Graphenenanoribbon band-gap expansion: Broken-bond-induced edge strain and quantum entrapment

Abstract

An edge-modified tight-binding (TB) approximation has been developed, enabling us to clarify the energetic origin of the width-dependent band gap (E_G) expansion of the armchaired and the reconstructed zigzag-edged graphene nanoribbons with and without hydrogen termination. Consistency between the TB and the density-function theory calculations affirmed that: (i) the E_G expansion originates from the Hamiltonian perturbation due to the shorter and stronger bonds between undercoordinated atoms, (ii) the combination of the edge-to-width ratio with a local bond strain up to 30% and the associated 152% potential well depression determines the width dependent E_G change; and, (iii) hydrogen termination affects insignificantly the band gap width as the H-passivation minimizes the midgap impurity states.