Kinetic Stabilization of the First Sn(II)-Perovskite Oxide as a Nanoshell

18 July 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The synthesis of kinetically-stabilized, i.e., metastable, dielectric semiconductors, represents a major frontier within key technologically-important fields as compared to thermodynamically-stable solids that have received considerably more attention. Of longstanding theoretical interest are Sn(II) perovskites (e.g., Sn(Zr1/2Ti1/2)O3, SZT), which are Pb-free analogues of (Pb(Zr1/2Ti1/2)O3, PZT), a commercial piezoelectric composition that is dominant in the electronics industry. Herein, we describe the synthesis of this metastable SZT dielectric through a low-temperature flux reaction technique. The SZT has been found, for the first time, to grow and to be stabilized as a nanoshell at the surfaces of Ba(Zr1/2Ti1/2)O3 (BZT) particles, i.e., forming as BZT-SZT core-shell particles, as a result of Sn(II) cation exchange. In situ powder X-ray diffraction (XRD) and transmission electron microscopy data show that the SZT nanoshells result from the controlled cation diffusion of Sn(II) cations into the BZT particles, with tunable thicknesses of ~25 nm to 100 nm. The SZT nanoshell is calculated to possess a metastability of ~ 0.5 eV atom–1 with respect to decomposition to SnO, ZrO2, and TiO2, and thus cannot currently be prepared as stand-alone particles. Rietveld refinements of the XRD data are consistent with a two-phase BZT-SZT model, with each phase possessing a generally cubic perovskite-type structure and nearly identical lattice parameters. Mössbauer spectroscopic data (119Sn) are consistent with Sn(II) cations within the SZT nanoshells and an outer ~5 to 10 nm surface region comprised of oxidized Sn(IV) cations from exposure to air and water. The optical band gap of the SZT shell was found to be ~2.2 eV, which is redshifted by ~1.2 eV as compared to BZT. This closing of the band gap was probed by X-ray photoelectron spectroscopy and found to stem from a shift of the valence band edge to higher energies (~1.07 eV) as a result of the addition of the Sn 5s2 orbitals forming a new higher-energy valence band. In summary, a novel synthetic tactic is demonstrated to be effective in preparing highly metastable SZT and representing a generally useful strategy for the kinetic stabilization of other predicted, metastable dielectrics.

Keywords

Metastability
Perovskites
Flux synthesis
Core-Shell Particles

Supplementary materials

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Supplementary Data
Description
Electron microscopy, powder X-ray diffraction structure refinements and results of EDS data.
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