The electronic structure of zircon-type orthovanadates: Effects of high-pressure and cation substitution

TL;DR

This study investigates how high pressure and cation substitution affect the electronic structure of zircon-type orthovanadates using optical measurements and first-principles calculations, revealing phase transitions and band-gap changes.

Contribution

It provides new insights into the pressure-induced electronic and structural transitions in zircon-type orthovanadates with different cation substitutions.

Findings

Cation substitution influences electronic states near the Fermi level.

Most studied orthovanadates undergo zircon-scheelite phase transition with band-gap collapse.

NdVO4 exhibits a zircon-monazite-scheelite sequence with two band-gap collapses.

Abstract

The electronic structure of four ternary-metal oxides containing isolated vanadate ions is studied. Zircon-type YVO4, YbVO4, LuVO4, and NdVO4 are investigated by high-pressure optical-absorption measurements up to 20 GPa. First-principles calculations based on density-functional theory were also performed to analyze the electronic band structure as a function of pressure. The electronic structure near the Fermi level originates largely from molecular orbitals of the vanadate ion, but cation substitution influence these electronic states. The studied ortovanadates, with the exception of NdVO4, undergo a zircon-scheelite structural phase transition that causes a collapse of the band-gap energy. The pressure coefficient dEg/dP show positive values for the zircon phase and negative values for the scheelite phase. NdVO4 undergoes a zircon-monazite-scheelite structural sequence with two associated band-gap collapses.