Charge Transfer and Functionalization of Monolayer InSe by Physisorption of Small Molecules for Gas Sensing

First-principles calculations are performed to investigate the effects of the adsorption of gas molecules (CO, NO, NO2, H2S, N-2, H2O, O-2, NH3, and H-2) on the electronic properties of atomically thin indium selenium (InSe). Our study shows that the lone-pair states of Se are located at the top of the valence band of InSe and close to the Fermi energy level, implying its high sensitivity to external adsorbates. Among these gas molecules, H-2 and H2S are strong donors; NO, NO2, H2O, and NH3 are effective acceptors; while CO and N-2 exhibit negligible charge transfer. The O-2 molecule has very limited oxidizing ability and a relatively weak interaction with InSe which is comparable to the N-2 adsorption. A clear band gap narrowing is found for the H2S, NO2, and NH3 adsorbed systems, whereas a Fermi level shifting to the conduction band is observed upon a moderate uptake of H-2 molecules. Our analysis suggests several interesting applications of InSe: (1) due to the different interaction behaviors with these external molecules, InSe can be used for gas sensing applications; (2) by monitoring the adsorption/desorption behavior of these gas molecules, the population of hole states in InSe due to photon stimulation or defect production can be quantitatively estimated; and (3) it is promising for novel electronic and optoelectronic applications since the adsorption-induced in-gap states and strong charge transfer are able to change the content and polarity of charged carriers and lead to different optical properties.