
[65] Katsumi Suzuki *, Takeshi Araki, Takaharu Konno, Takeo Suzuki, Izumi Hirabayashi, Youichi Enomoto, Physica C 372- 376 (2002) 623-625
[66] Mcintyre P.C., Cima M.J., Ng M.F., J. Appl. Phys. 68, 1990, 84183.
[67] Araki T., Yamagiwa K., Suzuki K., et al., Supercond. Sci. Technol. 14, 2001, 21.
[68] Shi D.L., Y.L. Xu, Lian L.M.,et al., Superconductor Science &Technology 15, 2002,660.
[69] Shi D.L., Y.L. Xu, S.X. wang, et al., Physica C 371, 2002,97.
[70] Peir Yung Chu, Relva C.,Buchanan, et al., J. Mater. Res. 8, 1993,2134.
[71] Gupta A. , Jagannathan R., Cooper E.I., et al., Appl. Phys. Lett. 52, 1998, 2077.