Large Electronic Anisotropy and Enhanced Chemical Activity of Highly Rippled Phosphorene

TL;DR

This study reveals that highly rippled phosphorene exhibits significant electronic anisotropy and enhanced chemical activity due to curvature effects, with potential applications in optoelectronics and catalysis.

Contribution

It provides first-principles insights into how large ripples and strains modulate phosphorene's electronic and chemical properties, highlighting its bendability and anisotropic behavior.

Findings

Band gap varies with strain and ripple direction.

Semiconductor to metal transition along zigzag ripples.

Enhanced chemical activity at ripple peaks.

Abstract

We investigate the electronic structure and chemical activity of rippled phosphorene induced by large compressive strains via first-principles calculation. It is found that phosphorene is extraordinarily bendable, enabling the accommodation of ripples with large curvatures. Such highly rippled phosphorene shows a strong anisotropy in electronic properties. For ripples along the armchair direction, the band gap changes from 0.84 to 0.51 eV for the compressive strain up to -20% and further compression shows no significant effect, for ripples along the zigzag direction, semiconductor to metal transition occurs. Within the rippled phosphorene, the local electronic properties, such as the modulated band gap and the alignments of frontier orbitals, are found to be highly spatially dependent, which may be used for modulating the injection and confinement of carriers for optical and photovoltaic applications. The examination of the interaction of a physisorbed NO molecule with the rippled phosphorene under different compressive strains shows that the chemical activities of the phosphorene are significantly enhanced at the top and bottom peaks of the ripples, indicated by the enhanced adsorption and charge transfer between them. All these features can be ascribed to the effect of curvatures, which modifies the orbital coupling between atoms at the ripple peaks.