Coupled valence and spin state transition in (Pr0.7Sm0.3)0.7Ca0.3CoO3

TL;DR

This study investigates the coupled valence and spin state transitions in (Pr0.7Sm0.3)0.7Ca0.3CoO3 using X-ray absorption spectroscopy, revealing sharp temperature-dependent changes in valence and spin states that influence the material's conductivity.

Contribution

The paper provides detailed experimental insights into the temperature-driven valence and spin state transitions in (Pr0.7Sm0.3)0.7Ca0.3CoO3, highlighting the mechanisms stabilizing different states.

Findings

Sharp valence transition at T*=89.3 K involving Pr and Co ions.

Co4+ remains in an intermediate spin state across all temperatures.

Low-temperature behavior resembles EuCoO3 with stable low-spin Co3+.

Abstract

The coupled valence and spin state transition (VSST) taking place in (Pr0.7Sm0.3)0.7Ca0.3CoO3 was investigated by soft x-ray absorption spectroscopy (XAS) experiments carried out at the Pr-M4,5, Co-L2,3, and O-1s edges. This VSST is found to be composed of a sharp Pr/Co valence and Co spin state transition centered at T*=89.3 K, followed by a smoother Co spin-state evolution at higher temperatures. At T < T*, we found that the praseodymium displays a mixed valence Pr3+/Pr4+ with about 0.13 Pr4+/f.u., while all the Co3+ is in the low-spin (LS) state. At T around T*, the sharp valence transition converts all the Pr4+ to Pr3+ with a corresponding Co3+ to Co4+ compensation. This is accompanied by an equally sharp spin state transition of the Co3+ from the low to an incoherent mixture of low and high spin (HS) states. An involvement of the intermediate spin (IS) state can be discarded for the Co3+. While above T* and at high temperatures the system shares rather similar properties as Sr-doped LaCoO3, at low temperatures it behaves much more like EuCoO3 with its highly stable LS configuration for the Co3+. Apparently, the mechanism responsible for the formation of Pr4+ at low temperatures also helps to stabilize the Co3+ in the LS configuration despite the presence of Co4+ ions. We also found out that that the Co4+ is in an IS state over the entire temperature range investigated in this study (10-290 K). The presence of Co3+ HS and Co4+ IS at elevated temperatures facilitates the conductivity of the material.