Tailoring the optical properties of MoS2 and WS2 single layers via organic functionalization

Tailoring the structural and electronic properties of 2D materials is fundamental to boost their use in a wide range of technological applications. In this paper, by means of first principles simulations, we show how methyl functionalization of MoS2 and WS2 monolayers can be employed to change their energy gap, tune their optoelectronic properties and modify the relative stability of their structural phases (or polytypes). In particular for both compound monolayers, we find that the most stable semiconducting H phase becomes metallic upon methyl functionalization, while in the metastable T′ phase the band gap increases as a function of the -CH3 coverage; correspondingly the phase stability is reversed and the on-set of the optical absorption is blue-shifted.