Investigation of the Electronic Structure and Spin-State Crossover in LaCoO3 Using Photoemission Spectroscopy

TL;DR

This study uses advanced photoemission spectroscopy techniques to investigate the electronic structure and spin-state crossover in LaCoO3, revealing temperature-dependent changes in orbital states and quantifying the high-spin fraction at elevated temperatures.

Contribution

It provides a comprehensive analysis combining multiple photoemission methods to elucidate the spin-state transition mechanisms in LaCoO3, including quantitative spin-state fraction estimation.

Findings

Identification of Co 3d and O 2p features and their evolution with photon energy.

Observation of a temperature-dependent suppression of specific spectral features.

Quantification of the high-spin state reaching about 30% at 400 K.

Abstract

Photoemission spectroscopy is a powerful technique for studying electronic structure and spin-state transitions, as it reveals changes in the orbital configuration accompanying a spin-state crossover. In this report, we combine excitation-energy-, temperature-, and geometry-dependent photoemission measurements to probe the electronic structure of LaCoO3 across its thermally driven spin-state transition. By systematically comparing valence-band spectra across a wide photon-energy window - from surface-sensitive soft x-ray photoemission spectroscopy (SXPS) to bulk-sensitive hard x-ray photoemission spectroscopy (HAXPES) - we identify the Co 3d-derived feature (A) along with the O 2p-dominated features (B and C), and explain their relative evolution in terms of photon-energy-dependent photo-ionization cross-section ratios. The thermally induced spin-state crossover is demonstrated using temperature-dependent SXPS valence-band spectra, which show a progressive suppression of the feature A with heating. Geometry-dependent HAXPES measurements further clarify how the signature of the spin-state transition in LaCoO3 is intricately linked to the orbital-selective response of the t2g and eg states. Additionally, angular-dependent photo-ionization cross-section analysis provides a consistent description of the polarization dependence observed in HAXPES. Finally, configuration-interaction analysis of the Co 2p core-level spectra reveals that LaCoO3 evolves from a predominantly low-spin ground state at low temperature to a mixed low-spin/high-spin configuration at elevated temperatures, with the high-spin fraction reaching about 30 percent at 400 K. The temperature evolution of the core-level line shape thus establishes Co 2p photoemission as a sensitive quantitative probe of spin-state transitions in LaCoO3.