Resonant Degenerate Four-Wave Mixing at the Defect Energy Levels of 2D Organic-Inorganic Hybrid Perovskite Crystals.

Two-dimensional organic-inorganic lead halide perovskites are generating great interest due to their optoelectronic characteristics such as high solar energy conversion efficiency and a tunable direct band gap in the visible regime. However, the presence of defect states within the two-dimensional crystal structure can affect these properties, resulting in changes to their band gap emission as well as the emergence of nonlinear optical phenomena. Here, we have investigated the effects of the presence of defect states on the nonlinear optical phenomena of the 2D hybrid perovskite (BA)2(MA)2Pb3Br10. When two pulses, one narrowband pump pulse centered at 800 nm and one supercontinuum pulse with bandwidth from 800-1100 nm, are incident on a perovskite flake, degenerate four-wave mixing (FWM) occurs, with peaks corresponding to the energy levels of the defect states present within the crystal. The longer carrier lifetime of the defect state, in comparison to that of virtual transitions that take place in nonresonant FWM processes, allows for a larger population of electrons to be excited by the second pump photon, resulting in increased FWM signal at the defect energy levels. The quenching of the two-photon luminescence as flake thickness increases is also observed and attributed to the increased presence of defects within the flake at larger thicknesses. This technique shows the potential of detecting defect energy levels in crystals using FWM for a variety of optoelectronic applications.