Skip to main content

Enhanced giant dielectric properties and improved nonlinear electrical response in acceptor-donor (Al3+, Ta5+)-substituted CaCu3Ti4O12 ceramics

Abstract

The giant dielectric behavior of CaCu3Ti4O12 (CCTO) has been widely investigated owing to its potential applications in electronics; however, the loss tangent (tanδ) of this material is too large for many applications. A partial substitution of CCTO ceramics with either Al3+ or Ta5+ ions generally results in poorer nonlinear properties and an associated increase in tanδ (to ∼0.29–1.15). However, first-principles calculations showed that self-charge compensation occurs between these two dopant ions when co-doped into Ti4+ sites, which can improve the electrical properties of the grain boundary (GB). Surprisingly, in this study, a greatly enhanced breakdown electric field (∼200–6588 V/cm) and nonlinear coefficient (∼4.8–15.2) with a significantly reduced tanδ (∼0.010–0.036) were obtained by simultaneous partial substitution of CCTO with acceptor-donor (Al3+, Ta5+) dopants to produce (Al3+, Ta5+)-CCTO ceramics. The reduced tanδ and improved nonlinear properties were attributed to the synergistic effects of the co-dopants in the doped CCTO structure. The significant reduction in the mean grain size of the (Al3+, Ta5+)-CCTO ceramics compared to pure CCTO was mainly because of the Ta5+ ions. Accordingly, the increased GB density due to the reduced grain size and the larger Schottky barrier height (Φb) at the GBs of the co-doped CCTO ceramics were the main reasons for the greatly increased GB resistance, improved nonlinear properties, and reduced tanδ values compared to pure and single-doped CCTO. In addition, high dielectric constant values (ε′ ≈ (0.52–2.7) × 104) were obtained. A fine-grained microstructure with highly insulating GBs was obtained by Ta5+ doping, while co-doping with Ta5+ and Al3+ resulted in a high Φb. The obtained results are expected to provide useful guidelines for developing new giant dielectric ceramics with excellent dielectric properties.

References

  1. [1]

    Guo BC, Liu P, Cui X, et al. Enhancement of breakdown electric field and DC bias of (In0.5Nb0.5)0.005(Ti1−xZrx)0.995O2 colossal permittivity ceramics. J Alloys Compd 2018, 740: 1108–1115.

    CAS  Article  Google Scholar 

  2. [2]

    Liang P, Wang X, Chao X, et al. Electric response and improved dielectric properties in BiCu3Ti3FeO12. J Alloys Compd 2018, 734: 9–15.

    CAS  Article  Google Scholar 

  3. [3]

    Wang XW, Jia PB, Sun LY, et al. Improved dielectric properties in CaCu3Ti4O12 ceramics modified by TiO2. J Mater Sci: Mater Electron 2018, 29: 2244–2250.

    CAS  Google Scholar 

  4. [4]

    Hu W, Liu Y, Withers RL, et al. Electron-pinned defect-dipoles for high-performance colossal permittivity materials. Nat Mater 2013, 12: 821–826.

    CAS  Article  Google Scholar 

  5. [5]

    Boonlakhorn J, Kidkhunthod P, Chanlek N, et al. (Al3+, Nb5+) co-doped CaCu3Ti4O12: An extended approach for acceptor-donor heteroatomic substitutions to achieve high-performance giant-dielectric permittivity. J Eur Ceram Soc 2018, 38: 137–143.

    Article  CAS  Google Scholar 

  6. [6]

    Wen A, Yuan D, Zhu X, et al. Electrical and dielectric properties of aluminum/niobium co-doped CaCu3Ti4O12 ceramics. Ferroelectrics 2016, 492: 1–9.

    CAS  Article  Google Scholar 

  7. [7]

    Boonlakhorn J, Kidkhunthod P, Thongbai P. Effects of co-doping on dielectric and electrical responses of CaCu3Ti4−x(Nb1/2In1/2)xO12 ceramics. J Phys: Conf Ser 2017, 901: 012078.

    Google Scholar 

  8. [8]

    Boonlakhorn J, Srepusharawoot P, Thongbai P. Distinct roles between complex defect clusters and insulating grain boundary on dielectric loss behaviors of (In3+/Ta5+) co-doped CaCu3Ti4O12 ceramics. Results Phys 2020, 16: 102886.

    Article  Google Scholar 

  9. [9]

    Sun J, Xu C, Zhao X, 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: 1400–1408.

    CAS  Article  Google Scholar 

  10. [10]

    Hasan MK, Shant SH, Islam MZ, et al. Influence of Nb and Zr co-doping on the structural, morphological and dielectric properties of CaCu3Ti4O12 ceramics. IOP Conf Ser: Mater Sci Eng 2021, 1045: 012004.

    CAS  Article  Google Scholar 

  11. [11]

    Mao P, Wang J, Xiao P, et al. Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics. Ceram Int 2021, 47: 111–120.

    CAS  Article  Google Scholar 

  12. [12]

    Xu Z, Qiang H, Chen Y, et al. Microstructure and enhanced dielectric properties of yttrium and zirconium co-doped CaCu3Ti4O12 ceramics. Mater Chem Phys 2017, 191: 1–5.

    CAS  Article  Google Scholar 

  13. [13]

    Bai L, Wu Y, Zhang L. Influence of FeNb codoping on the dielectric and electrical properties of CaCu3Ti4O12 ceramics. J Alloys Compd 2016, 661: 6–13.

    CAS  Article  Google Scholar 

  14. [14]

    Qu Y, Wu Y, Wu J, et al. Simultaneous epsilon-negative and mu-negative property of Ni/CaCu3Ti4O12 metacomposites at radio-frequency region. J Alloys Compd 2020, 847: 156526.

    CAS  Article  Google Scholar 

  15. [15]

    Qu Y, Du Y, Fan G, et al. Low-temperature sintering Graphene/CaCu3Ti4O12 nanocomposites with tunable negative permittivity. J Alloys Compd 2019, 771: 699–710.

    CAS  Article  Google Scholar 

  16. [16]

    Qu Y, Lin J, Wu J, et al. Graphene-carbon black/CaCu3Ti4O12 ternary metacomposites toward a tunable and weakly ε-negative property at the radio-frequency region. J Phys Chem C 2020, 124: 23361–23367.

    CAS  Article  Google Scholar 

  17. [17]

    Hu W, Lau K, Liu Y, et al. Colossal dielectric permittivity in (Nb+Al) codoped rutile TiO2 ceramics: Compositional gradient and local structure. Chem Mater 2015, 27: 4934–4942.

    CAS  Article  Google Scholar 

  18. [18]

    Song Y, Wang X, Zhang X, et al. Colossal dielectric permittivity in (Al + Nb) co-doped rutile SnO2 ceramics with low loss at room temperature. Appl Phys Lett 2016, 109: 142903.

    Article  CAS  Google Scholar 

  19. [19]

    Wu J, Nan CW, Lin Y, et al. Giant dielectric permittivity observed in Li and Ti doped NiO. Phys Rev Lett 2002, 89: 217601.

    Article  CAS  Google Scholar 

  20. [20]

    Peng Z, Liang P, Wang X, et al. Fabrication and characterization of CdCu3Ti4O12 ceramics with colossal permittivity and low dielectric loss. Mater Lett 2018, 210: 301–304.

    CAS  Article  Google Scholar 

  21. [21]

    Jumpatam J, Somphan W, Boonlakhorn J, et al. Non-ohmic properties and electrical responses of grains and grain boundaries of Na1/2Y1/2Cu3Ti4O12 ceramics. J Am Ceram Soc 2017, 100: 157–166.

    CAS  Article  Google Scholar 

  22. [22]

    Peng Z, Wu D, Liang P, et al. Grain boundary engineering that induces ultrahigh permittivity and decreased dielectric loss in CdCu3Ti4O12 ceramics. J Am Ceram Soc 2020, 103: 1230–1240.

    CAS  Article  Google Scholar 

  23. [23]

    Peng Z, Liang P, Wang J, et al. Interfacial effect inducing thermal stability and dielectric response in CdCu3Ti4O12 ceramics. Solid State Ion 2020, 348: 115290.

    CAS  Article  Google Scholar 

  24. [24]

    Winkler E, Rivadulla F, Zhou JS, et al. Evolution of polaron size in La2−xSrxNiO4. Phys Rev B 2002, 66: 094418.

    Article  CAS  Google Scholar 

  25. [25]

    Wang CC, Zhang LW. Surface-layer effect in CaCu3Ti4O12. Appl Phys Lett 2006, 88: 042906.

    Article  CAS  Google Scholar 

  26. [26]

    Lunkenheimer P, Fichtl R, Ebbinghaus S, et al. Nonintrinsic origin of the colossal dielectric constants in CaCu3Ti4O12. Phys Rev B 2004, 70: 172102.

    Article  CAS  Google Scholar 

  27. [27]

    Sun L, Zhang R, Wang Z, et al. Microstructure and enhanced dielectric response in Mg doped CaCu3Ti4O12 ceramics. J Alloys Compd 2016, 663: 345–350.

    CAS  Article  Google Scholar 

  28. [28]

    Tuichai W, Thongyong N, Danwittayakul S, et al. Very low dielectric loss and giant dielectric response with excellent temperature stability of Ga3+ and Ta5+ co-doped rutile-TiO2 ceramics. Mater Des 2017, 123: 15–23.

    CAS  Article  Google Scholar 

  29. [29]

    Boonlakhorn J, Kidkhunthod P, Thongbai P. A novel approach to achieve high dielectric permittivity and low loss tangent in CaCu3Ti4O12 ceramics by co-doping with Sm3+ and Mg2+ ions. J Eur Ceram Soc 2015, 35: 3521–3528.

    CAS  Article  Google Scholar 

  30. [30]

    Silva Junior E, La Porta FA, Liu MS, et al. A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials. Dalton Trans 2015, 44: 3159–3175.

    CAS  Article  Google Scholar 

  31. [31]

    Boonlakhorn J, Chanlek N, Thongbai P, et al. Strongly enhanced dielectric response and structural investigation of (Sr2+, Ge4+) co-doped CCTO ceramics. J Phys Chem C 2020, 124: 20682–20692.

    CAS  Article  Google Scholar 

  32. [32]

    Subramanian MA, Li D, Duan N, et al. High dielectric constant in ACu3Ti4O12 and ACu3Ti3FeO12 phases. J Solid State Chem 2000, 151: 323–325.

    CAS  Article  Google Scholar 

  33. [33]

    Thongbai P, Jumpatam J, Yamwong T, et al. Effects of Ta5+ doping on microstructure evolution, dielectric properties and electrical response in CaCu3Ti4O12 ceramics. J Eur Ceram Soc 2012, 32: 2423–2430.

    CAS  Article  Google Scholar 

  34. [34]

    Moulson AJ, Herbert JM. Electroceramics: Materials, Properties, Applications, 2nd edn. New York; Wiley, 2003: 243–337

    Book  Google Scholar 

  35. [35]

    Xu Z, Qiang H. Enhanced dielectric properties of Zn and Mn co-doped CaCu3Ti4O12 ceramics. J Mater Sci: Mater Electron 2017, 28: 376–380.

    CAS  Google Scholar 

  36. [36]

    Li M, Liu Q, Li CX. Study of the dielectric responses of Eu-doped CaCu3Ti4O12. J Alloys Compd 2017, 699: 278–282.

    CAS  Article  Google Scholar 

  37. [37]

    Adams T, Sinclair D, West A. Characterization of grain boundary impedances in fine- and coarse-grained CaCu3Ti4O12 ceramics. Phys Rev B 2006, 73: 094124.

    Article  CAS  Google Scholar 

  38. [38]

    Moreno H, Cortés JA, Praxedes FM, et al. Tunable photoluminescence of CaCu3Ti4O12 based ceramics modified with tungsten. J Alloys Compd 2021, 850: 156652.

    CAS  Article  Google Scholar 

  39. [39]

    Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst Sect A 1976, 32: 751–767.

    Article  Google Scholar 

  40. [40]

    Rahaman MN. Ceramic Processing and Sintering, 2nd edn. CRC Press, 2017.

  41. [41]

    Yu R, Xue H, Cao Z, et al. Effect of oxygen sintering atmosphere on the electrical behavior of CCTO ceramics. J Eur Ceram Soc 2012, 32: 1245–1249.

    CAS  Article  Google Scholar 

  42. [42]

    Lee SY, Kim HE, Yoo SI. Subsolidus phase relationship in the CaO-CuO-TiO2 ternary system at 950 °C in air. J Am Ceram Soc 2014, 97: 2416–2419.

    CAS  Article  Google Scholar 

  43. [43]

    Rahaman MN, Manalert R. Grain boundary mobility of BaTiO3 doped with aliovalent cations. J Eur Ceram Soc 1998, 18: 1063–1071.

    CAS  Article  Google Scholar 

  44. [44]

    Chiang YM, Takagi T. Grain-boundary chemistry of Barium titanate and strontium titanate: I, high-temperature equilibrium space charge. J Am Ceram Soc 1990, 73: 3278–3285.

    CAS  Article  Google Scholar 

  45. [45]

    Li M, Sinclair DC, West AR. Extrinsic origins of the apparent relaxorlike behavior in CaCu3Ti4O12 ceramics at high temperatures: A cautionary tale. J Appl Phys 2011, 109: 084106.

    Article  CAS  Google Scholar 

  46. [46]

    Nachaithong T, Thongbai P, Maensiri S. Colossal permittivity in (In1/2Nb1/2)xTi1−xO2 ceramics prepared by a glycine nitrate process. J Eur Ceram Soc 2017, 37: 655–660.

    CAS  Article  Google Scholar 

  47. [47]

    Hong SH, Kim DY, Park HM, et al. Electric and dielectric properties of Nb-doped CaCu3Ti4O12 ceramics. J Am Ceram Soc 2007, 90: 2118–2121.

    CAS  Article  Google Scholar 

  48. [48]

    Chung SY, Choi JH, Choi JK. Tunable current-voltage characteristics in polycrystalline calcium copper titanate. Appl Phys Lett 2007, 91: 091912.

    Article  CAS  Google Scholar 

  49. [49]

    Mao P, Wang J, Liu S, et al. Improved dielectric and nonlinear properties of CaCu3Ti4O12 ceramics with Cu-rich phase at grain boundary layers. Ceram Int 2019, 45: 15082–15090.

    CAS  Article  Google Scholar 

  50. [50]

    Cortés JA, Moreno H, Orrego S, et al. Dielectric and non-ohmic analysis of Sr2+ influences on CaCu3Ti4O12-based ceramic composites. Mater Res Bull 2021, 134: 111071.

    Article  CAS  Google Scholar 

  51. [51]

    Cotrim G, Cortés JA, Moreno H, et al. Tunable capacitor-varistor response of CaCu3Ti4O12/CaTiO3 ceramic composites with SnO2 addition. Mater Charact 2020, 170: 110699.

    CAS  Article  Google Scholar 

  52. [52]

    Sinclair DC, Adams TB, Morrison FD, et al. CaCu3Ti4O12: One-step internal barrier layer capacitor. Appl Phys Lett 2002, 80: 2153.

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Basic Research Fund of Khon Kaen University. It was partially supported by the Research Network NANOTEC (RNN) program of the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of Higher Education, Science, Research, and Innovation (MHESI, Thailand) (Grant No. P1851882), and Khon Kaen University, Thailand. J. Boonlakhorn would like to thank the Graduate School of Khon Kaen University (Grant No. 581T211) for his Ph.D. scholarship.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Prasit Thongbai.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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). https://doi.org/10.1007/s40145-021-0499-5

Download citation

Keywords

  • CaCu3Ti4O12 (CCTO)
  • impedance spectroscopy
  • nonlinear electrical properties
  • dielectric constant
  • loss tangent
  • first-principles calculations