Phase stability of two-dimensional monolayer As1-xPx solid solutions revealed by a first-principles cluster expansion

Open Access

Abstract

The phase stability of two-dimensional monolayer As1-xPx solid solutions, exhibiting the puckered (alpha phase) and buckled (beta phase) structures are investigated using a first-principles cluster-expansion method. Canonical Monte Carlo simulations, together with harmonic approximation, are performed to capture the influences of thermally induced configurational disorder and lattice vibrations on the phase stability of monolayer As1-xPx. We first demonstrate that, as the temperature approaches 0 K, the monolayer As1-xPx displays a tendency toward phase separation into its constituent elemental phases, and thus no stable ordered structures of As1-xPx, both alpha and beta phases, are predicted to be thermodynamically stable. We further reveal with the inclusion of the lattice vibrational contributions that beta-As1-xPx is thermodynamically favored over alpha-As1-xPx, across the entire composition range even at 0 K and increasingly so at higher temperature, and a continuous series of disordered solid solution of beta-As1-xPx, where 0 amp;lt;= x amp;lt;= 1, is predicted at the temperature above 550 K. These findings not only indicate that the ordered structures of monolayer alpha-As1-xPx, and beta-As1-xPx, frequently studied in the literature, may not exist in nature, but also presumably suggest that monolayer alpha-As1-xPx is metastable with respect to monolayer beta-As1-xPx. ; Funding Agencies|Swedish Research Council (VR) [2014-6336]; Marie Sklodowska Curie Actions, Cofund, Project [INCA 600398]; Swedish Foundation for Strategic Research (SSF) through the Future Research Leaders 6 programme; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Kungl. Ingenjorsvetenskapsakademiens Hans Werthen-Fond