Tuning of the Ru$^{\mathbf{4+}}$ ground-state orbital population in the $\mathbf{4d^4}$ Mott insulator Ca$_2$RuO$_4$ achieved by La doping

TL;DR

This study investigates how La doping influences the orbital occupancy and electronic structure of Ca$_2$RuO$_4$, revealing that structural changes, rather than free carrier injection, drive the transition from insulating to metallic phases.

Contribution

It combines X-ray absorption spectroscopy with theoretical modeling to elucidate how crystal field variations affect orbital populations in La-doped Ca$_2$RuO$_4$.

Findings

Orbital occupancy ratio increases with doping in insulating samples.

Metallic phase shows temperature-independent spectra not explained by simple models.

Structural changes, not free carriers, primarily drive the phase transition.

Abstract

The ground-state orbital occupancy of the Ru$^{4+}$ ion in Ca$_{2-x}$La$_x$RuO$_4$ [x=0, 0.05(1), 0.07(1) and 0.12(1)] was investigated by performing X-ray absorption spectroscopy (XAS) in the vicinity of the O K edge as a function of angle between the incident beam and the surface of the crystals. A minimal model of the hybridization between the O 2p states probed at the K edge and the Ru 4d orbitals was used to analyze the XAS data, allowing the ratio of hole occupancies $n_{xy}/n_{yz,zx}$ to be determined as a function of doping and temperature. For the samples displaying a low-temperature insulating ground-state ($x\leq0.07$), $n_{xy}/n_{yz,zx}$ is found to increase significantly with increasing doping. For x=0.12, which has a metallic ground-state, the XAS spectra are found to be independent of temperature, and not to be describable by the minimal hybridization model. To understand the origin of the evolution of the electronic structure across the phase diagram, we have performed theoretical calculations based on a model Hamiltonian, comprising electron-electron correlations, crystal field ($\Delta$) and spin-orbit coupling ($\lambda$), of a Ru-O-Ru cluster. Our calculations of the Ru hole occupancy as a function of $\Delta/\lambda$ establish that the enhancement of $n_{xy}/n_{yz,zx}$ is driven by significant changes to the crystal field as the tetragonal distortion of the RuO$_6$ octahedral changes from compressive to tensile with La doping. It also shows that the hole occupancy of the O 2p and Ru 4d orbitals display the same trend as a function of $\Delta/\lambda$, thus validating the minimal hybridization model. In essence, our results suggest that the predominant mechanism driving the emergence of the low-temperature metallic phase in La doped Ca$_2$RuO$_4$ is the structurally induced redistribution of holes within the t2g orbitals, rather that the injection of free carriers.