Journal of the Korean Ceramic Society (한국세라믹학회지)

The Korean Ceramic Society (한국세라믹학회)
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Microstructure Evolution and Dielectric Characteristics of CaCu3Ti4O12 Ceramics with Sn-Substitution

  • Kim, Cheong-Han (The Center of Green Materials Technology, Department of Materials Science and Engineering, Andong National University) ;
  • Oh, Kyung-Sik (The Center of Green Materials Technology, Department of Materials Science and Engineering, Andong National University) ;
  • Paek, Yeong-Kyeun (The Center of Green Materials Technology, Department of Materials Science and Engineering, Andong National University)
  • Received : 2012.11.13
  • Accepted : 2013.01.09
  • Published : 2013.01.31
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Abstract

The doping effect of Sn on the microstructure evolution and dielectric properties was studied in $CaCu_3Ti_{4-x}Sn_xO_{12}$ polycrystals. Samples were produced by a conventional solid-state reaction method. Sintering was carried out at $1115^{\circ}C$ for 2-16 h in air. The dielectric constant and loss were examined at room temperature over a frequency range between $10^2$ and $10^6$ Hz. The microstructure was found to evolve into three stages. Addition of $SnO_2$ led to an increase in density and advanced formation of abnormal grains. The formation of coarse grains with a reduced thickness of the boundary brought about an enhanced dielectric constant and a lower dielectric loss below ~1 kHz. EDS data showed the Cu-rich phase along the grain boundary, which should contribute to the improved dielectric constant according to the internal barrier layer capacitor model. After all, $SnO_2$ was an effective dopant to elevate the dielectric characteristics of $CaCu_3Ti_{4-x}Sn_xO_{12}$ polycrystals as a promoter for abnormal grain growth.

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References

  1. T. B. Adams, D. C. Sinclair, and A. R. West, "Influence of Processing Conditions on the Electrical Properties of $CaCu_{3}Ti_{4}O_{12}$ Ceramics," J. Am. Ceram. Soc., 89 [10] 3129-35 (2006). https://doi.org/10.1111/j.1551-2916.2006.01184.x
  2. S. H. Hong, D. Y. Kim, H. M. Park, and Y. M. Kim, "Electric and Dielectric Properties of Nb-Doped $CaCu_{3}Ti_{4}O_{12}$ Ceramics," J. Am. Ceram. Soc., 90 [7] 2118-21 (2007). https://doi.org/10.1111/j.1551-2916.2007.01709.x
  3. B. A. Bender and M. J. Pan, "The Effect of Processing on the Giant Dielectric Properties of $CaCu_{3}Ti_{4}O_{12}$," Mater. Sci. Eng. B, 117 339-47 (2005). https://doi.org/10.1016/j.mseb.2004.11.019
  4. W. Hao, J. Zhang, Y. Tan, and W. Su, "Giant Dielectric-Permittivity Phenomena of Compositionally and Structurally $CaCu_{3}Ti_{4}O_{12}$-Like Oxide Ceramics," J. Am. Ceram. Soc., 92 [12] 2937-43 (2009). https://doi.org/10.1111/j.1551-2916.2009.03298.x
  5. M. A. Rubia, P. L. J. Frutos, and J. F. Fernandez, "Effect of the Synthesis Route on the Microstructure and the Dielectric Behavior of $CaCu_{3}Ti_{4}O_{12}$ Ceramics," J. Am. Ceram. Soc., 95 [6] 1866-70 (2012). https://doi.org/10.1111/j.1551-2916.2012.05144.x
  6. J. J. Romero, P. Leret, F. Rubio-Marcos, A. Quesada, and J. F. Fernandez, "Evolution of the Intergranular Phase During Sintering of $CaCu_{3}Ti_{4}O_{12}$ Ceramics," J. Eur. Ceram. Soc., 30 737-42 (2010). https://doi.org/10.1016/j.jeurceramsoc.2009.08.024
  7. L. Wu, Y. Zhu, S. Park, S. Shapiro, G. Shirane, and J. Tafto, "Defect Structure of the High-Dielectric-Constant Perovskite $CaCu_{3}Ti_{4}O_{12}$," Physical Review B, 71 014118(2005). https://doi.org/10.1103/PhysRevB.71.014118
  8. D. C. Sinclair, T. B. Adams, F. D. Morrison, and A. R. West, "$CaCu_{3}Ti_{4}O_{12}$ : One-step Internal Barrier Layer Capacitor," Appl. Phys. Lett., 80 [12] 2153-5 (2002). https://doi.org/10.1063/1.1463211
  9. G. Chiodelli, V. Massarotti, D. Capsoni, M. Bini, C. B. Azzoni, M. C. Mozzati, and P. Lupotto, "Electric and Dielectric Properties of Pure and Doped $CaCu_{3}Ti_{4}O_{12}$ Perovskite Materials," Solid State Communications, 132 241-6 (2004). https://doi.org/10.1016/j.ssc.2004.07.058
  10. S. Y. Chung, S. Y. Choi, T. Yamamoto, Y. Ikuhara, and S. J. L. Kang, "Site-Selectivity of 3d Metal Cation Dopants and Dielectric Response in Calcium Copper Titanate," Appl. Phys. Lett., 88 091917 (2006). https://doi.org/10.1063/1.2179110
  11. J. W. Choi, J. Y. Ha, S. J. Yoon, H. J. Kim, and K. H. Yoon, "Microwave Dielectric Characteristics of $0.75(Al_{1/2}Ta_{1/2})O_{2}-0.25(Ti_{1-x}Sn_{x})O_{2}$Ceramics," J. Eur. Ceram. Soc., 23 2507-10 (2003). https://doi.org/10.1016/S0955-2219(03)00170-5
  12. L. Ni, X. M. Chen, and X. Q. Liu, "Structure and Modified Giant Dielectric Response in $CaCu_{3}(Ti_{1-x}Sn_{x})_{4}O_{12}$ Ceramics," Mater.Chem. Phys., 124 982-6 (2010). https://doi.org/10.1016/j.matchemphys.2010.08.010
  13. W. C. Ribeiro, R. G. C. Araujo, and P. R. Bueno, "The Dielectric Suppress and the Control of Semiconductor Non-Ohmic Feature of $CaCu_{3}Ti_{4}O_{12}$ by Means of Tin Doping," Appl. Phys. Lett., 98 132906 (2011). https://doi.org/10.1063/1.3574016
  14. L. Liu, Y. Huang, Y. Li, D. Shi, S. Zheng, S. Wu, L. Fang, and C. Hu, "Dielectric and Non-Ohmic Properties of $CaCu_{3}Ti_{4}O_{12}$ Ceramics Modified with NiO, $SnO_{2}$, $SiO_{2}$, and $Al_{2}O_{3}$ Additives, " J. Mater. Sci., 47 2294-9 (2012). https://doi.org/10.1007/s10853-011-6043-1
  15. P. R. Rios, T. Yamamoto, T. Kondo, and T. Sakuma, "Abnormal Grain Growth Kinetics of $BaTiO_{3}$ with an Excess $TiO_{2}$," Acta Mater., 46 [5] 1617-23 (1998). https://doi.org/10.1016/S1359-6454(97)00340-6
  16. M. F. Yan, "Microstructural Control in the Processing of Electronic Ceramics," Mater. Sci. Eng., 48 53-72 (1981). https://doi.org/10.1016/0025-5416(81)90066-5
  17. Y. K. Cho, S. J. L. Kang, and D. Y. Yoon, "Dependence of Grain Growth and Grain-Boundary Structure on the Ba/Ti Ratio in $BaTiO_{3}$," J. Am. Ceram. Soc., 87 [1] 119-24 (2004). https://doi.org/10.1111/j.1551-2916.2004.00119.x
  18. M. Baurer, S. J. Shin, C. Bishop, M. P. Harmer, D. Cockayne, and M. J. Hoffmann, "Abnormal Grain Growth in Undoped Strontium and Barium Titanate," Acta Mater., 58 290-300 (1997).
  19. Y. S. Yoo, H. Kim, and D. Y. Kim, "Effect of $SiO_{2}$ and $TiO_{2}$ Addition on the Exaggerated Grain Growth of $BaTiO_{3}$," J. Eur. Ceram. Soc., 17 [6] 805-11 (2003).
  20. D. E. Rase and R. Roy, "Phase Equilibria in the System $BaO-TiO_{2}$," J. Am. Ceram. Soc., 38 [3] 102 (1955)
  21. B. S. Prakash and K. B. R. Varma, "Influence of Sintering Conditions and Doping on the Dielectric Relaxation Originating from the Surface Layer Effects in $CaCu_{3}Ti_{4}O_{12}$ Ceramics," J. Phys. Chem. Solids, 68 490-502 (2007). https://doi.org/10.1016/j.jpcs.2007.01.006
  22. C. C. Calvert, W. M. Rainforth, D. C. Sinclair and A. R. West, "Characterisation of Grain Boundaries in $CaCu_{3}Ti_{4}O_{12}$ Using HRTEM, EDS and EELS," J. Phys.: Conference Series, 26 65-68 (2006). https://doi.org/10.1088/1742-6596/26/1/015
  23. T. T. Fang and H. K. Shiau, "Mechanism for Developing the Boundary Barrier Layers of $CaCu_{3}Ti_{4}O_{12}$," J. Am. Ceram. Soc., 87 [11] 2072-79 (2004).