First-Principles Study of Electronic and Vibrational Properties of BaHfN$_2$

TL;DR

This study uses first-principles calculations to explore the electronic and vibrational properties of BaHfN$_2$, revealing its potential as a high-temperature superconductor upon doping, with detailed insights into its band structure and phonon behavior.

Contribution

It provides the first detailed electronic structure and vibrational analysis of BaHfN$_2$, highlighting its similarities to known superconducting nitrides and exploring doping effects.

Findings

BaHfN$_2$ has an indirect band gap of 0.8 eV.

The conduction band is mainly Hf 5$d_{xy}$ character.

Anisotropic Born effective charges and phonon properties are characterized.

Abstract

The transition metal nitride BaHfN$_2$, which consists of weakly bonded neutral slabs of closed shell ions, has structural and chemical similarities to other layered nitrides which have impressive superconducting T$_c$ when electron doped: A$_x$HfNCl, A$_x$ZrNCl, A$_x$TiNCl, with $T_c= 25.5$, $15.2$ and $16.5$ K, respectively for appropriate donor (A) concentrations $x$. These similarities suggest the possibility of BaHfN$_2$ being another relatively high T$_c$ nitride upon doping, with effects of structure and the role of specific transition metal ions yet to be understood. We report first-principles electronic structure calculations for stoichiometric BaHfN$_2$ using density functional theory with plane-wave basis sets and separable dual-space Gaussian pseudopotentials. An indirect band gap of 0.8 eV was obtained and the lowest conduction band is primarily of Hf 5$d_{xy}$ character, similar to $\beta$-ZrNCl and $\alpha$-TiNCl. The two N sites, one in the Hf layer and another one in the Ba layer, were found to have very anisotropic Born effective charges (BEC):deviations from the formal charge (-3) are opposite for the two sites, and opposite for the two orientations (in-plane, out of plane). LO-TO splittings and comparison of BECs and dielectric constant tensors to those of related compounds are discussed, and the effect of electron doping on the zone-center phonons is reported.