Epitaxial growth of black phosphorene enabled on black-phosphorene-like group IV-VI substrates

Black Phosphorene (BlackP) has been widely explored due to its unprecedented properties; however, the method of synthesizing high-quality samples in a large-area is still a daunting challenge. Here we use first-principles approaches to identify a highly desirable semiconducting SnSe substrate which is shown to be an ideal candidate for direct growth of BlackP. Our systematic energetic studies reveal that although both BlackP and its isomer, namely blue phosphorene (BlueP) can be stabilized on SnSe at low temperature, the later monolayer fails to maintain the ordered structure against thermal perturbation due to its weak interaction with the substrate. In contrast, the former retains the structure intact, as confirmed by our molecular dynamics simulations. We further study the atomistic growth mechanisms of the grown structure and find that the mutual interaction between the two phosphorus adatoms is attractive on SnSe(001), leading to the formation of dimers which is essentially favorable to achieve large-area samples. Furthermore, we show that in the ultraviolet region, such system possesses significantly improved optical properties than that of the BlackP, implying that this proposed system has promising potential in industrial applications.