Multiphoton Absorption Order of CsPbBr₃ As Determined by Wavelength-Dependent Nonlinear Optical Spectroscopy

CsPbBr₃ is a direct-gap semiconductor where optical absorption takes place across the fundamental bandgap, but this all-inorganic halide perovskite typically exhibits above-bandgap emission when excited over an energy level, lying above the conduction-band minimum. We probe this bandgap anomaly using wavelength-dependent multiphoton absorption spectroscopy and find that the fundamental gap is strictly two-photon forbidden, rendering it three-photon absorption (3PA) active. Instead, two-photon absorption (2PA) commences when the two-photon energy is resonant with the optical gap, associated with the level causing the anomaly. We determine absolute nonlinear optical dispersion over this 3PA-2PA region, which can be explained by two-band models in terms of the optical gap. The polarization dependence of 3PA and 2PA is also measured and explained by the relevant selection rules. CsPbBr₃ is highly luminescent under multiphoton absorption at room temperature with marked polarization and wavelength dependence at the 3PA-2PA crossover and therefore has potential for nonlinear optical applications.