Abstract
The fabrication of TiO2 modified CaCu3Ti4O12 (w = 0, 0.01, 0.1, 2%) ceramics were obtained by a sol–gel process. The influence of TiO2 amount on the microstructures and dielectric properties was studied. The results indicate that TiO2 modified CaCu3Ti4O12 ceramics exhibits higher density, more obvious grain boundaries, and larger grains, and show improved dielectric properties, including colossal permittivity (~ 104) and comparably low dielectric loss (~ 0.1–2.3) at room temperature over the frequency range from 100 Hz to 1 MHz. The colossal permittivity could be explained by an internal boundary layer capacitance effect. CaCu3Ti4O12 modified with w = 0.01% TiO2 shows improved dielectric constant (~ 6.81 × 104) and low dielectric loss (~ 0.12) at room temperature and 1 kHz, and it also exhibits good performance over a broad temperature from 20 to 200 °C. The results show that TiO2 modification can make an improvement in both microstructures and dielectric properties for CaCu3Ti4O12.
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References
G.L. Tan, H.H. Sheng, Multiferroic La0.2Pb0.7Fe12O19 ceramics: ferroelectricity, ferromagnetism and colossal magneto-capacitance effect. Data Brief 10, 69–74 (2017). doi:10.1016/j.dib.2016.11.067
G.L. Song, Y.C. Song, J. Su, X.H. Song, N. Zhang, T.X. Wang, F.G. Chang, Crystal structure refinement, ferroelectric and ferromagnetic properties of Ho3+ modified BiFeO3 multiferroic material. J. Alloys Compd. 696, 503–509 (2017). doi:10.1016/j.jallcom.2016.11.155
S. Lather, A. Gupta, J. Dalal, V. Verma, R. Tripathi, A. Ohlan, Effect of mechanical milling on structural, dielectric and magnetic properties of BaTiO3–Ni0.5Co0.5Fe2O4 multiferroic nanocomposites. Ceram. Int. 43(3), 3246–3251 (2017). doi:10.1016/j.ceramint.2016.11.152
P. Liu, Y. Lai, Y. Zeng, S. Wu, Z. Huang, J. Han, Influence of sintering conditions on microstructure and electrical properties of CaCu3Ti4O12 (CCTO) ceramics. J. Alloys Compd. 650, 59–64 (2015). doi:10.1016/j.jallcom.2015.07.247
L.M. Jesus, J.C.A. Santos, D.V. Sampaio, L.B. Barbosa, R.S. Silva, J.C. M’Peko, Polymeric synthesis and conventional versus laser sintering of CaCu3Ti4O12 electroceramics: (micro)structures, phase development and dielectric properties. J. Alloys Compd. 654, 482–490 (2016). doi:10.1016/j.jallcom.2015.09.027
T. Li, H.F. He, T. Zhang, B. Zhao, Z.Q. Chen, H.Y. Dai, R.Z. Xue, Z.P. Chen, Effect of synthesizing temperatures on the microstructure and electrical property of CaCu3Ti4O12 ceramics prepared by sol-gel process. J. Alloys Compd. 684, 315–321 (2016). doi:10.1016/j.jallcom.2016.05.177
J.Q. Wang, X. Huang, X.H. Zheng, D.P. Tang, Structure and electric properties of CaCu3Ti4O12 ceramics prepared by rapid sintering. J. Mater. Sci.: Mater. Electron. 27(2), 1345–1349 (2015). doi:10.1007/s10854-015-3895-1
M. Xiao, H. Huang, Effects of temperature and Ti-nonstoichiometry on electric properties of CaCu3Ti4O12 thin films. J. Mater. Sci.: Mater. Electron. 27(12), 12550–12556 (2016). doi:10.1007/s10854-016-5806-5
J. Zhao, J. Liu, G. Ma, Preparation, characterization and dielectric properties of CaCu3Ti4O12 ceramics. Ceram. Int. 38(2), 1221–1225 (2012). doi:10.1016/j.ceramint.2011.08.052
L. Sun, Z. Wang, Y. Shi, E. Cao, Y. Zhang, H. Peng, L. Ju, Sol–gel synthesized pure CaCu3Ti4O12 with very low dielectric loss and high dielectric constant. Ceram. Int. 41(10), 13486–13492 (2015). doi:10.1016/j.ceramint.2015.07.140
R. Kumar, M. Zulfequar, T.D. Senguttuvan, Structural and impedance spectroscopic studies of spark plasma sintered CaCu3Ti4O12 dielectric ceramics: an evidence of internal resistive barrier effect. J. Mater. Sci.: Mater. Electron. 27(5), 5233–5237 (2016). doi:10.1007/s10854-016-4418-4
Z. Liu, G. Jiao, X. Chao, Z. Yang, Preparation, microstructure, and improved dielectric and nonlinear electrical properties of Na1/2La1/2Cu3Ti4O12 ceramics by sol–gel method. Mater. Res. Bull. 48(11), 4877–4883 (2013). doi:10.1016/j.materresbull.2013.06.056
D. Xu, K. He, B. Chen, C. Xu, S. Mu, L. Jiao, X. Sun, Y. Yang, Microstructure and electric characteristics of AETiO3 (AE = Mg, Ca, Sr) doped CaCu3Ti4O12 thin films prepared by the sol–gel method. Prog. Nat. Sci.: Mater. Int. 25(5), 399–404 (2015). doi:10.1016/j.pnsc.2015.09.015
C. Wang, W. Ni, D. Zhang, X. Sun, J. Wang, H. Li, N. Zhang, Dielectric properties of pure and Mn-doped CaCu3Ti4O12 ceramics over a wide temperature range. J. Electroceram. 36(1–4), 46–57 (2016). doi:10.1007/s10832-016-0024-3
A.K. Thomas, K. Abraham, J. Thomas, K.V. Saban, Structural and dielectric properties of A- and B-sites doped CaCu3Ti4O12 ceramics. Ceram. Int. 41(8), 10250–10255 (2015). doi:10.1016/j.ceramint.2015.04.138
L. Sun, Z. Wang, W. Hao, E. Cao, Y. Zhang, H. Peng, Influence of Zirconium doping on microstructure and dielectric properties of CaCu3Ti4O12 synthesized by the sol–gel method. J. Alloys Compd. 651, 283–289 (2015). doi:10.1016/j.jallcom.2015.08.111
X. Ouyang, M. Habib, P. Cao, S. Wei, Z. Huang, W. Zhang, W. Gao, Enhanced extrinsic dielectric response of TiO2 modified CaCu3Ti4O12 ceramics. Ceram. Int. 41(10), 13447–13454 (2015). doi:10.1016/j.ceramint.2015.07.133
Y.-H. Lin, J. Cai, M. Li, C.-W. Nan, J. He, High dielectric and nonlinear electrical behaviors in TiO2-modified CaCu3Ti4O12 ceramics. Appl. Phys. Lett. 88(17), 172902 (2006). doi:10.1063/1.2198479
H. Yu, H. Liu, H. Hao, D. Luo, M. Cao, Dielectric properties of CaCu3Ti4O12 ceramics modified by SrTiO3. Mater. Lett. 62(8–9), 1353–1355 (2008). doi:10.1016/j.matlet.2007.08.052
X.W. Wang, P.B. Jia, X.E. Wang, B.H. Zhang, L.Y. Sun, Q.B. Liu, Calcining temperature dependence on structure and dielectric properties of CaCu3Ti4O12 ceramics. J. Mater. Sci.: Mater. Electron. 27(11), 12134–12140 (2016). doi:10.1007/s10854-016-5366-8
A. Nautiyal, C. Autret, C. Honstettre, S. De Almeida-Didry, M. El Amrani, S. Roger, B. Negulescu, A. Ruyter, Local analysis of the grain and grain boundary contributions to the bulk dielectric properties of Ca(Cu3–yMgy)Ti4O12 ceramics: importance of the potential barrier at the grain boundary. J. Eur. Ceram. Soc. 36(6), 1391–1398 (2016). doi:10.1016/j.jeurceramsoc.2015.12.035
M.M. Ahmad, Giant dielectric constant in CaCu3Ti4O12 nanoceramics. Appl. Phys. Lett. 102(23), 232908 (2013). doi:10.1063/1.4811154
T. Fang, L. Mei, H. Ho, Effects of Cu stoichiometry on the microstructures, barrier-layer structures, electrical conduction, dielectric responses, and stability of CaCu3Ti4O12. Acta Mater. 54(10), 2867–2875 (2006). doi:10.1016/j.actamat.2006.02.037
D.P. Singh, Y.N. Mohapatra, D.C. Agrawal, Dielectric and leakage current properties of sol–gel derived calcium copper titanate (CCTO) thin films and CCTO/ZrO2 multilayers. Mater. Sci. Eng. B 157(1–3), 58–65 (2009). doi:10.1016/j.mseb.2008.12.017
M. Nath, A. Roy, Interfacial and electrical properties of radio frequency sputtered ultra-thin TiO2 film for gate oxide applications. J. Mater. Sci.: Mater. Electron. 26(11), 9107–9116 (2015). doi:10.1007/s10854-015-3598-7
B.C. Luo, D.Y. Wang, M.M. Duan, S. Li, Growth and characterization of lead-free piezoelectric BaZr0.2Ti0.8O3–Ba0.7Ca0.3TiO3 thin films on Si substrates. Appl. Surf. Sci. 270, 377–381 (2013). doi:10.1016/j.apsusc.2013.01.033
L. Singh, U.S. Rai, K.D. Mandal, Dielectric, modulus and impedance spectroscopic studies of nanostructured CaCu2.70Mg0.30Ti4O12 electro-ceramic synthesized by modified sol–gel route. J. Alloys Compd. 555, 176–183 (2013). doi:10.1016/j.jallcom.2012.12.023
R. Schmidt, M.C. Stennett, N.C. Hyatt, J. Pokorny, J. Prado-Gonjal, M. Li, D.C. Sinclair, Effects of sintering temperature on the internal barrier layer capacitor (IBLC) structure in CaCu3Ti4O12 (CCTO) ceramics. J. Eur. Ceram. Soc. 32(12), 3313–3323 (2012). doi:10.1016/j.jeurceramsoc.2012.03.040
S.I.R. Costa, M. Li, J.R. Frade, D.C. Sinclair, Modulus spectroscopy of CaCu3Ti4O12 ceramics: clues to the internal barrier layer capacitance mechanism. RSC Adv. 3(19), 7030 (2013). doi:10.1039/c3ra40216a
Y. Li, P. Liang, X. Chao, Z. Yang, Preparation of CaCu3Ti4O12 ceramics with low dielectric loss and giant dielectric constant by the sol–gel technique. Ceram. Int. 39(7), 7879–7889 (2013). doi:10.1016/j.ceramint.2013.03.049
P. Liang, Z. Yang, X. Chao, Improved dielectric properties and grain boundary response in neodymium-doped Y2/3Cu3Ti4O12 ceramics. J. Alloys Compd. 678, 273–283 (2016). doi:10.1016/j.jallcom.2016.03.294
Acknowledgements
This work has been supported by the National Natural Science Foundation of China (Nos. 51402091, 51601059, 11304082 and 11404102), the scientific research foundation for newly graduated PhD students in Henan Normal University (No. 11114), and the National University Student Innovation Program.
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Wang, X.W., Jia, P.B., Sun, L.Y. et al. Improved dielectric properties in CaCu3Ti4O12 ceramics modified by TiO2 . J Mater Sci: Mater Electron 29, 2244–2250 (2018). https://doi.org/10.1007/s10854-017-8139-0
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DOI: https://doi.org/10.1007/s10854-017-8139-0