Quantum size confinement in gallium selenide nanosheets: band gap tunability versus stability limitation

Gallium selenide is one of the most promising candidates to extend the window of band gap values provided by existing two-dimensional semiconductors deep into the visible potentially reaching the ultraviolet. However, the tunability of its band gap by means of quantum confinement effects is still unknown, probably due to poor nanosheet stability. Here, we demonstrate that the optical band gap band of GaSe nanosheets can be tuned by ∼120 meV from bulk to 8 nm thick. The luminescent response of very thin nanosheets (<8 nm) is strongly quenched due to early oxidation. Oxidation favors the emergence of sharp material nanospikes at the surface attributable to strain relaxation. Simultaneously, incorporated oxygen progressively replaces selenium giving rise to Ga₂O_3, with a residual presence of Ga₂Se₃ that tends to desorb. These results are relevant for the development and design of visible/ultraviolet electronics and optoelectronics with tunable functionalities based on atomically thin GaSe.