Abstract
CaCu3Ti4O12 (CCTO) ceramics have been widely demonstrated due to their high dielectric constant and are considered potential materials for capacitor applications. However, its high dielectric loss (tanδ), which is greater than 0.1, makes it unsuitable for a lot of uses. Generally, CCTO doped with Ni ions exhibits low nonlinear properties and a high tanδ. In this work, CaCu2.9Ni0.1Ti4O12 (with x = 0/0.1/0.2) ceramics were synthesized by a semi-wet route. Significantly, the CaCu2.8Ni0.2Ti4O12 (Ni02) ceramic revealed an enhancement in breakdown electric voltage (Eb≈ 4208 V/cm) and nonlinear coefficient (α ≈ 7.69) with a considerably decrease in dielectric loss (tanδ ≈ 0.017). The mean grain size for Ni02 ceramic decreased from 6.15 to 2.23 μm. Density increased at first from 91.05 to 92.88% and then decreased by 89.6% with grain size reduction. The decrease in its mean grain size was attributed to the incorporation of Ni ions into Ti sites, as explained by DRX, EDS, and Raman results. The band gap energy increased from 2.25 eV for undoped CCTO ceramic to 3.54 eV for Ni02 ceramic. Additionally, all the ceramic samples present a high dielectric constant (ε) in the range of 104–105. According to the complex impedance spectroscopy results, the electrically heterogeneous CCTO microstructure is responsible for the high dielectric response. Moreover, the enhancement of dielectric and electric properties is attributed to the grain boundary effect.
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References
H.S. Mohanty, S.K. Sharm, RaviKant, P.K. Kulriya, A. Kumar, R. Thomas, D.K. Pradhan, Enhanced functional properties of soft polymer–ceramic composites by swift heavy ion irradiation. Phys. Chem. Chem. Phys. 21(24629), 24642 (2019). https://doi.org/10.1039/C9CP04206G
H.S. Mohanty, Ravikant, A. Kumar, P.K. Kulriya, R. Thomas, D.K. Pradhan, Dielectric/ferroelectric properties of ferroelectric ceramic dispersed poly (vinylidene fluoride) with enhanced β-phase formation. Mater. Chem. Phys. 230, 221–230 (2019). https://doi.org/10.1016/j.matchemphys.2019.03.055
M.A. Subramanian, D. Li, N. Duan, B.A. Reisner, A.W. Sleight, High dielectric constant in ACu3Ti4O12 and ACu3Ti3FeO12 phases. J Solid State Chem. 151, 323–325 (2000). https://doi.org/10.1006/jssc.2000.8703
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). https://doi.org/10.1063/1.1463211
R. Yu, H. Xue, Z. Cao, L. Chen, Z. Xiong, Effect of oxygen sintering atmosphere on the electrical behavior of CCTO ceramics. J. Eur. Ceram. Soc. 32, 1245–1249 (2012). https://doi.org/10.1016/j.jeurceramsoc.2011.11.039
Z. Yang, L. Zhang, X. Chao, L. Xiong, J. Liu, High permittivity and low dielectric loss of the Ca1 – xSrxCu3Ti4O12 ceramics. J. Alloys Compd. 509, 8716–8719 (2011). https://doi.org/10.1016/j.jallcom.2011.06.039
B. Bochu, M.N. Deschizeaux, J.C. Joubert, A. Collomb, J. Chenavas, M. Marezio, Synthesis and characterization of a series of perovskite titanates isostructural with CaCu3(Mn4)O12. J Solid State Chem. 29, 291–298 (1979)
C.C. Homes, T. Vogt, S.M. Shapiro, S. Wakimoto, A.P. Ramirez, Optical response of high-dielectric-constant perovskite-related oxide. Science 293, 673–676 (2001). https://doi.org/10.1126/science.1061655
A.P. Litvinchuk, C.L. Chen, N. Kolev, V.N. Popov, V.G. Hadjiev, M.N. Lliev, R.P. Bontchev, A.J. Jacobson, Optical properties of high-dielectric-constant CaCu3Ti4O12 films. Phys. Status Solidi A 195, 453–458 (2003). https://doi.org/10.1002/pssa.200305930
T.T. Fang, H.K. Shiau, Mechanism for developing the boundary barrier layers of CaCu3Ti4O12. J. Am. Ceram. Soc. 87, 2072–2079 (2004). https://doi.org/10.1111/j.1151-2916.2004.tb06362.x
P. Lunkenheimer, V. Bobnar, A.V. Pronin, A.I. Ritus, A.A. Volkov, A. Loidi, Origin of apparent colossal dielectric constants. Phys. Rev. B 66, 052105 (2002). https://doi.org/10.1103/PhysRevB.66.052105
G. Chiodelli, V. Massarotti, D. Capsoni, M. Bini, C.B. Azzoni, M.C. Mozzati, P. Lupotto, Electric and dielectric properties of pure and doped CaCu3Ti4O12 perovskite materials. Solid State Commun. 132, 241–246 (2004). https://doi.org/10.1016/j.ssc.2004.07.058
D. Capsoni, M. Bini, V. Massarotti, G. Chiodelli, M.C. Mozzati, C.B. Azzoni, Role of doping and CuO segregation in improving the giant permittivity of CaCu3Ti4O12. J. Solid State Chem. 177, 4494–4500 (2004). https://doi.org/10.1016/j.jssc.2004.09.009
B.S. Prakash, K.B. Varma, The influence of the segregation of Cu-rich phase on the microstructural and impedance characteristics of CaCu3Ti4O12 ceramics. J. Mater. Sci. 42, 7467–7477 (2007). https://doi.org/10.1007/s10853-006-1251-9
D. Xu, K. He, R. Yu, L. Jiao, H. Yuan, X. Sun, G. Zhao, H. Xu, X. Cheng, Effect of AETiO (AE = Mg, Ca, Sr) doping on dielectric and varistor characteristics of CaCu3Ti4O12 ceramic prepared by the sol–gel process. J. Alloys Compd. 592, 220–225 (2014). https://doi.org/10.1016/j.jallcom.2013.12.264
T. Li, D. Liu, H. Dai, H. Xiang, Z. Chen, H. He, Z. Chen, Effect of defect on the nonlinear and dielectric property of ca(1–x)SrxCu3Ti4O12 ceramics synthesized by sol–gel process. J. Alloys Compd. 599, 145–149 (2014). https://doi.org/10.1016/j.jallcom.2014.02.076
L.F. Xu, P.B. Qi, S.S. Chen, R.L. Wang, C.P. Yang, Dielectric properties of bismuth doped CaCu3Ti4O12 ceramics. Mater. Sci. Eng. B 177, 494–498 (2012). https://doi.org/10.1016/j.mseb.2012.02.001
Z. Yang, Y. Zhang, G. You, K. Zhang, R. Xiong, J. Shil, Dielectric and electrical transport properties of the Fe3+-doped CaCu3Ti4O12. J. Mater. Sci. Technol. 28, 1145–1150 (2012). https://doi.org/10.1016/S1005-0302(12)60184-4
C.H. Zhang, K. Zhang, H.X. Xu, Q. Song, Y.T. Yang, R.H. Yu, D. Xu, X.N. Cheng, Microstructure and electrical properties of sol-gel derived Ni-doped CaCu3Ti4O12 ceramics. Trans. Nonferrous Met. Soc. China 22, 127–132 (2012). https://doi.org/10.1016/S1003-6326(12)61696-3
A.K. Rai, K.D. Mandala, D. Kumarb, O. Parkashb, Characterization of nickel doped CCTO: CaCu2.9Ni0.1Ti4O12 and CaCu3Ti3.9Ni0.1O12 synthesized by semi-wet route. J. Alloys Compd. 491, 507–512 (2010). https://doi.org/10.1016/j.jallcom.2009.10.247
T. Li, J. Chen, D. Liu, Z. Zhang, Z. Chen, Z. Li, X. Cao, B. Wang, Effect of NiO-doping on the microstructure and the dielectric properties of CaCu3Ti4O12 ceramics. Ceram. Int. 40, 9061–9067 (2014). https://doi.org/10.1016/j.ceramint.2014.01.119
S. Senda, S. Rhouma, E. Torkani, A. Megriche, C. Autret, Effect of nickel substitution on electrical and microstructural properties of CaCu3Ti4O12 ceramic. J. Alloys Compd. 698, 152–158 (2017). https://doi.org/10.1016/j.jallcom.2016.12.096
A.K. Rai, K.D. Mandala, D. Kumarb, O. Parkash, Dielectric properties of CaCu3Ti4 – xCoxO12 (x = 0.10, 0.20, and 0.30) synthesized by semi-wet route. Mat. Chem. Phys. 122, 217–223 (2010). https://doi.org/10.1016/j.matchemphys.2010.02.037
N.A. Zhuk, N.A. Sekushin, M.G. Krzhizhanovskaya, V.A. Belyy, R.I. Korolev, Electrical properties of Ni-doped CaCu3Ti4O12 ceramics. Solid State Ion 364, 115633 (2021). https://doi.org/10.1016/j.ssi.2021.115633
L. Sun, R. Zhang, Z. Wang, E. Cao, Y. Zhang, L. Ju, Microstructure, dielectric properties and impedance spectroscopy of Ni doped CaCu3Ti4O12 ceramics. RSC Adv. 6, 55984–55989 (2016). https://doi.org/10.1039/C6RA07726A
J. Boonlakhorn, B. Putasaeng, P. Thongbai, Origin of significantly enhanced dielectric response and nonlinear electrical behavior in Ni2+–doped CaCu3Ti4O12: influence of DC bias on electrical properties of grain boundary and associated giant dielectric properties. Ceram. Int. 45, 69446949 (2019). https://doi.org/10.1016/j.ceramint.2018.12.192
J. Wang, Z. Lu, T. Deng, C. Zhong, Z. Chen, Improved dielectric properties in a’-site nickel-doped CaCu3Ti4O12 ceramics. J. Am. Ceram. Soc. 100, 4021–4032 (2017). https://doi.org/10.1111/jace.14960
L. Liu, Y. Huang, Y. Li, D. Shi, S. Zheng, S. Wu, L. Fang, C. Hu, Dielectric and non-ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives. J. Mater. Sci.: Mater. Electron. 47, 2294–2299 (2012). https://doi.org/10.1007/s10853-011-6043-1
N.A. Zhuk, S.V. Nekipelov, V.N. Sivkov, B.A. Makeev, R.I. Korolev, V.A. Belyy, M.G. Krzhizhanovskaya, M.M. Ignatova, Magnetic susceptibility, XPS and NEXAFS spectroscopy of Ni-doped CaCu3Ti4O12 ceramics. Mater. Chem. Phys. 252, 123310 (2020). https://doi.org/10.1016/j.matchemphys.2020.123310
M. Amir, A. Baykal, S. Guner, M. Sertkol, H. Sozeri, M. Toprak, Synthesis and characterization of CoxZn12xAlFeO4 nanoparticles. J. Inorg. Organomet. Polym. 25, 747–754 (2015). https://doi.org/10.1007/s10904-014-0153-6
S.F. Bdewi, O.G. Abdullah, B.K. Aziz, A.A.R. Mutar, Synthesis, structural and optical characterization of MgO Nanocrystalline embedded in PVA Matrix. J. Inorg. Organomet. Polym. 26, 326–334 (2016). https://doi.org/10.1007/s10904-015-0321-3
A. Manikandan, E. Hema, M. Durka, M.A. Selvi, T. Alagesan, S.A. Ant, Mn2+ Doped NiS (MnxNi1–xS: x = 0.0, 0.3 and 0.5) nanocrystals: structural, morphological, opto-magnetic and Photocatalytic Properties. J. Inorg. Organomet. Polym. 25, 804–815 (2015). https://doi.org/10.1007/s10904-014-0163-4
S. Saleem, M.H. Jameel, A. Rehman, M.B. Tahir, M.I. Irshad, Z.Y. Jiang, R.Q. Malik, A.A. Hussain, A. Rehman, A.H. Jabbar, A.Y. Alzahrani, M.A. Salem, M.M. Hessien, Evaluation of structural, morphological, optical, and electrical properties of zinc oxide semiconductor nanoparticles with microwave plasma treatment for electronic device applications. J. Mater. Res. Technol. 19, 2126–2134 (2022). https://doi.org/10.1016/j.jmrt.2022.05.190
S. Saleem, M.H. Jameel, N. Akhtar, N. Nazir, A. Ali, A. Zaman, A. Rehman, S. Butt, F. Sultana, M. Mushtaq, J.H. Zeng, M. Amami, K. Althubeiti, Modification in structural, optical, morphological, and electrical properties of zinc oxide (ZnO) nanoparticles (NPs) by metal (Ni, Co) dopants for electronic device applications. Arab. J. Chem. 15, 103518 (2022). https://doi.org/10.1016/j.arabjc.2021.103518
V. Kumara, S. Pandeya, A. Kumara, M. Kumar Vermaa, S. Singha, V. Shankar Raia, D. Prajapatia, T. Dasb, A. Sharmac, C. Lal Prajapatd, A. Gangware, K.D. Mandala, Investigation of dielectric, magnetic and impedance spectroscopic properties of CaCu3 – XMnXTi4–XMnXO12 (X = 0.10) nano-ceramic synthesized through semi-wet route. J. Mater. Res. Technol. 9, 12936–12945 (2020). https://doi.org/10.1016/j.jmrt.2020.09.032
L. Singh, U.S. Rai, N.B. Singh, Y. Lee, D.K. Mahato, et al. Dielectric properties of CaCu3 – xMgxTi4O12 (x = 0.20 and 0.50) material synthesized by the semi-wet route for energy storage capacitor. Proc. SPIE Smart Biomedical and Physiological Sensor Technology XVI, Vol. 11020, (2019) https://doi.org/10.1117/12.2515634
S. Rhouma, A. Megriche, M.E. Amrani, S. Said, S. Roger, C. Autret-Lambert, Effect of Sr/Mg co-doping on the structural, dielectric, and electrical properties of CaCu3Ti4O12 ceramics. J. Mater. Sci.: Mater. Electron. 33, 4535–4549 (2022). https://doi.org/10.1007/s10854-021-07645-0
S. Rhouma, A. Megriche, M. El Amrani, S. Said, C. Autret-Lambert, Influence of SrTiO3 on microstructure and electrical properties of Ca0.9Sr0.1Cu2.9Mg0.1Ti4O12 ceramics. J. Mater. Sci.: Mater. Electron. 34, 700 (2023). https://doi.org/10.1007/s10854-023-10097-3
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, 13447–13454 (2015). https://doi.org/10.1016/j.ceramint.2015.07.133
S. Rhouma, S. Saîd, C. Autret, S. De Almeida-Didry, M. El Amrani, A. Megriche, Comparative studies of pure, Sr-doped, Ni-doped and co-doped CaCu3Ti4O12 ceramics: enhancement of dielectric properties. J Alloys Compd. 717, 121–126 (2017). https://doi.org/10.1016/j.jallcom.2017.05.053
M. Matos, L. Walmsley, Cation-oxygen interaction and oxygen stability in CaCu3Ti4O12 and CdCu3Ti4O12 lattices. J. Phys. Condens. Matter 18, 1793–1803 (2006). https://doi.org/10.1088/0953-8984/18/5/030
A. Zaafouri, M. Megdiche, M. Gargouri, Studies of electric, dielectric, and conduction mechanism by OLPT model of Li4P2O7. Ionics 21, 1867–1879 (2015). https://doi.org/10.1007/s11581-015-1365-7
P. Thongbai, C. Masingboon, S. Maensiri, T. Yamwong, S. Wongsaenmai, R. Yimnirun, Giant dielectric behaviour of CaCu3Ti4O12 subjected to post-sintering annealing and uniaxial stress. J Phys: Condens Matter 19, 236208 (2007). https://doi.org/10.1088/0953-8984/19/23/236208
P. Thongbai, J. Jumpatam, T. Yamwong, S. Maensiri, Effects of Ta5+ doping on microstructure evolution, dielectric properties and electrical response in CaCu3Ti4O12 ceramics. J. Eur. Ceram. Soc. 32, 2423–2430 (2012). https://doi.org/10.1016/j.jeurceramsoc.2012.02.048
T.B. Adams, D.C. Sinclair, A.R. West, Characterization of grain boundary impedances in fine-and coarse-grained CaCu3Ti4O12 ceramics. Phys. Rev. B: Condens. Matter Mater. Phys. 73, 094124 (2006). https://doi.org/10.1016/j.jeurceramsoc.2012.02.048
T. Li, Z. Chen, Y. Su, L. Su, J. Zhang, Effect of grain size and Cu-rich phase on the electric properties of CaCu3Ti4O12 ceramics. J. Mater. Sci. 44, 6149–6154 (2009). https://doi.org/10.1007/s10853-009-3850-8
R. Mauczok, R. Wernicke, Ceramic boundary-layer capacitors. Philips Tech. Rev. 41, 338–346 (1983)
L. Marchin, S. Guillemet-Fritsch, B. Durand, A.A. Levchenko, A. Navrotsky, T. Lebey, Grain growth-controlled giant permittivity in soft chemistry CaCu3Ti4O12 ceramics. J. Am. Ceram. Soc. 91, 485–489 (2008). https://doi.org/10.1111/j.1551-2916.2007.02174.x
S. DeAlmeida-Didry, C. Autret, A. Lucas, C. Honstettre, F. Pacreau, F. Gervais, Leading role of grain boundaries in colossal permittivity of doped and undoped CCTO. J. Eur. Ceram. Soc. 34, 3649–3654 (2014). https://doi.org/10.1016/j.jeurceramsoc.2014.06.009
J. Guo, L. Sun, Q. Ni, E. Cao, W. Hao, Y. Zhang, Y. Tian, L. Ju, Dielectric properties and nonlinear I–V electrical behavior of (Ni2+,Zr4+) co-doping CaCu3Ti4O12 ceramics. Appl. Phys. A 124, 635 (2018). https://doi.org/10.1007/s00339-018-2060-0
J. Boonlakhorn, P. Kidkhunthod, P. Thongbai, Significantly improved giant dielectric response in giant dielectric response in CaCu2.95Ni0.05Ti4–xGexO12 (x = 0.05, 0.10) ceramics. Mater. Today Commun. 21, 100633 (2019). https://doi.org/10.1016/j.mtcomm.2019.100633
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, 2867–2875 (2006). https://doi.org/10.1016/j.actamat.2006.02.037
E.A. Patterson, S. Kwon, C.C. Huang, D.P. Cann, Effects of ZrO2 additions on the dielectric properties of CaCu3Ti4O12. Appl. Phys. Lett. 87, 182911 (2005). https://doi.org/10.1063/1.2126142
C. Mua, H. Zhang, Y. He, P. Liu, J. Shen, The origin of multiple dielectric relaxation processes in Fe-substituted CaCu3Ti4O12 ceramics. Mater. Sci. Eng. B 162, 195–199 (2009). https://doi.org/10.1016/j.mseb.2009.04.012
P. Mao, J. Wang, S. Liu, L. Zhang, Y. Zhao, K. Wu, Z. Wang, J. Li, Improved dielectric and nonlinear properties of CaCu3Ti4O12 ceramics with Cu-rich phase at grain boundary layers. Ceram. Int. 45, 1508215090 (2019). https://doi.org/10.1016/j.ceramint.2019.04.247
J.C.C. Abrantes, J.A. Labrincha, J.R. Frade, Representations of impedance spectra of ceramics Part I. Simulated study cases. Mater. Res. Bull. 35, 955–964 (2000). https://doi.org/10.1088/0022-3727/42/5/055404
J.T.S. Irvine, D.C. Sinclair, A.R. West, Electroceramics: characterization by impedance spectroscopy. Adv. Mater. 2, 132–138 (1990). https://doi.org/10.1002/adma.19900020304
Y. Yu, Q. Wang, W.Q. Khan, Dielectric properties of Ni and Nb doped CaCu. Ceram. J. Phys. Conf. Ser. 1885, 032055 (2021). https://doi.org/10.1088/1742-6596/1885/3/032055
Y. Yan, L. Jin, L. Feng, G. Cao, Decrease of dielectric loss in giant dielectric constant CaCu3Ti4O12 ceramics by adding CaTiO3. Mater. Sci. Eng. B 130, 146–150 (2006). https://doi.org/10.1016/j.mseb.2006.02.060
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Rhouma, S., Megriche, A., Souidi, E. et al. Improvement of the Nonlinear and Dielectric Properties of CaCu3Ti4O12 Ceramics by Nickel Doping. J Inorg Organomet Polym 34, 221–234 (2024). https://doi.org/10.1007/s10904-023-02816-4
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DOI: https://doi.org/10.1007/s10904-023-02816-4