Optical Third-Harmonic Generation in Graphene

We report strong third-harmonic generation in monolayer graphene grown by chemical vapor deposition and transferred to an amorphous silica (glass) substrate; the photon energy is in three-photon resonance with the exciton-shifted van Hove singularity at the M point of graphene. The polarization selection rules are derived and experimentally verified. In addition, our polarization- and azimuthal-rotation-dependent third-harmonic-generation measurements reveal in-plane isotropy as well as anisotropy between the in-plane and out-of-plane nonlinear optical responses of graphene. Since the third-harmonic signal exceeds that from bulk glass by more than 2 orders of magnitude, the signal contrast permits background-free scanning of graphene and provides insight into the structural properties of graphene.