Prediction of novel semi-conducting two-dimensional MX 2 phosphides and chalcogenides (M = Zn, Cd; X = P, S, Se) with 5-membered rings

• Published in: Physical chemistry chemical physics : PCCP 2023-11, Vol.25 (43), p.29506-29515
• Main Authors: Amaki, Esmail, Mahdavifar, Zabiollah, Frapper, Gilles
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D3CP04196D

The discovery of novel two-dimensional (2D) materials is a significant obstacle for contemporary materials science. Research in the field of 2D materials has mainly focused on materials possessing 6-membered rings, high symmetry, and isotropic features. The examination of 2D materials presenting 5-membered rings, low symmetry and anisotropic characteristics properties has received scarce attention. In this study, we employed evolutionary algorithms and heuristic approaches combined with first-principles calculations to predict penta-MX 2 structures (M = Zn, Cd; X = P, S, Se). All selected 2D penta-MX 2 phases are dynamically, thermodynamically, mechanically, and thermally stable. Further discussion focuses on their structural, bonding, electronic and optoelectronic features. Our HSE06 calculations reveal that the penta-MP 2 , ZnPS, and MSSe structures are semiconductors with a band gap of 0.80–3.08 eV. Conversely, the 2D penta-MPSe (M = Zn, Cd) and CdPS phases are metallic. We additionally note that penta β-ZnP 2 and CdP 2 display direct band gaps (1.39 eV and 1.18 eV, respectively), while the penta α-ZnP 2 , ZnPS, ZnSSe, α-CdSSe and β-CdSSe possess indirect band gaps. Remarkably, 2D pentagonal MP 2 (M = Zn, Cd), MSSe (M = Zn, Cd) and ZnPS 2D monolayers exhibit substantial optical absorption (>10 5 cm −1 ) throughout a broad range of the visible light spectra. Our results for crystal structure prediction expand the 2D penta-family of phosphides and chalcogenides, and demonstrate the potential of 2D penta-MX 2 materials for optoelectronic applications.