Outstanding nonlinear optical properties of methylammonium- and Cs-PbX3 (X = Br, I, and Br–I) perovskites: Polycrystalline thin films and nanoparticles

Abstract

Metal Halide Perovskites (MHPs) have arisen as promising materials to construct cost-effective photovoltaic and light emission devices. The study of nonlinear optical properties of MHPs is necessary to get similar success in nonlinear photonic devices, which is practically absent in the literature. The determination of the third order nonlinear coefficients is typically done by the Z-scan technique, which is limited by the scattering of polycrystalline thin films. In this work, we have studied nonlinear optical properties of polycrystalline CH3NH3PbX3 (MAPbX3) thin films and colloidal CsPbX3 nanoparticles with three different bandgaps (X3 = I3, Br3, and Br1.5I1.5). Their bright generation of photoluminescence under infrared illumination demonstrates an excellent efficiency of multiphoton absorption. The nonlinear absorption coefficient (β) was studied by analyzing the transmitted light through the samples, observing the expected Eg−3 dependence with values as high as β = 1500 cm/GW. In addition, we proposed the use of a modified Z-scan technique with imaging processing to analyze the nonlinear refraction coefficient (n2) under the laser damage threshold. Our experimental data agree quite well with theoretical predictions, demonstrating the accuracy of the method and potential applications to other thin films. Moreover, n2 parameter reaches values of 3.5 cm2/GW, indicating the suitability of MHPs for nonlinear photonics.

Giant Nonlinear Optical Response in Triple Cation Halide Mixed Perovskite Films

“…The photoluminescence of MAPbBr 3 single crystal has also been observed in the green region (522–550 nm) with 1044 nm femtosecond laser excitation due to 2PA 26. Similar nonlinear optical properties were reported in inorganic perovskites, including CsPbI 3 and CsPbBr 3 22,27,28…”

Optical Amplification in Hollow-Core Negative-Curvature Fibers Doped with Perovskite CsPbBr3 Nanocrystals

“…Although the application of PNCs in optical nonlinear devices is currently at its very beginning, the few experimental studies show promising properties [52]. The values reported for colloidal solutions of CsPbBr 3 materials are about 2 × 10 −17 m 2 /W [52] and 1.2 × 10 −16 m 2 /W [53] for femtosecond and nanosecond excitation, respectively, but it is necessary to take into account that the concentration of PNCs in such colloidal solutions is usually low. Therefore, the nonlinear optical parameters can be much higher in thin films, as it is in our device.…”

Nonlinear Photonics Using Low‐Dimensional Metal‐Halide Perovskites: Recent Advances and Future Challenges

“…Excellent 2PA capability of CsPbBr 3 was quantified utilizing the OA Z‐scan method with fs pulsed laser excitation at 800 nm, and giant σ 2 value of ≈1.2 × 10 5 GM and ≈4.2 × 10 5 GM before and after the local field effect correction was revealed. Following this intriguing report, so far more than 34 other research works [ 92–96,99,101–111,138,189,234–248 ] on the 2PA response of NCs of 3D metal‐halide perovskites have been carried out and published. 2PA performance from NCs of 3D organic–inorganic MAPbX 3 and all‐inorganic CsPbX 3 (X = Cl, Br, I, or mixed halide) was the research focus in most of the published articles.…”

“…[ 98–100 ] Paired with the imaginary part of third‐order nonlinearity (2PA and SA), the corresponding real part (nonlinear refraction) has likewise expressed itself in the NCs with attractive merits. [ 101–104 ] What's more, greatly efficient higher‐order multiphoton absorption (MPA, from three‐photon up to five‐photon) have been demonstrated in 3D metal‐halide perovskite NCs by our group and other researchers. [ 92,93,105–107 ] In order to tune and optimize the MPA properties of 3D metal‐halide perovskite NCs, their dependence on sizes, [ 95,96 ] shape, [ 106 ] composition(e.g., Pauling electronegativity of halide anions at X sites), [ 92,105,107,108 ] bandgap, [ 95,104,107,108 ] and excitation wavelengths [ 92,95,96,106 ] have been investigated in detail.…”