Abstract
CaCu3Ti4O12/CaTiO3/TiO2 (CCTO/CTO/TiO2) composite ceramics were fabricated by an in situ route and sintered at 1040 °C for 8 h. The micrographs of FESEM show that the ceramics are dense and delicate, with an average particle size of about 0.9–1.4 μm. XPS found the existence of Cu+ and Ti3+, which was caused by the charge compensation reaction derived from part of Ti4+ ions entering the V″Cu to form the donor \({{\rm {Ti}}^{\cdot\cdot}}_{\rm {Cu}}\). The impedance analysis shows that excessive CTO and TiO2 significantly reduce the grain boundary resistance of CCTO/CTO/TiO2 ceramics. Furthermore, it can be found that due to excessive CTO, TiO2 reacts with segregated CuO to form CCTO again and reduce the CuO concentration at the grain boundaries. Therefore, this significantly reduces the grain boundary width, resulting in a colossal dielectric constant of 9.0 × 105 at 30 Hz.
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References
P. Mao, J. Wang, P. Xiao, L. Zhang, F. Kang, H. Gong, Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics. Ceram. Int. 47, 111–120 (2021)
J.A. Cortés, H. Moreno, S. Orrego, V.D.N. Bezzon, M.A. Ramírez, Dielectric and non-ohmic analysis of Sr2+ influences on CaCu3Ti4O12-based ceramic composites, Materials Research Bulletin, 134 (2021)
P. Mao, J. Wang, S. Liu, L. Zhang, Y. Zhao, L. He, Grain size effect on the dielectric and non-ohmic properties of CaCu3Ti4O12 ceramics prepared by the sol-gel process. J. Alloy. Compd. 778, 625–632 (2019)
J. Zhao, J. Liu, G. Ma, Preparation, characterization and dielectric properties of CaCu3Ti4O12 ceramics. Ceram. Int. 38, 1221–1225 (2012)
L.F. Xu, K. Sun, X. Feng, H.B. Xiao, R.L. Wang, C.P. Yang, Abnormal capacitance–voltage behaviors of bismuth-doped CaCu3Ti4O12 ceramics. Int. J. Modern Phys. B, 31 (2017)
X.W. Wang, P.B. Jia, L.Y. Sun, B.H. Zhang, X.E. Wang, Y.C. Hu, J. Shang, Y.Y. Zhang, Improved dielectric properties in CaCu3Ti4O12 ceramics modified by TiO2. J. Mater. Sci.: Mater. Electron. 29, 2244–2250 (2017)
J. Zhao, H. Zhao, Z. Zhu, Influence of sintering conditions and CuO loss on dielectric properties of CaCu3Ti4O12 ceramics. Mater. Res. Bull. 113, 97–101 (2019)
J. Yang, M. Shen, L. Fang, The electrode/sample contact effects on the dielectric properties of the CaCu3Ti4O12 ceramic. Mater. Lett. 59, 3990–3993 (2005)
C.C. Calvert, W.M. Rainforth, D.C. Sinclair, A.R. West, EELS characterization of bulk CaCu3Ti4O12 ceramics. Micron 37, 412–419 (2006)
Z. Kafi, A. Kompany, H. Arabi, A. Khorsand Zak, The effect of cobalt-doping on microstructure and dielectric properties of CaCu3Ti4O12 ceramics. J. Alloys Compd. 727, 168–176 (2017)
S. Orrego, J.A. Cortés, R.A.C. Amoresi, A.Z. Simões, M.A. Ramírez, Photoluminescence behavior on Sr2+ modified CaCu3Ti4O12 based ceramics. Ceram. Int. 44, 10781–10789 (2018)
M.K. Pradhan, T.L. Rao, L. Karna, S. Dash, Giant dielectric response in (Sr, Sb) codoped CaCu3Ti4O12 ceramics: a novel approach (2018)
A. Skwarek, R.P. Socha, D. Szwagierczak, P. Zachariasz, Investigation of the microstructure and chemical composition of CaCu3Ti4O12 multilayer elements using SEM, EDS, and XPS. Acta Phys. Pol., A 134, 318–321 (2018)
L. Zhao, R. Xu, Y. Wei, X. Han, C. Zhai, Z. Zhang, X. Qi, B. Cui, J.L. Jones, Giant dielectric phenomenon of Ba0.5Sr0.5TiO3/CaCu3Ti4O12 multilayers due to interfacial polarization for capacitor applications. J. Eur. Ceramic Soc. 39, 1116–1121 (2019)
R. Djafar, K. Boumchedda, A. Chaouchi, D. Fasquelle, K. Sedda, S. Brahimi, K. Khalfaoui, M. Bououdina, CuO addition and sintering temperature dependence of structural, microstructural and dielectric properties of CaCu3Ti4O12 ceramics. Mater. Chem. Phys. 256 (2020)
H. Moreno, J.A. Cortés, F.M. Praxedes, S.M. Freitas, M.V.S. Rezende, A.Z. Simões, V.C. Teixeira, M.A. Ramirez, Tunable photoluminescence of CaCu3Ti4O12 based ceramics modified with tungsten. J. Alloys Compd. 850 (2021).
P. Fiorenza, R. Lo Nigro, A. Sciuto, P. Delugas, V. Raineri, R.G. Toro, M.R. Catalano, G. Malandrino, Perovskite CaCu3Ti4O12 thin films for capacitive applications: From the growth to the nanoscopic imaging of the permittivity. J. Appl. Phys. 105 (2009).
C. Mu, H. Zhang, Y. Liu, Y. Song, P. Liu, Rare earth doped CaCu3Ti4O12 electronic ceramics for high frequency applications. J. Rare Earths 28, 43–47 (2010)
J.-W. Lee, J.-H. Koh, Grain size effects on the dielectric properties of CaCu3Ti4O12 ceramics for supercapacitor applications. Ceram. Int. 41, 10442–10447 (2015)
D.S. Saidina, A. Norshamira, M. Mariatti, Dielectric and thermal properties of CCTO/epoxy composites for embedded capacitor applications: mixing and fabrication methods. J. Mater. Sci.: Mater. Electron. 26, 8118–8129 (2015)
S. Kaur, A. Kumar, A.L. Sharma, D.P. Singh, Dielectric and energy storage behavior of CaCu3Ti4O12 nanoparticles for capacitor application. Ceram. Int. 45, 7743–7747 (2019)
L. Zhang, F. Song, X. Lin, D. Wang, High-dielectric-permittivity silicone rubbers incorporated with polydopamine-modified ceramics and their potential application as dielectric elastomer generator. Mater. Chem. Phys. 241 (2020)
X. Yue, W. Long, J. Liu, S. Pandey, S. Zhong, L. Zhang, S. Du, D. Xu, Enhancement of dielectric and non-ohmic properties of graded Co doped CaCu3Ti4O12 thin films. J. Alloys Compd. 816 (2020)
G. Wu, Z. Yu, K. Sun, R. Guo, X. Jiang, C. Wu, Z. Lan, Effect of CaCu3Ti4O12 dopant on the magnetic and dielectric properties of high-frequency MnZn power ferrites. J. Magnet. Magnet. Mater. 513 (2020)
P. Mao, J. Wang, L. Zhang, Z. Wang, F. Kang, S. Liu, D.B.K. Lim, X. Wang, H. Gong, Significantly enhanced breakdown field with high grain boundary resistance and dielectric response in 0.1Na0.5Bi0.5TiO3–0.9BaTiO3 doped CaCu3Ti4O12 ceramics. J. Eur. Ceram. Soc. 40, 3011–3018 (2020)
M.M. Ahmad, Giant dielectric constant in CaCu3Ti4O12 nanoceramics. Appl. Phys. Lett. 102 (2013)
W.C. Ribeiro, E. Joanni, R. Savu, P.R. Bueno, Nanoscale effects and polaronic relaxation in CaCu3Ti4O12 compounds. Solid State Commun. 151, 173–176 (2011)
P.R. Bueno, R. Tararan, R. Parra, E. Joanni, M.A. Ramírez, W.C. Ribeiro, E. Longo, J.A. Varela, A polaronic stacking fault defect model for CaCu3Ti4O12material: an approach for the origin of the huge dielectric constant and semiconducting coexistent features. J. Phys. D Appl. Phys. 42 (2009)
C.C. Wang, L.W. Zhang, Surface-layer effect in CaCu3Ti4O12. Appl. Phys. Lett. 88 (2006)
D.C. Sinclair, T.B. Adams, F.D. Morrison, A.R. West, CaCu3Ti4O12: one-step internal barrier layer capacitor. Appl. Phys. Lett. 80, 2153–2155 (2002)
P. Lunkenheimer, R. Fichtl, S.G. Ebbinghaus, A. Loidl, Nonintrinsic origin of the colossal dielectric constants in CaCu3Ti4O12. Phys. Rev. B 70 (2004)
H. Lin, W. Xu, H. Zhang, C. Chen, Y. Zhou, Z. Yi, Origin of high dielectric performance in fine grain-sized CaCu3Ti4O12 materials. J. Eur. Ceram. Soc. 40, 1957–1966 (2020)
Y. Wang, L. Ni, X.M. Chen, Effects of Nd-substitution on microstructures and dielectric characteristics of CaCu3Ti4O12 ceramics. J. Mater. Sci.: Mater. Electron. 22, 345–350 (2010)
L. Ni, X.M. Chen, Enhanced giant dielectric response in Mg-substituted CaCu3Ti4O12 ceramics. Solid State Commun. 149, 379–383 (2009)
D. Xu, K. He, R. Yu, X. Sun, Y. Yang, H. Xu, H. Yuan, J. Ma, High dielectric permittivity and low dielectric loss in sol–gel derived Zn doped CaCu3Ti4O12 thin films. Mater. Chem. Phys. 153, 229–235 (2015)
Y. Su, W. Zhang, Dielectric properties and electrical conductivity of CaCu3Ti4O12 ceramics doped with Zr4+. J. Wuhan Univ. Technol-Mater. Sci. Ed. 28, 343–346 (2013)
M.F.A. Rahman, M.J. Abu, S.A. Karim, R.A. Zaman, M.F. Ain, Z.A. Ahmad, J.J. Mohamed, Microwave dielectric properties of CaCu3Ti4O12-Al2O3 composite (2016)
B. Ghosh, R.M. Tamayo Calderón, R. Espinoza-González, S.A. Hevia, Enhanced dielectric properties of PVDF/CaCu3Ti4O12: Ag composite films. Mater. Chem. Phys. 196, 302–309 (2017)
J. Wang, Y. Long, Y. Sun, X. Zhang, H. Yang, B. Lin, Fabrication and enhanced dielectric properties of polyimide matrix composites with core–shell structured CaCu3Ti4O12@TiO2 nanofibers. J. Mater. Sci.: Mater. Electron. 29, 7842–7850 (2018)
A. Rajabtabar-Darvishi, R. Bayati, O. Sheikhnejad-Bishe, L.D. Wang, W.L. Li, J. Sheng, W.D. Fei, Giant dielectric response and low dielectric loss in Al2O3 grafted CaCu3Ti4O12 ceramics. J. Appl. Phys. 117 (2015).
J. Li, R. Jia, L. Hou, L. Gao, K. Wu, S. Li, The dimensional effect of dielectric performance in CaCu3Ti4O12 ceramics: Role of grain boundary. J. Alloy. Compd. 644, 824–829 (2015)
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. Alloy. Compd. 650, 59–64 (2015)
M.J. Abu, J.J. Mohamed, M.F. Ain, Z.A. Ahmad, Phase structure, microstructure and broadband dielectric response of Cu nonstoichiometry CaCu3Ti4O12 ceramic. J. Alloy. Compd. 683, 579–589 (2016)
Acknowledgements
This work was supported by the Natural Science Foundation of China (51562037) and Yunnan University Graduate Research and Innovation Fund (2020Z41). The authors thank Advanced Analysis and Measurement Center of Yunnan University for the sample testing service.
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Guo, Y., Tan, J. & Zhao, J. Microstructure, morphology, and dielectric properties of in situ synthesized CCTO/CTO/TiO2 composite ceramics. J Mater Sci: Mater Electron 33, 1807–1816 (2022). https://doi.org/10.1007/s10854-021-07346-8
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DOI: https://doi.org/10.1007/s10854-021-07346-8