J. Semicond. > 2022, Volume 43 > Issue 3 > 032001

ARTICLES

Fe3+-substitution effect on the thermal variation of JE characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12

Kunal B. Modi1, , Pooja Y. Raval2, Dolly J. Parekh1, Shrey K. Modi3, Niketa P. Joshi1, Akshay R. Makadiya1, Nimish H. Vasoya4 and Utpal S. Joshi5

+ Author Affiliations

 Corresponding author: Kunal B. Modi, kunalbmodi2003@yahoo.com

DOI: 10.1088/1674-4926/43/3/032001

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Abstract: The electrical properties of cubic perovskite series, CaCu3–xTi4–xFe2xO12 with x = 0.0, 0.1, 0.3, 0.5, and 0.7, have been studied by employing current density as a function of electric field characteristics registered at different temperatures and thermal variations of direct current electrical resistivity measurements. All of the compositions exhibit strong non-ohmic behavior. The concentration dependence of breakdown field, the temperature at which switching action takes place, and maximum value of current density (Jmax) has been explained on account of structural, microstructural, and positron lifetime parameters. The highest ever reported value of Jmax = 327 mA/cm2 has been observed for pristine composition. The values of the nonlinear coefficient advise the suitability of ceramics for low-voltage varistor applications. The Arrhenius plots show typical semiconducting nature. The activation energy values indicate that electric conduction proceeds through electrons with deformation in the system.

Key words: perovskitesmagnetic materialsJ–E characteristicscapacitor



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Fig. 1.  (Color online) Plots of JE characteristic recorded at different temperatures for a series of cubic perovskites, CaCu3–xTi4–xFe2xO12 (x = 0.0–0.7).

Fig. 2.  Williamson-Hall plots for all the samples of a series CaCu3–xTi4–xFe2xO12.

Fig. 3.  (Color online) ln J against E1/2 plots at different temperatures for polycrystalline samples of quadruple perovskite series, CaCu3–xTi4–xFe2xO12.

Fig. 4.  (Color online) Plots of ln Jo against temperature for the different compositions.

Fig. 5.  (Color online) Arrhenius plots for a quadruple perovskite series, CaCu3–xTi4–xFe2x O12.

Table 1.   Structural, microstructural, and electric parameters for a series of cubic perovskites.

Fe3+_ content (x)Strain 10–4a (Å) ±0.002 Ådx (g/cm3)d (g/cm3)fD (μm)δ (1010 m–2)TsL (K)Es (V/cm)
T = 473 K
Jmax
(mA/cm2)
Ea1 (eV)Ea2 (eV)
0.0–4.547.3915.0564.7440.0623.77.304739783270.330.43
0.1–6.167.3885.0614.7120.0693735702700.290.29
0.3–6.777.3875.0644.7040.0717.51.783735252250.220.21
0.5–5.967.4005.0384.5560.0967.91.603732612250.250.15
0.7–6.957.4115.0164.5660.0903.48.653733002250.270.21
TsL is the lowest temperature at which switching action takes place.
Es is the threshold value of the electric field beyond which non-ohmic behavior is observed.
Jmax is the maximum current density value.
Ea1 and Ea2 are the activation energies determined from Arrhenius plots below and above the transition temperature, respectively.
DownLoad: CSV

Table 2.   Distribution of metallic cations (Ca+2, Cu+2, Ti+4 and Fe+3) among the available crystallographic sites determined from Rietvield refinement of X-ray powder diffraction data ( T = 300 K) for CaCu3–xTi4Fe2xO12 ( x = 0.0–0.7) system.

Fe3+ content (x)Cation distribution
0.0$ {\mathrm{C}\mathrm{a}}^{2+} $[$ {\mathrm{C}\mathrm{u}}_{3}^{2+} $] {$ {\mathrm{T}\mathrm{i}}_{4}^{4+} $}$ {\mathrm{O}}_{12}^{2-} $
0.1$ {\mathrm{C}\mathrm{a}}^{2+} $[$ {\mathrm{C}\mathrm{u}}_{2.86}^{2+}{\mathrm{F}\mathrm{e}}_{0.14}^{3+} $] {$ {\mathrm{T}\mathrm{i}}_{3.90}^{4+}{\mathrm{F}\mathrm{e}}_{0.06}^{3+}{\mathrm{C}\mathrm{u}}_{0.04}^{2+} $}$ {\mathrm{O}}_{12}^{2-} $
0.3$ {\mathrm{C}\mathrm{a}}^{2+} $[$ {\mathrm{C}\mathrm{u}}_{2.41}^{2+}{\mathrm{T}\mathrm{i}}_{0.24}^{4+}{\mathrm{F}\mathrm{e}}_{0.35}^{3+} $] {$ {\mathrm{T}\mathrm{i}}_{3.46}^{4+}{\mathrm{F}\mathrm{e}}_{0.25}^{3+}{\mathrm{C}\mathrm{u}}_{0.29}^{2+} $}$ {\mathrm{O}}_{12}^{2-} $
0.5$ {\mathrm{C}\mathrm{a}}^{2+} $[$ {\mathrm{C}\mathrm{u}}_{2.03}^{2+}{\mathrm{T}\mathrm{i}}_{0.17}^{4+}{\mathrm{F}\mathrm{e}}_{0.80}^{3+} $] {$ {\mathrm{T}\mathrm{i}}_{3.33}^{4+}{\mathrm{F}\mathrm{e}}_{0.20}^{3+}{\mathrm{C}\mathrm{u}}_{0.47}^{2+} $}$ {\mathrm{O}}_{12}^{2-} $
0.7$ {\mathrm{C}\mathrm{a}}^{2+} $[$ {\mathrm{C}\mathrm{u}}_{1.53}^{2+}{\mathrm{T}\mathrm{i}}_{0.12}^{4+}{\mathrm{F}\mathrm{e}}_{1.35}^{3+} $] {$ {\mathrm{T}\mathrm{i}}_{3.18}^{4+}{\mathrm{F}\mathrm{e}}_{0.05}^{3+}{\mathrm{C}\mathrm{u}}_{0.77}^{2+} $}$ {\mathrm{O}}_{12}^{2-} $
DownLoad: CSV
[1]
Subramanian M A, Li D, Duan N, et al. High dielectric constant in ACu3Ti4O12 and ACu3Ti3FeO12 phases. J Solid State Chem, 2000, 151, 323 doi: 10.1006/jssc.2000.8703
[2]
Ramirez A P, Subramanian M A, Gardel M, et al. Giant dielectric constant response in a copper-titanate. Solid State Commun, 2000, 115, 217 doi: 10.1016/S0038-1098(00)00182-4
[3]
Prompa K, Swatsitang E, Saiyasombat C, et al. Very high performance dielectric and non-Ohmics properties of CaCu3Ti4.2O12 ceramics for X8R capacitors. Ceram Int, 2018, 44, 13267 doi: 10.1016/j.ceramint.2018.04.156
[4]
Kretly L C, Almeida A F L, de Oliveira R S, et al. Electrical and optical properties of CaCu3Ti4O12 (CCTO) substrates for microwave devices and antennas. Microw Opt Technol Lett, 2003, 39, 145 doi: 10.1002/mop.11152
[5]
Chung S Y, Kim I D, Kang S J L. Strong nonlinear current-voltage behaviour in perovskite-derivative calcium copper titanate. Nat Mater, 2004, 3, 774 doi: 10.1038/nmat1238
[6]
Felix A A, Rupp J L M, Varela J A, et al. Multi-functional properties of CaCu3Ti4O12 thin films. J Appl Phys, 2012, 112, 054512 doi: 10.1063/1.4751344
[7]
Kushwaha H S, Madhar N A, Ilahi B, et al. Efficient solar energy conversion using CaCu3Ti4O12 photoanode for photocatalysis and photoelectrocatalysis. Sci Rep, 2016, 6, 1 doi: 10.1038/s41598-016-0001-8
[8]
Chhetry A, Sharma S, Yoon H, et al. Enhanced sensitivity of capacitive pressure and strain sensor based on CaCu3Ti4O12 wrapped hybrid sponge for wearable applications. Adv Funct Mater, 2020, 30, 1910020 doi: 10.1002/adfm.201910020
[9]
Chattopadhyay A, Nayak J. Synthesis of CCTO powder for application in humidity sensor. AIP Conference Proceedings, 2020, 040020
[10]
Prompa K, Swatsitang E, Putjuso T. Enhancement of nonlinear electrical properties with high performance dielectric properties of CaCu2.95Cr0.05Ti4.1O12 ceramics. Ceram Int, 2018, 44, S72 doi: 10.1016/j.ceramint.2018.08.237
[11]
Ren L L, Yang L J, Xu C, et al. Improvement of breakdown field and dielectric properties of CaCu3Ti4O12 ceramics by Bi and Al co-doping. J Alloys Compd, 2018, 768, 652 doi: 10.1016/j.jallcom.2018.07.293
[12]
Boonlakhorn J, Thongbai P. Dielectric properties, nonlinear electrical response and microstructural evolution of CaCu3Ti4– xSn xO12 ceramics prepared by a double ball-milling process. Ceram Int, 2020, 46, 4952 doi: 10.1016/j.ceramint.2019.10.233
[13]
Cortés J A, Cotrim G, Orrego S, et al. Dielectric and non-ohmic properties of Ca2Cu2Ti4– xSn xO12 (0.0 ≤ x ≤ 4.0) multiphasic ceramic composites. J Alloys Compd, 2018, 735, 140 doi: 10.1016/j.jallcom.2017.11.089
[14]
Rhouma S, Saîd S, Autret C, et al. Comparative studies of pure, Sr-doped, Ni-doped and co-doped CaCu3Ti4O12 ceramics: Enhancement of dielectric properties. J Alloys Compd, 2017, 717, 121 doi: 10.1016/j.jallcom.2017.05.053
[15]
Wu S, Liu P, Lai Y M, et al. Effect of Ba2+ doping on microstructure and electric properties of calcium copper titanate (CaCu3Ti4O12) ceramics. J Mater Sci: Mater Electron, 2016, 27, 10336 doi: 10.1007/s10854-016-5118-9
[16]
Barman N, Varma K B R. Enhanced non-linear current-voltage response of Te-doped calcium copper titanate ceramics. Ceram Int, 2017, 43, 6363 doi: 10.1016/j.ceramint.2017.02.045
[17]
Grzebielucka E C, Leandro Monteiro J F H, de Souza E C F, et al. Improvement in varistor properties of CaCu3Ti4O12 ceramics by chromium addition. J Mater Sci Technol, 2020, 41, 12 doi: 10.1016/j.jmst.2019.08.055
[18]
Sun J J, Xu C, Zhao X T, et al. Improved dielectric properties of indium and tantalum co-doped CaCu3Ti4O12 ceramic prepared by spark plasma sintering. IEEE Trans Dielectr Electr Insul, 2020, 27, 1400 doi: 10.1109/TDEI.2020.008451
[19]
Sripakdee C, Prompa K, Swatsitang E, et al. Very high-performance dielectric and non-ohmic properties of novel X8R type Ca1–1.5 xHo xCu3Ti4O12/TiO2 ceramics. J Alloys Compd, 2019, 779, 521 doi: 10.1016/j.jallcom.2018.11.298
[20]
Boonlakhorn J, Chanlek N, Manyam J, et al. Enhanced giant dielectric properties and improved nonlinear electrical response in acceptor-donor (Al3+, Ta5+)-substituted CaCu3Ti4O12 ceramics. J Adv Ceram, 2021, 10, 1243 doi: 10.1007/s40145-021-0499-5
[21]
Löhnert R, Bartsch H, Schmidt R, et al. Microstructure and electric properties of CaCu3Ti4O12 multilayer capacitors. J Am Ceram Soc, 2015, 98, 141 doi: 10.1111/jace.13260
[22]
Zheng Q, Fan H Q, Long C B. Microstructures and electrical responses of pure and chromium-doped CaCu3Ti4O12 ceramics. J Alloys Compd, 2012, 511, 90 doi: 10.1016/j.jallcom.2011.09.002
[23]
Amhil S, Choukri E, Ben Moumen S, et al. Evidence of large hopping polaron conduction process in strontium doped calcium copper titanate ceramics. Phys B, 2019, 556, 36 doi: 10.1016/j.physb.2018.12.032
[24]
Fan H Q, Zheng Q, Peng B L. Microstructure, dielectric and pyroelectric properties of CaCu3Ti4O12 ceramics fabricated by tape-casting method. Mater Res Bull, 2013, 48, 3278 doi: 10.1016/j.materresbull.2013.05.026
[25]
Chen L, Chen C L, Lin Y, et al. High temperature electrical properties of highly epitaxial CaCu3Ti4O12 thin films on (001) LaAlO3. Appl Phys Lett, 2003, 82, 2317 doi: 10.1063/1.1565702
[26]
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    Received: 15 September 2021 Revised: 19 November 2021 Online: Uncorrected proof: 31 December 2021Published: 10 March 2022

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      Kunal B. Modi, Pooja Y. Raval, Dolly J. Parekh, Shrey K. Modi, Niketa P. Joshi, Akshay R. Makadiya, Nimish H. Vasoya, Utpal S. Joshi. Fe3+-substitution effect on the thermal variation of J–E characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12[J]. Journal of Semiconductors, 2022, 43(3): 032001. doi: 10.1088/1674-4926/43/3/032001 ****K B Modi, P Y Raval, D J Parekh, S K Modi, N P Joshi, A R Makadiya, N H Vasoya, U S Joshi, Fe3+-substitution effect on the thermal variation of J–E characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12[J]. J. Semicond., 2022, 43(3): 032001. doi: 10.1088/1674-4926/43/3/032001.
      Citation:
      Kunal B. Modi, Pooja Y. Raval, Dolly J. Parekh, Shrey K. Modi, Niketa P. Joshi, Akshay R. Makadiya, Nimish H. Vasoya, Utpal S. Joshi. Fe3+-substitution effect on the thermal variation of JE characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12[J]. Journal of Semiconductors, 2022, 43(3): 032001. doi: 10.1088/1674-4926/43/3/032001 ****
      K B Modi, P Y Raval, D J Parekh, S K Modi, N P Joshi, A R Makadiya, N H Vasoya, U S Joshi, Fe3+-substitution effect on the thermal variation of J–E characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12[J]. J. Semicond., 2022, 43(3): 032001. doi: 10.1088/1674-4926/43/3/032001.

      Fe3+-substitution effect on the thermal variation of JE characteristics and DC resistivity of quadruple perovskite CaCu3Ti4O12

      DOI: 10.1088/1674-4926/43/3/032001
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      • Kunal B. Modi:is currently a professor of physics at Saurashtra University, Rajkot, India. His research interests focus on the synthesis and characterization of spinel ferrites and CaCu3Ti4O12 – based perovskites. Dr. Modi has published more than 120 research papers in internationally-reputed journals. Dr. Modi has received three national awards
      • Corresponding author: kunalbmodi2003@yahoo.com
      • Received Date: 2021-09-15
      • Accepted Date: 2021-12-30
      • Revised Date: 2021-11-19
      • Published Date: 2022-03-10

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