First-Principles Study of Two-Dimensional Ferroelectrics Using Self-Consistent Hubbard Parameters

TL;DR

This study uses a self-consistent Hubbard parameter approach within DFT to accurately predict electronic properties of 2D ferroelectrics, improving band gap predictions and understanding surface interactions relevant for catalysis.

Contribution

It introduces a first-principles method with self-consistent Hubbard parameters to enhance electronic structure predictions of 2D ferroelectrics, including band gaps and surface adsorption energies.

Findings

ACBN0 improves band gap predictions for 2D ferroelectrics.

Inter-site Coulomb interaction V is crucial for heterostructure electronic descriptions.

Self-consistent U corrections significantly affect molecule adsorption energies.

Abstract

The discovery of two-dimensional (2D) materials possessing switchable spontaneous polarization with atomic thickness opens up exciting opportunities to realize ultrathin, high-density electronic devices with potential applications ranging from memories and sensors to photocatalysis and solar cells. First-principles methods based on density functional theory (DFT) have facilitated the discovery and design of 2D ferroelectrics (FEs). However, DFT calculations employing local and semilocal exchange-correlation functionals failed to predict accurately the band gaps for this family of low-dimensional materials. Here, we present a DFT+$U$+$V$ study on 2D FEs represented by single-layer $\alpha$-In$_2$Se$_3$ and its homologous III$_2$-VI$_3$ compounds with both out-of-plane and in-plane polarization, using Hubbard parameters computed from first-principles. We find that ACBN0, a pseudo-hybrid density functional that allows self-consistent determination of $U$ parameters, improves the prediction of band gaps for all investigated 2D FEs with a computational cost much lower than the hybrid density functional. The inter-site Coulomb interaction $V$ becomes critical for accurate descriptions of the electronic structures of van der Waals heterostructures such as bilayer In$_2$Se$_3$ and In$_2$Se$_3$/InTe. Pertinent to the study of FE-based catalysis, we find that the application of self-consistent $U$ corrections can strongly affect the adsorption energies of open-shell molecules on the polar surfaces of 2D FEs.