Anisotropic linear and nonlinear excitonic optical properties of buckled monolayer semiconductors

The optical properties of two-dimensional materials are exceptional in several respects. They are highly anisotropic and frequently dominated by excitonic effects. Dipole-allowed second-order nonlinear optical properties require broken inversion symmetry. Hence, several two-dimensional materials show strong in-plane (IP) nonlinearity but negligible out-of-plane (OOP) response due to vertical symmetry. By considering buckled hexagonal monolayers, we analyze the critical role of broken vertical symmetry on their excitonic optical response. Both linear as well as second-order shift current and second-harmonic response are studied. We demonstrate that substantial OOP nonlinear response can be obtained, in particular, through off-diagonal tensor elements coupling IP excitation to OOP response. Our findings are explained by excitonic selection rules for OOP response and the impact of dielectric screening on excitons is elucidated.