Using first-principles calculations, we have investigated the evolution of
band-edges in few-layer phosphorene as a function of the number of P layers.
Our results predict that monolayer phosphorene is an indirect band gap
semiconductor and its valence band edge is extremely sensitive to strain. Its
band gap could undergo an indirect-to-direct transition under a lattice
expansion as small as 1% along zigzag direction. A semi-empirical interlayer
coupling model is proposed, which can well reproduce the evolution of valence
band-edges obtained by first-principles calculations. We conclude that the
interlayer coupling plays a dominated role in the evolution of the band-edges
via decreasing both band gap and carrier effective masses with the increase of
phosphorene thickness. A scrutiny of the orbital-decomposed band structure
provides a better understanding of the upward shift of valence band maximum
surpassing that of conduction band minimum.Comment: 25 pages, 9 figure