H2 O incorporation in the phosphorene/a-SiO2 interface: A first-principles study

TL;DR

This study uses first-principles calculations to analyze the stability and electronic properties of phosphorene on amorphous SiO2, focusing on water incorporation effects at the interface, revealing charge puddles and chemical bond formations.

Contribution

It provides new insights into water's role at the phosphorene/SiO2 interface, including hydroxyl and P--O--Si bond formation, based on first-principles modeling.

Findings

Phosphorene bonds via van der Waals interactions on amorphous SiO2.

Type-I band alignment with charge puddles influenced by oxygen vacancies.

Water incorporation leads to hydroxyl groups and stable P--O--Si bonds.

Abstract

Based on first-principles calculations, we investigate the energetic stability and the electronic properties of (i) a single layer phosphorene (SLP) adsorbed on the amorphous sio2 surface (SLP/a-sio2), and (ii) the further incorporation of water molecules at the phosphorene/a-sio2 interface. In (i), we find that the phosphorene sheet bonds to a-sio2 through van der Waals interactions, even upon the presence of oxygen vacancy on the surface. The \slp/a-\sio\ system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-\sio\ substrate. The structural, and the surface-potential corrugations promote the formation of electron-rich and -poor regions on the phosphorene sheet and at the SLP/a-sio2 interface. Such charge density puddles have been strengthened by the presence of oxygen vacancies in a-sio2. In (ii), due to the amorphous structure of the surface, we have considered a number of plausible geometries of water embedded in the SLP/a-sio2 interface. There is an energetic preference to the formation of hydroxyl (OH) groups on the a-sio2 surface. Meanwhile, upon the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we find the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P--O--Si chemical bonds at the SLP/a-sio2 interface. Further x-ray absorption spectra (XAS) simulations have been done, aiming to provide additional structural/electronic informations of the oxygen atoms forming hydroxyl groups or P--O--Si chemical bonds at the interface region.