Semiconducting edges and flake-shape evolution of monolayer GaSe: role of edge reconstructions

Group-III metal monochalcogenides have emerged as a new class of two-dimensional (2D) semiconductor materials. For the integration of 2D materials for various potential device applications, there is an inevitable need to reduce their dimensionality into specific sized nanostructures with edges. Owing to the properties of finite-sized 2D nanostructures strongly related to the edge configurations, the precise understanding of the edge geometric structures at an atomic level is of particular importance. By means of first-principles calculations, the geometric structures and electronic properties of stable zigzag and armchair edges in a prototype example GaSe monolayer have been identified. Our results demonstrate that both Ga- and Se-terminated zigzag edges prefer to the (3 × 1) reconstructions, and the armchair edges with the perfect flat configuration are energetically favorable. It is unexpectedly found that both zigzag and armchair GaSe nanoribbons with reconstructed edges are semiconductors, which is different from previous recognition where the zigzag edges are metallic. Moreover, the edge-dependent flake shape in GaSe has been plotted using the Wulff construction theory, and the shape evolution with chemical potentials can be applied to explain broad experimental observations on the morphologies of GaSe flakes. Importantly, similar reconstructions and electronic properties also appeared at InSe edges, suggesting that the reconstruction induced semiconducting edges are a fundamental phenomenon for 2D group-III metal monochalcogenides.