Issue 22, 2024

Transition metal-doped SrTiO3: when does a tiny chemical impact have such a great structural response?

Abstract

The effect of doping on the chemical and physical properties of semiconductors, alloys, ferroelectrics, glasses, and other substances has been a classic topic in materials science for centuries. Strontium titanate, SrTiO3, is an archetypal perovskite of interest for both fundamental science as quantum paraelectric and numerous outstanding physical properties and applications, including dielectrics, tunable microwave and photovoltaic devices, superconductors, thermoelectrics, potential multiferroics. Its chemical doping with transition metals leads to new functionalities, but intrinsic mechanisms of structural responses, activated by impurities, have not been systematically investigated. Herein, we present the results of a comparative study of the crystal structure, vibrational spectra, and dielectric properties of SrTiO3:M (M = Mn, Ni, and Fe, 2 at%) single crystals. It is shown that impurities constitute a different tendency to off-centering and the formation of dipoles: Mn and Fe atoms are shifted from the center of the oxygen octahedron, while Ni atoms remain on-centered. As a result, small chemical doping has a dramatic effect on the dielectric response through various structural mechanisms, including the pseudo Jahn–Teller effect, the first-order Jahn–Teller effect, and defect-induced distortion. These findings open up fundamentally new possibilities for the practical solution of a difficult problem: controlling the dielectric responses of quantum paraelectrics by choosing the type of chemical additive.

Graphical abstract: Transition metal-doped SrTiO3: when does a tiny chemical impact have such a great structural response?

Supplementary files

Article information

Article type
Paper
Submitted
13 Jan 2024
Accepted
14 May 2024
First published
15 May 2024

J. Mater. Chem. C, 2024,12, 8105-8118

Transition metal-doped SrTiO3: when does a tiny chemical impact have such a great structural response?

M. V. Talanov, A. I. Stash, S. A. Ivanov, E. S. Zhukova, Boris. P. Gorshunov, B. M. Nekrasov, A. V. Melentev, V. I. Kozlov, V. M. Cherepanov, S. Yu. Gavrilkin, A. Yu. Tsvetkov, I. A. Zavidovskiy, M. K. Tatmyshevskiy, M. Savinov, V. M. Talanov and A. A. Bush, J. Mater. Chem. C, 2024, 12, 8105 DOI: 10.1039/D4TC00180J

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