Functionalization reveals potential opportunities for modifying essential properties and designing materials due to the strong interaction between functionalized atoms and the surface. Among them, hydrogenation possesses such a way to control electronic and optical characteristics. In this paper, the stability and transformed electronic, optical properties of H-functionalized GaSe in two cases (single and double sites) were reported that exhibit the effects of hydrogen functionalization via first-principles calculations. Formation energies suggest that H-functionalized GaSe systems are stable for construction. H-GaSe and 2H-GaSe display distinct properties based on the functionalized way (single- or double-site functionalization). Accordingly, H-GaSe is metallic, while 2H-GaSe belongs to a semiconductor. The magnetic configuration with ferro- and anti-ferromagnetic could be found in H- and 2H-functionalized cases through spin distribution, respectively. Especially, the chemical hybridized bonds of Se-H, Ga-Se, and Ga-Ga corresponding to s-sp3 and sp3-sp3 bondings, respectively, are clearly verified in the orbital-projected density of states and charge density. The optical properties of 2H-GaSe could provide the main characteristics of a semiconductor, which is the limited range of transparency by electronic absorption at short and long wavelengths. Moreover, increasing the number of GaSe segments (L) could change the band gap leading to application in the band gap engineering of the 2H-GaSe systems. Thus, hydrogen functionalization could provide the possible manner for adjusting and controlling features of GaSe, promising for the development of electronic devices and applications.
© 2022 The Authors. Published by American Chemical Society.