Multiphoton Absorption Coefficients of Organic–Inorganic Lead Halide Perovskites CH3NH3PbX3 (X = Cl, Br, I) Single Crystals

Hybrid organic–inorganic lead halide perovskites have recorded unprecedented improvement in efficiency as fourth-generation photovoltaic materials. Recently, they have attracted enormous interest in nonlinear optics stemming basically from their excellent optoelectronic properties. Here, we investigate multiphoton absorption (MPA) in high-quality MAPbX3 (MA = CH3NH3 and X = Cl, Br, I) bulk single crystals synthesized by an inverse-temperature crystallization (ITC) method. The two-photon absorption (2PA) coefficients under picosecond pulse excitation are determined to be β = 23 ± 2 cm/GW and 9 ± 1 cm/GW for MAPbI3 and MAPbBr3 at λ = 1064 nm, and 13 ± 2 cm/GW for MAPbCl3 at λ = 532 nm. The 2PA coefficients are comparable to those of conventional semiconductors having similar bandgaps and can be explained by a two-band model. Furthermore, we characterize the three-photon absorption behavior of MAPbCl3 at λ = 1064 nm, yielding γ = 0.05 ± 0.01 cm3/GW2. The polarization dependence of MPA is also probed to exper...