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A review on (Sr,Ca)TiO3-based dielectric materials: crystallography, recent progress and outlook in energy-storage aspects

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Abstract

In pursuit of developing high-performance lead-free energy storage capacitors, strontium titanate (SrTiO3) and calcium titanate (CaTiO3) are widely recognised as promising dielectric ceramics. Both end members are completely miscible for the entire doping concentration which results in the successful formation of (Sr1 − xCax)TiO3 solid solutions. Most importantly, the Ca dopant irons the electric fields, temperature and frequency stabilities of SrTiO3 ceramic. This review encompasses up to date knowledge of crystallography, dielectric properties and recent progress on energy storage aspects of various (Sr1 − xCax)TiO3 materials. Firstly, the structural phase transition (with special attention to room temperature) behaviour has been discussed which is essential to understand the origin of functional dielectric properties. Thereafter, various strategies to improve the energy storage properties of bulk (Sr1 − xCax)TiO3-based materials have been discussed. Further, leverage of the improved properties in the bulk ceramics into the thin film regime will be essential for creating next-generation high-performance power electronic devices. In this perspective, some interesting developments reported in thin film form are also discussed. Finally, challenges and outlook of (Sr1 − xCax)TiO3-based bulk ceramics and thin films towards future research and the applications are presented.

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Figure 1

reproduced with permission from Yang et al. (Prog Mater Sci 102:72, 2019). Copyright ©2018, Elsevier Ltd [18]. Bar chart representation for the number of articles published on energy storage devices and dielectric capacitors between 2010 and 2020 [Source: Scopus database; title, abstract and keywords searched: “energy storage devices” and “dielectric capacitors” (filter: lead-free)] (b), sketch for various applications of capacitors (c) and bar chart representation for the number of papers published between 2011 and 2020 with “SrTiO3” or “strontium titanate” and “CaTiO3” or "calcium titanate" (filter: capacitors) as the topic (d)

Figure 2

reproduced with permission from McCalla et al. (Chem. Mater. 28:7973, 2016). Copyright© 2016, American Chemical Society [86]

Figure 3

reproduced with permission from Anwar et al. (J Phys: Condens Matter 20:325231, 2008). Copyright © 2008, IOP publishing [114]

Figure 4

reproduced with permission from Anwar et al. (Appl Phys Lett 92:212901, 2008). Copyright©2008, American Institute of Physics [109]. Schematic representation of the domain memory effect for occurrence of Pbcm symmetry (c), reproduced with permission from Ren et al. (Phys Rev Lett 85:1016, 2000). Copyright ©2000, American Physical Society [119]. Comparison of XRD data for 0.20⩽x⩽0.35 with (right panel) and without oxygenation (left panel) (d), reproduced with permission from Anwar et al. (Appl Phys Lett 92:212901, 2008). Copyright© 2008, AIP publishing [109]. Pseudocubic sub-cell parameter of Sr1−xCaxTiO3 solid solutions (e)

Figure 5

reproduced with permission from Geneste et al. (Phys Rev B 77:174101, 2008). Copyright©2008, American Physical Society [78]. The specific heat jump caused by the AFD phase transition in SrTiO3 (top) and Sr1−xCaxTiO3 (bottom) (d), reproduced with permission from Lima et al. (Phys Rev B 91:045108, 2015). Copyright ©2015, American Physical Society [79]. The ɛ′(T) curve for three different x with the maximum marks the Curie temperature; FE P-E loops at T = 5 K (inset) (e) and the dielectric loss ε"(T) with three different x in the frequency range, 1 Hz–1 kHz (f), reproduced with permission Lima et al. (Phys Rev B 91:045108, 2015). Copyright ©2015, American Physical Society [79]

Figure 6

reproduced with permission from Bednorz et al. (Phys Rev Lett 52:2289, 1984). Copyright © 1984, American Physical Society [93] and (x = 0.18 ≤ x ≤ 0.40) at 10 kHz (b), reproduced with permission from Ranjan et al. (Phys Rev Lett 84:3726, 2000). Copyright ©2000 American Physical Society [97]. Transition temperature (Tm) curve as a function of composition range, 0 ≤ x ≤ 0.40 (c) and Curie temperature (Tc) curve as a function of composition range, 0 ≤ x ≤ 0.35 (d), reproduced with permission from Ranjan et al. (J Phys: Condens Matter 13:4239, 2001). Copyright © 2001, IOP publishing [76]. The ε′(T) curves for the un-oxygenated (left panel) and oxygenated (right panel) ceramics at 1 kHz of heating–cooling P-E loops (e), reproduced with permission from Anwar et al. (Appl Phys Lett 92(21):212901, 2008). Copyright ©2008, American Institute of Physics [109]

Figure 7
Figure8
Figure 9

reproduced with permission from Cai et al. (J Am Ceram Soc 101:5487, 2018). Copyrights ©2018, American Ceramic Society [179]. The introduction of Zr4+ inhibits grain growth, and grain boundary barrier effects is enhanced via oxygen treatment for Ca0.5Sr0.5Ti0.85Zr0.15O3 ceramics (e), reproduced with permission from Pu et al. (J Mater Chem C 7:14384, 2019). Copyright © 2019, Royal Society of Chemistry [43]. Schematic outline of dielectric breakdown mechanism in various dielectric materials (f), reproduced with permission from Tan et al. (J Appl Polym Sci 137:49379, 2020). Copyright © 2020, Wiley Periodicals LLC [180]

Figure 10

reproduced with permission from Chen et al. (Appl Phys Lett 117:112902, 2020). Copyright ©2020, American Institute of Physics [68]

Figure 11

reproduced with permission from Moriana et al. (J Materiom 4:277, 2018). Copyright © 2018, Elsevier B.V [190]. Schematic of the migration of oxygen vacancies at SrTiO3/LSMO interface (b), reproduced with permission from Hou et al. (ACS Appl Mater Interfaces 9:20484, 2017).Copyright © 2017, American Chemical Society [142]. Three types of interfacial engineering in the epitaxial thin films: (i) buffer layer, (ii) artificial dead layer, and (iii) barrier layer (c)

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Acknowledgements

We acknowledge the Pôle Métropolitain de la Côte d'Opale (PMCO)—Université du Littoral Côte d'Opale (ULCO), France, for the financial support of Parthiban Palani’s PhD Grant.

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  1. Unité de Dynamique et Structure des Matériaux Moléculaires, Université du Littoral Côte d’Opale, 50 Rue Ferdinand Buisson, 62228, Calais, France

    Parthiban Palani, Didier Fasquelle & Amina Tachafine

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Palani, P., Fasquelle, D. & Tachafine, A. A review on (Sr,Ca)TiO3-based dielectric materials: crystallography, recent progress and outlook in energy-storage aspects. J Mater Sci 57, 12279–12317 (2022). https://doi.org/10.1007/s10853-022-07350-1

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