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High Permittivity and Dielectric Response of CaCu₃Ti_3.9(Y_0.5Nb_0.5)_0.1O₁₂ Ceramics

Y. Liu, X. Huang

School of Civil Engineering, Shaoguan University, Shaoguan 512005, China

received November 19, 2016, received in revised form January 9, 2017, accepted March 1, 2017

Vol. 8, No. 2, Pages 243-248   DOI: 10.4416/JCST2016-00112

Abstract

CaCu₃Ti_3.9(Y_0.5Nb_0.5)_0.1O₁₂ (CCTYNO) ceramics were prepared with the conventional solid-state method. Dielectric properties and electric responses at temperatures from - 80 to 200 °C were investigated in the frequency range of 100 – 1 MHz. A body-centered cubic structure was confirmed by means of X-ray diffraction. High dielectric permittivity (∼ 6000) and low dielectric loss (∼ 0.082) were observed at room temperature. Impedance spectroscopy measurements showed the resistance of the grain boundaries is higher by 2 – 3 orders of magnitude than that of the grains, indicating the different microstructure and electric property. The activation energy for the dc conduction process (0.593 eV) is comparable to that for the relaxation process (0.662 eV), implying that strong interfacial polarization at insulating grain boundaries may be responsible for the dielectric response of CCTYNO ceramic. Polyvalent cations (i.e. Cu⁺, Cu²⁺, Ti³⁺ and Ti⁴⁺) may cause changes in the conduction of semiconducting grains at high temperature.

Keywords

Dielectric properties, impedance, co-doping, grain boundary, interfacial polarization

References

¹ Subramanian, M.A., Li, D., Duan, N., Reisner, B.A., Sleight, A.W.: High dielectric constant in ACu₃Ti₄O₁₂ and ACu₃Ti₃FeO₁₂ phases, J. Solid State Chem., 151, 323 – 325, (2000).

² Subramanian, M.A., Sleight, A.W.: ACu₃Ti₄O₁₂ and ACu₃Ru₄O₁₂ perovskites: high dielectric constants and valence degeneracy, Solid State Sci., 4, 347 – 351, (2002).

³ Hutagalung, S.D., Ibrahim, M.I.M., Ahmad, Z.A.: Microwave assisted sintering of CaCu₃Ti₄O₁₂, Ceram. Int., 34, 939 – 942, (2008).

⁴ Adams, T.B., Sinclair, D.C., West, A.R.: Giant barrier layer capacitance effects in CaCu₃Ti₄O₁₂ ceramics, Adv. Mater., 14, 1321 – 1323, (2002).

⁵ Wu, Y.J., Su, S.H., Wu, S.Y., Chen, X.M.: Microstructures and dielectric properties of spark plasma sintered Ba_0.4Sr_0.6TiO₃/CaCu₃Ti₄O₁₂ composite ceramics, Ceram. Int., 37, 1979 – 1983, (2011).

⁶ Jumpatam, J., Putasaeng, B., Yamwong, T., Thongbai, P., Maensiri, S.: A novel route to greatly enhanced dielectric permittivity with reduce loss tangent in CaCu_3-xZn_xTi₄O₁₂/CaTiO₃ composites, J. Am. Ceram. Soc., 97, 2368 – 2371, (2014).

⁷ Ni, L., Chen, X.M.: Dielectric relaxations and formation mechanism of giant dielectric constant step in CaCu₃Ti₄O₁₂ ceramics, Appl. Phys. Lett., 91, 122905, (2007).

⁸ Fang, T.T., Mei, L.T.: Evidence of cu deficiency: A key point for the understanding of the mystery of the giant dielectric constant in CaCu₃Ti₄O₁₂, J. Am. Ceram. Soc., 90, 638 – 640, (2007).

⁹ Fang, T.T., Liu, C.P.: Evidence of the internal domains for inducing the anomalously high dielectric constant of CaCu₃Ti₄O₁₂, Chem. Mater., 17, 5167 – 5171, (2005).

¹⁰ Zheng, J.C., Frenkel, A.I., Wu, L., Hanson, J., Ku, W., Bozin, E.S., Billinge, S.J.L., Zhu, Y.: Nanoscale disorder and local electronic properties of CaCu₃Ti₄O₁₂: An integrated study of electron, neutron, and x-ray diffraction, x-ray absorption fine structure, and first-principles calculations, Phys. Rev. B, 81, 144203, (2010).

¹¹ Sinclair, D.C., Adams, T.B., Morrison, F.D., West, A.R.: CaCu₃Ti₄O₁₂: One-step internal barrier layer capacitor, Appl. Phys. Lett., 80, 2153 – 2155, (2002).

¹² Boonlakhorn, J., Putasaeng, B., Kidkhunthod, P., Thongbai, P.: Improved dielectric properties of (Y+ Mg) co-doped CaCu₃Ti₄O₁₂ ceramics by controlling geometric and intrinsic properties of grain boundaries, Mater. Design, 92, 494 – 498, (2016).

¹³ Ardakani, H.A., Alizadeh, M., Amini, R., Ghazanfari, M.R.: Dielectric properties of CaCu₃Ti₄O₁₂ improved by chromium/lanthanum co-doping, Ceram. Int., 38, 4217 – 4220, (2012).

¹⁴ Wen, A., Yuan, D., Zhu, X., Zhu, J., Xiao, D., Zhu, J.: Electrical and dielectric properties of Aluminum/Niobium Co-doped CaCu₃Ti₄O₁₂ ceramics, Ferroelectrics, 492, 1 – 9, (2016).

¹⁵ Liu, J., Duan, C.G., Yin, W.G., Mei, W.N., Smith, R.W., Hardy, J.R.: Large dielectric constant and Maxwell-Wagner relaxation in Bi_2/3Cu₃Ti₄O₁₂, Phys. Rev. B, 70, 144106, (2004).

¹⁶ Thongbai, P., Masingboon, C., Maensiri, S., Yamwong, T., Wongsaenma, S., Yimnirun, R.: Giant dielectric behaviour of CaCu₃Ti₄O₁₂ subjected to post-sintering annealing and uniaxial stress, J Phys.: Condens. Matter., 19, 236208, (2007).

¹⁷ Liu, P., He, Y., Zhou, J.P., Mu, C.H., Zhang, H.W.: Dielectric relaxation and giant dielectric constant of Nb-doped CaCu₃Ti₄O₁₂ ceramics under dc bias voltage, Phys. Status. Solidi. A, 206, 562 – 566, (2009).

¹⁸ Marchin, L., Guillemet-Fritsch, S., Durand, B., Levchenko, A.A., Navrotsky, A., Lebey, T.: Grain growth-controlled giant permittivity in soft chemistry CaCu₃Ti₄O₁₂ ceramics, J. Am. Ceram. Soc., 91, 485 – 489, (2008).

¹⁹ Krohns, S., Lunkenheimer, P., Kant, C., Pronin, A.V., Brom, H.B., Nugroho, A.A., Diantoro, M., Loidl, A.: Colossal dielectric constant up to GHz at room temperature, Appl. Phys. Lett., 94, 122903, (2009).

²⁰ Wu, Y., Miao, J., Liu, Z., Li, Y.: Colossal permittivity and dielectric relaxations in BaTi_0.99(Nb_0.5Ga_0.5)_0.02O₃ ceramics, Ceram. Int., 41, 846 – 850, (2015).

²¹ Liu, J., Duan, C.G., Mei, W.N., Smith, R.W., Hardy, J.R.: Dielectric properties and Maxwell-Wagner relaxation of compounds ACu₃Ti₄O₁₂ (A= Ca, Bi_2/3, Y_2/3, La_2/3), J. Appl. Phys., 98, 093703, (2005).

²² Zheng, Q., Fan, H., Long, C.: Microstructures and electrical responses of pure and chromium-doped CaCu₃Ti₄O₁₂ ceramics, J. Alloy. Compd., 511, 90 – 94, (2012).

²³ Zhang, L.: Electrode and grain-boundary effects on the conductivity of CaCu₃Ti₄O₁₂, Appl. Phys. Lett., 87, 022907, (2005).

²⁴ Liu, Y., Zhao, X.G.: Dielectric properties and impedance characteristics of BaO-Cr₂O₃-Sb₂O₅ ceramics, J. Mater. Sci. Mater. El., 26, 6712 – 6717, (2015).

²⁵ Lin, Y.H., Cai, J., Li, M., Nan, C.W., He, J.: Grain boundary behavior in varistor-capacitor TiO₂-rich CaCu₃Ti₄O₁₂ ceramics, J. Appl. Phys., 103, 074111, (2008).

²⁶ Li, W., Schwartz, R.W.: Ac conductivity relaxation processes in CaCu₃Ti₄O₁₂ ceramics: grain boundary and domain boundary effects, Appl. Phys. Lett., 89, 242906, (2006).

²⁷ León, C., Rivera, A., Várez, A., Sanz, J., Santamaria, J., Ngai, K.L.: Origin of constant loss in ionic conductors, Phys. Rev. Lett., 86, 1279 – 1282, (2001).

²⁸ Thongbai, P., Tangwancharoen, S., Yamwong, T., Maensiri, S.: Dielectric relaxation and dielectric response mechanism in (Li, Ti)-doped NiO ceramics, J. Phys.: Condens. Matter., 20, 395227, (2008).

²⁹ Kum-onsa, P., Thongbai, P., Putasaeng, B., Yamwong, T., Maensiri, S.: Na_1/3Ca_1/3Bi_1/3Cu₃Ti₄O₁₂: A new giant dielectric perovskite ceramic in ACu₃Ti₄O₁₂ compounds, J. Eur. Ceram. Soc., 35, 1441 – 1447, (2015).

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