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通过对克劳修斯-莫索蒂方程的近似, 分析了钙钛矿结构微波介质陶瓷频率温度系数 (τf) 的主要影响因素, 发现改变材料介电响应中离子位移极化和电子位移极化的比例, 可调节频率温度系数的正负与大小. 通过电子结构计算和容忍因子分析, 预测引入(Zn1/3Nb2/3)4+对具有正温度系数 的CaTiO3进行B位取代将提高材料电子极化响应比例, 调节τf由正变负. 采用偏铌酸盐为前驱体, 通过固相反应法合成了Ca[(Zn1/3Nb2/3)xTi(1-x)]O3钙钛矿结构陶瓷, 并对其进行结构分析和性能测试, 实验结果与理论分析一致, 获得了具有近零频率温度系数的Ca[(Zn1/3Nb2/3)0.7Ti0.3]O3介质陶瓷材料.The determinants of resonant frequency temperature coefficient (τf) have been analyzed by the approximate treatment of Clausius-Mossotti equation. It is suggested that the value of τf can be adjusted by changing the contribution proportion of ionic polarization or electronic polarization for the dielectric constant. Results of electronic structure calculation and tolerance factor analysis show that B-site substitution of CaTiO3 with (Zn1/3Nb2/3)4+ could turn the value of τf from positive to negative, by enhancing the covalency in the BO6 octahedron and improving the contribution proportion of electronic polarization. Ca[(Zn1/3Nb2/3)xTi(1-x)]O3 dielectric ceramics were prepared by solid-state reaction method with niobate as precursor. Results of structure analysis and property measurement conform to the theoretical analysis. The Ca[(Zn1/3Nb2/3)0.7Ti0.3]O3 dielectric ceramic with near-zero τf was obtained.
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Keywords:
- B-site complex perovskite ceramics /
- resonant frequency-temperature stability /
- polarization /
- BO6octahedron tilting
[1] Ying H, Zhang Q L, Wang J B, You Y, Huang W 2003 J. Chin. Ceram. Soc. 31 965 (in Chinese) [杨辉, 张启龙, 王家邦, 尤源, 黄伟 2003 硅酸盐学报 31 965]
[2] Zhu J H, Liang F, Wang X H, Lv W Z 2005 Electron. Compon. Mater. 24 32(in Chinese) [朱建华, 梁飞, 汪小红, 吕文中 2005 电子元件与材料 24 32]
[3] Reaney I M, Wise P, Ubic R, Breeze J, McN Alford N , Iddles D, Cannell D, Price T 2001 Philos. Mag. A 81 501
[4] Pashkin A, Kamba S, Berta M, Petzelt J, Csete de Györgyfalva G D C, Zheng H, Bagshaw H, Reaney I M 2005 J. Phys. D: Appl. Phys. 38 741
[5] Hirotaka O, Hidekazu T, Akinori K, Akinori F, Georgios Z 2005 J. Eur. Ceram. Soc. 25 2859
[6] Bosman A J, Havinga E E 1963 Phys. Rev. 129 1593
[7] Buttner R H, Maslen E N 1992 Acta Crystallogr. Sect. B: Struct. Sci. 48 644
[8] Liu D, Hou R Z, Xu X, Li X Q 2004 J. Am. Ceram. Soc. 87 2208
[9] Wang Z L, Kang Z C 2002 Functional and Smart Materials-Structure Evolution and Structure Analysis (Beijing: Science Press) p87 (in Chinese) [王中林, 康振川 2002 功能与智能材料结构演化与结构分析 (北京: 科学出版社) 第87页]
[10] Reaney I M, Colla E L, Setter N 1994 J. Appl. Phys. 33 3984
[11] Moreira R L, Dias A 2005 J. Eur. Ceram. Soc. 25 2843
[12] Shannon R D 1976 Acta Crystallogr. Sect. A: Found. Crystallogr. 32 751
[13] Jahn H A, Teller E 1937 Math. Phys. Sci. 161 220
[14] Shannon R D 1993 J. Appl. Phys. 73 348
[15] Hu M Z, Zhou D X, Jiang L S, Cai X Q, Huang J 2005 J. Inorg. Mater. 20 126 (in Chinese) [胡明哲, 周东祥, 姜胜林, 蔡雪卿, 黄静 2005 无机材料学报 20 126]
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[1] Ying H, Zhang Q L, Wang J B, You Y, Huang W 2003 J. Chin. Ceram. Soc. 31 965 (in Chinese) [杨辉, 张启龙, 王家邦, 尤源, 黄伟 2003 硅酸盐学报 31 965]
[2] Zhu J H, Liang F, Wang X H, Lv W Z 2005 Electron. Compon. Mater. 24 32(in Chinese) [朱建华, 梁飞, 汪小红, 吕文中 2005 电子元件与材料 24 32]
[3] Reaney I M, Wise P, Ubic R, Breeze J, McN Alford N , Iddles D, Cannell D, Price T 2001 Philos. Mag. A 81 501
[4] Pashkin A, Kamba S, Berta M, Petzelt J, Csete de Györgyfalva G D C, Zheng H, Bagshaw H, Reaney I M 2005 J. Phys. D: Appl. Phys. 38 741
[5] Hirotaka O, Hidekazu T, Akinori K, Akinori F, Georgios Z 2005 J. Eur. Ceram. Soc. 25 2859
[6] Bosman A J, Havinga E E 1963 Phys. Rev. 129 1593
[7] Buttner R H, Maslen E N 1992 Acta Crystallogr. Sect. B: Struct. Sci. 48 644
[8] Liu D, Hou R Z, Xu X, Li X Q 2004 J. Am. Ceram. Soc. 87 2208
[9] Wang Z L, Kang Z C 2002 Functional and Smart Materials-Structure Evolution and Structure Analysis (Beijing: Science Press) p87 (in Chinese) [王中林, 康振川 2002 功能与智能材料结构演化与结构分析 (北京: 科学出版社) 第87页]
[10] Reaney I M, Colla E L, Setter N 1994 J. Appl. Phys. 33 3984
[11] Moreira R L, Dias A 2005 J. Eur. Ceram. Soc. 25 2843
[12] Shannon R D 1976 Acta Crystallogr. Sect. A: Found. Crystallogr. 32 751
[13] Jahn H A, Teller E 1937 Math. Phys. Sci. 161 220
[14] Shannon R D 1993 J. Appl. Phys. 73 348
[15] Hu M Z, Zhou D X, Jiang L S, Cai X Q, Huang J 2005 J. Inorg. Mater. 20 126 (in Chinese) [胡明哲, 周东祥, 姜胜林, 蔡雪卿, 黄静 2005 无机材料学报 20 126]
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