Ground- and excited-state properties of LiNb$_{1-x}$Ta$_x$O$_3$ solid solutions

TL;DR

This study combines first-principles calculations and optical spectroscopy to analyze the structural and electronic properties of LiNb$_{1-x}$Ta$_x$O$_3$ solid solutions across compositions, revealing deviations from Vegard's law and unique polarization features.

Contribution

It provides a comprehensive theoretical and experimental analysis of LiNb$_{1-x}$Ta$_x$O$_3$ solid solutions, highlighting deviations from expected linear behavior and discovering a unique composition with unusual polarization.

Findings

Deviations from Vegard's law in lattice parameters and bandgap.

Optical spectroscopy confirms theoretical predictions.

LiNb$_{0.11}$Ta$_{0.89}$O$_3$ exhibits permanent polarization without birefringence.

Abstract

LiNb$_{1-x}$Ta$_x$O$_3$ solid solutions are investigated from first principles and by optical spectroscopy. The ground- and excited-state properties of the solid solutions are modelled within density functional theory as a function of the Ta concentration using special quasirandom structures spanning the entire composition range between LiNbO$_3$ and LiTaO$_3$. Deviations from a Vegard behavior are predicted for the lattice parameters, the heat capacity, the electronic bandgap, and consequently the absorption edge. The latter is measured for crystals of different composition by low temperature optical spectroscopy, qualitatively confirming the theoretical predictions. The LiNb$_{0.11}$Ta$_{0.89}$O$_3$ composition is found to be a highly unusual crystal with a permanent macroscopic electric polarization and nonetheless zero birefringence.