Second-order nonlinear optical properties of copper-based hybrid organic-inorganic perovskites induced by chiral amines.

Recently, chiral hybrid organic-inorganic perovskites (HOIPs) are drawing wide attention due to their intrinsic noncentrosymmetric structures which result in fascinating properties such as ferroelectronics and second-order nonlinear optics (NLO). However, previous research mainly focused on chiral lead-based halide perovskites ignoring that the toxic Pb element is harmful to humans and the environment. Herein, we successfully synthesized block-like (R-/S-NEA)2CuCl4 (NEA = 1-naphthylethylamine) and needle-like (R-/S-CYHEA)6Cu3Cl12 (CYHEA = 1-cyclohexylethylamine) single crystals, which crystallize in the Sohncke P21 and I2 space group, respectively. Each pair of chiral perovskite enantiomers shows mirror circular dichroism (CD) signals. The thin films show an efficient second harmonic generation (SHG) response and the NLO coefficients of (R-NEA)2CuCl4 and (R-CYHEA)6Cu3Cl12 are 11.74 and 3.04 pm V-1, respectively, under 920 nm excitation with Y-cut quartz as a reference, which shows that the chiral amine has a significant effect on the SHG behavior. The high SHG response of (R-NEA)2CuCl4 is perhaps due to the rigidity of the aromatic amine, which leads to highly asymmetrical space groups. Our results provide guidelines for designing and tuning the SHG response in chiral HOIPs.

Ligand Exchange Strategy to Achieve Chiral Perovskite Nanocrystals with a High Photoluminescence Quantum Yield and Regulation of the Chiroptical Property.

Chiral nanomaterials have drawn extensive attention on account of numerous application prospects in optoelectronics, asymmetric catalysis, chiral recognition, and three-dimensional (3D) display. Thereinto, chiral perovskite has been a hotspot due to brilliant optoelectronic properties, but some problems limit the development, including low quantum yield, low chiral intensity, and the lack of facile regulation. To overcome these issues, an effective ligand exchange strategy, i.e. the interface modification has been proposed for chiral perovskite nanocrystals (PNCs). With the surface modification of CsPbBr3 PNCs with chiral organic ammonium in methyl acetate in the typical purification process, excellent circular dichroism (CD) signals were obtained and defects were eliminated, leading to an increase in the photoluminescence quantum yield (PLQY) from 50% to nearly 100%. The CD signal can be regulated through a ligand exchange strategy in the longitudinal dimension, the chiral intensity, and the transverse dimension, the wavelength range. Here, the proper addition of R-α-PEAI into the R-α-PEABr-capped CsPbBr3 PNCs can produce a superstrong CD signal with the highest anisotropy factor (g-factor) of 0.0026 in the visible region among reported chiral colloidal PNCs. Simultaneously, the luminescence emission can be tuned from the green to red region with boosted PLQY through the approach. The density functional theory (DFT) calculation result supports that chirality comes from the hybridization between the energy level of a perovskite structure and that of chiral organic molecules. These properties can be used in the structural engineering of high-performance chiral optical materials, spin-polarized light-emitting devices, and polarized optoelectronic devices.