Coexistence of two types of short-range order in SiGeSn medium-entropy alloys

TL;DR

This study reveals that SiGeSn medium-entropy alloys naturally develop two distinct types of short-range order that coexist across various compositions, influencing their structural and electronic properties.

Contribution

It demonstrates the simultaneous presence of two different SROs in SiGeSn MEAs and explains their stability and implications for material properties.

Findings

Two types of SRO co-exist in SiGeSn alloys.

The two SROs have different energies and electronic structures.

Co-existence is due to near-degenerate thermodynamic stability.

Abstract

Short-range chemical order (SRO) has been recently demonstrated to play a decisive role in modulating a wide range of physical properties in medium-entropy alloy (MEA) and high-entropy alloy (HEA). The enormous configurational space of these alloys implies multiple forms of SRO are likely to develop concurrently but such structural diversity has not been reported. Here we show, through extensive {\em ab initio}-based sampling study, that SiGeSn medium-entropy alloys spontaneously develop two distinct forms of SRO. Remarkably, the two types of SROs, which carry different energies, distinct degrees of local ordering, and dissimilar electronic structures, are found to co-exist in a wide range of compositions of SiGeSn alloys. The co-existence of two SROs is rationalized through their virtual degeneracy of thermodynamic stability, due to the subtle balance in the change of enthalpy and configurational entropy upon the transformation between the two SROs. Such co-existence of SROs thus suggests an inherent structural heterogeneity, a diffuse electronic structure, and a new route for band engineering in SiGeSn MEA. More generally, our finding indicates the possible ubiquity of the co-existence of multiple forms of SRO in a broad range of MEAs and HEAs, which has profound implications on their diverse physical properties.