Optical second-harmonic generation from two-dimensional hexagonal crystals with broken space inversion symmetry

We propose a microscopic theory of the optical second-harmonic generation (SHG) from pi electrons in two-dimensional (2D) honeycomb lattice structures with broken space inversion symmetry, such as graphene epitaxially grown on a SiC substrate and boronitrene (a single sheet of hexagonal boron nitride (h-BN)). The approach developed is based on a simple two-band pi-electron tight-binding model combined with the original Genkin-Mednis formalism of the second-order nonlinear optical response theory, detailed in our recent paper (2010 Phys. Rev. B 82 235426). Within the framework of the approach, we derive an explicit expression for the SHG susceptibility chi((2))(SHG)(omega), which involves two distinct contributions originating from a mixture of interband and intraband motion of pi electrons. Both the contributions, and, hence, the chi((2))(SHG)(omega) on the whole, are found to tend to zero when the pi-electron energy bands involved are treated at the simplest level of approximation, neglecting the effect of their trigonal warping around the corners of the Brillouin zone of the 2D hexagonal lattice. Through numerical calculations, it is shown that this effect, though rather small, leads to a fairly large magnitude of the SHG susceptibility, reaching the order of 10(-4) esu for the graphene/SiC overlayer system and 10(-7) esu for monolayer h-BN, when the pump photon energy (h) over bar omega approaches half the bandgap energy E-g of those structures. These theoretical findings suggest that SHG can be used as a sensitive optical probe of the electronic structure of the examined 2D hexagonal crystals and simultaneously demonstrate that those crystals may be an appropriate material for practical uses in future optoelectronic nano-devices.