Graphether: A Two-Dimensional Oxocarbon as a Direct Wide-Gap Semiconductor with High Mechanical and Electrical Performances

TL;DR

Graphether is a newly designed two-dimensional oxocarbon with a wide direct band gap, high mechanical strength, and excellent stability, promising for optoelectronic and catalytic applications.

Contribution

This work introduces a novel 2D oxocarbon, graphether, with unique hyperconjugation-based structure, high stability, wide band gap, and superior mechanical and electronic properties.

Findings

Monolayer graphether is dynamically and thermally stable.

It has a direct band gap of 2.39 eV robust against strain.

Graphether exhibits high electron mobility and in-plane stiffness surpassing graphene.

Abstract

Although many graphene derivatives have sizable band gaps, their electrical or mechanical properties are significantly degraded due to the low degree of {\pi}-conjugation. Besides the {\pi}-{\pi} conjugation, there exists hyperconjugation interactions arising from the delocalization of {\sigma} electrons. Inspired by the structural characteristics of a hyperconjugated molecule, dimethyl ether, we design a two-dimensional oxocarbon (named graphether) by the assembly of dimethyl ether molecules. Our first-principle calculations reveal the following findings: (1) Monolayer graphether possesses excellent dynamical and thermal stabilities as demonstrated by its favourable cohesive energy, absence of the soft phonon modes, and high melting point. (2) It has a direct wide-band-gap of 2.39 eV, indicating its potential applications in ultraviolet optoelectronic devices. Interestingly, the direct band gap feature is rather robust against the external strains (-10% to 10%) and stacking configurations. (3) Due to the hyperconjugative effect, graphether has the high intrinsic electron mobility. More importantly, its in-plane stiffness (459.8 N m-1) is even larger than that of graphene. (4) The Pt(100) surface exhibits high catalytic activity for the dehydrogenation of dimethyl ether. The electrostatic repulsion serves as a driving force for the rotation and coalescence of two dehydrogenated precursors, which is favourable for the bottom-up growth of graphether. (5) Replacement of the C-C bond with an isoelectronic B-N bond can generate a stable Pmn21-BNO monolayer. Compared with monolayer hexagonal boron nitride, Pmn21-BNO has a moderate direct band gap (3.32 eV) and better mechanical property along the armchair direction.