Semiconducting SiGeSn High-Entropy Alloy: A Density Functional Theory Study

TL;DR

This study uses density functional theory to investigate the atomic structure, electronic properties, and vacancy energetics of a semiconducting SiGeSn high-entropy alloy, revealing its potential for mid-infrared optoelectronics.

Contribution

It provides the first detailed DFT analysis of SiGeSn HEA, demonstrating its semiconducting nature and unique vacancy properties compared to metallic HEAs.

Findings

SiGeSn HEA exhibits large local lattice distortion.

It remains semiconducting with a 0.38 eV band gap.

Vacancy formation energies show wide distribution with small lower bounds.

Abstract

High-entropy alloys (HEAs), which have been intensely studied due to their excellent mechanical properties, generally refer to alloys with multiple equimolar or nearly equimolar elements. According to this definition, Si-Ge-Sn alloys with equal or comparable concentrations of the three Group IV elements belong to the category of HEAs. As a result, the equimolar elements of Si-Ge-Sn alloys likely cause their atomic structures to exhibit the same core effects of metallic HEAs such as lattice distortion. Here we apply density functional theory (DFT) calculations to show that the SiGeSn HEA indeed exhibits a large local distortion effect. Unlike metallic HEAs, our Monte Carlo and DFT calculations show that the SiGeSn HEA exhibits no chemical short-range order due to the similar electronegativity of the constituent elements, thereby increasing the configurational entropy of the SiGeSn HEA. Hybrid density functional calculations show that the SiGeSn HEA remains semiconducting with a band gap of 0.38 eV, promising for economical and compatible mid-infrared optoelectronics applications. We then study the energetics of neutral single Si, Ge, and Sn vacancies and (expectedly) find wide distributions of vacancy formation energies, similar to those found in metallic HEAs. However, we also find anomalously small lower bounds (e.g., 0.04 eV for a Si vacancy) in the energy distributions, which arise from the bond reformation near the vacancy. Such small vacancy formation energies and their associated bond reformations retain the semiconducting behavior of the SiGeSn HEA, which may be a signature feature of a semiconducting HEA that differentiates from metallic HEAs.