Unusual negative formation enthalpies and atomic ordering in isovalent alloys of transition metal dichalcogenide monolayers

TL;DR

This study uses first-principles calculations to reveal that monolayer transition metal dichalcogenide alloys exhibit negative formation enthalpies and local atomic ordering, with implications for their optical and electronic properties.

Contribution

It uncovers the atomic ordering mechanisms in TMD alloys and explains why such ordering is locally present but not long-range, aiding future experimental and application efforts.

Findings

Negative formation enthalpies indicate atomic ordering tendencies.

Local ordering affects defect properties but not macroscopic optical features.

Quaternary alloys offer tunable bandgaps for optoelectronic use.

Abstract

Common substitutional isovalent semiconductor alloys usually form disordered metastable phases with positive excess formation enthalpies ({\Delta}H). In contrast, monolayer alloys of transition metal dichalcogenides (TMDs) MX2 (M = Mo, W; X = S, Se) always have negative {\Delta}H, suggesting atomic ordering, which is, however, not yet experimentally observed. Using first-principles calculations, we find that the negative {\Delta}H of cation-mixed TMD alloys results from the charge transfer from weak Mo-X to nearest strong W-X bonds and the negative {\Delta}H of anion-mixed TMD alloys comes from the larger energy gain due to the charge transfer from Se to nearest S atoms than the energy cost due to the lattice mismatch. Consequently, cation-mixed and anion-mixed alloys should energetically prefer to have Mo-X-W and S-M-Se ordering, respectively. The atomic ordering, however, is only locally ordered but disordered in the long range due to the symmetry of TMD monolayers, as demonstrated by many energetically degenerate structures for given alloy compositions. Besides, the local ordering and disordering effects on the macroscopic properties such as bandgaps and optical absorptions are negligible, making the experimental observation of locally ordered TMD alloys challenging. We propose to take the advantage of microscopic properties such as defects which strongly depend on local atomic configurations for experiments to identify the disordering and local ordering in TMD alloys. Finally, quaternary TMD alloys by mixing both cations and anions are studied to have a wide range of bandgaps for optoelectronic applications. Our work is expected to help the formation and utilization of TMD alloys.