Mechanism of small-polaron formation in the biferroic YCrO3 doped with calcium

TL;DR

This study investigates how calcium doping influences small-polaron formation in YCrO3 ceramics, revealing that Ca induces localized polarons through charge compensation, affecting electrical conductivity without altering magnetic transition temperatures.

Contribution

It provides a detailed mechanism of small-polaron formation in Ca-doped YCrO3, distinguishing it from undoped samples and linking structural changes to electrical properties.

Findings

Calcium doping decreases cell volume via Cr(III) to Cr(IV) transition.

Electrical conductivity increases with Ca content due to small-polaron formation.

Different origins of small-polarons in doped versus undoped YCrO3 are identified.

Abstract

The effects of Ca substitutions on the structure, magnetism and electrical properties of YCrO3 ceramics are investigated by X-ray diffraction, magnetic susceptibility and electrical conductivity measurements. The cell volume decrease occurs through the change from Cr(III) to Cr(IV) as a result of the charge compensation of the Ca doping. No changes are observed in the antiferromagnetic transition temperature while strong changes are observed in the transport measurements due to Ca content. The increase of the electrical conductivity as well as the decrease of the activation energy are caused by the formation of the small-polarons localized in the O-Cr-O lattice distortion. The origin of small-polarons in the undoped sample is different in nature from the calcium doped. "Local non-centrosymetry" is the source of the small-polaron formation in undoped sample, while the change from Cr(III) to Cr(IV) through the charge compensation of Ca(II) in the Y(III) site is the source of small-polarons formations. The decrease of the average bond length Cr-O as well as effective moments in the paramagnetic state and the increase of the electrical conductivity are clear evidence that the Ca doping induces localized polarons, which in turn, these quasiparticles move from site to site by a thermally activated process in the doped YCrO3 compound. Here, we also discuss a possible mechanism of small-polaron injections in YCrO3 matrix.