Tin‐Based Chiral Perovskites with Second‐Order Nonlinear Optical Properties

Abstract

Metal halide perovskites have attracted extensive attention as the most favorable candidate for nonlinear optical (NLO) effects, due to their superior infrared transparency, flexible structures, and high laser‐induced damage thresholds. Among the perovskite branches, the lead‐based perovskites dominate in virtue of their fascinating optoelectronic properties. However, the ambient instability and toxicity of lead impede their practical applications. Herein, a new class of air‐stable and lead‐free zero‐dimension chiral perovskites manifesting efficient second‐order NLO response is reported. Interestingly, the tin‐based perovskites demonstrate double‐step reversible phase transitions with an acentric space group P21 at room temperature, whereas their racemic counterparts undergo a distinct one‐step phase transition crystallizing in centric space group P21/c. These findings reveal an executable approach to designing multifunctional lead‐free perovskite‐type switchable materials with second harmonic generation (SHG) properties.

Regulating Optical Activity and Anisotropic Second-Harmonic Generation in Zero-Dimensional Hybrid Copper Halides

“…Therefore, these d eff values are only an approximation of the order of magnitude. It should be noted that our results have the same order of magnitude as chiral 2D lead-based perovskite nanowires and are slightly lower than chiral 0D tin-based perovskite crystals. , The larger d eff value of 1- R should be attributed to its larger d 22 / d 16 ratio, but further investigation is required to confirm this. In addition, the SHG anisotropy, which is quantified as ρ = ( I max – I min )/( I max + I min ), was determined to be ∼0.84 and ∼0.92 for 1- R and 2- R , respectively.…”

“…Under such circumstances, chiral HMHs have shown promise for use as SHG materials due to their inherent structural asymmetry. To date, efficient SHG has been demonstrated in lead-, ,− copper-, antimony-, bismuth-, and tin-based chiral HMHs . Furthermore, SHG is not only a significant nonlinear optical response but also a commonly used technique for revealing the structural symmetry of materials. − In particular, the second-order nonlinear susceptibility, represented by the d -coefficient, reflects the inherent structural symmetry of materials and can be divided into different symmetry classes by a d -matrix .…”

Tunable and Large Magneto‐Photoluminescence for Single‐Crystalline Chiral Perovskites

“…Nevertheless, the chiral perovskites with a variety of metal compositions such as lead (Pb), cadmium (Cd), and tin (Sn) are proven to be excellent candidates for chiroptical spintronics, nonlinear optics, photodetectors, ferroelectricity, ferroelastic switches, and spin-polarized electronic transport since they exhibit the so-called chirality-induced spin selectivity (CISS). [15][16][17][18][19][20][21][22][23][24][25][26][27] Such effect stems from the chiral induced spin orbit coupling (SOC). [28,29] Depending on the material chirality, only one channel of the spin angular momenta either spinup (↑) or spin-down (↓) can be well preserved for the selectively optical excitation and electronic/spin transport.…”

0D chiral hybrid indium(iii) halides for second harmonic generation

“…12,80 The value of the polarization ratio, ρ = (I max − I min )/(I max + I min ), was calculated to be (93.1 ± 0.1) % for p-analyzers, which suggests a high sensitivity of the SHG response to the crystal symmetry. 54 To further reveal the strength of the NLO response, we compared the SHG intensity between the (R-MPEA) 6 InCl 9 and Y-cut quartz at various wavelengths, under the same measurement conditions (Fig. 5d).…”

“…Very recently, various low-dimensional lead-free HOMHs have been explored for NLO applications, such as ( R -MPEA) 1.5 PbBr 3.5 (DMSO) 0.5 , 16 ( R -/ S -MBA) 2 CuCl 4 , 51 ( R -/ S -MBA)CuBr 2 , 12 ( R -/ S -1,1-NEA) 2 CuCl 4 , ( R -/ S -1,2-NEA) 2 CuCl 4 , 52 ( R / S -MBA) 4 Cu 4 I 8 ·2H 2 O, 53 ( R -/ S -MPEA) 2 SnBr 6 , 54 [(CH 3 ) 2 CHNH 3 ]GeI 3 , 55 NH(CH 3 ) 3 SnCl 3 , NH(CH 3 ) 3 SnBr 3 , 56 [NH 2 (CH 2 CH 3 ) 2 ] 3 BiCl 6 , and [NH 2 (CH 2 CH 3 ) 2 ] 3 BiBr 6 . 57 In 2020, Nicholas et al reported low-dimensional hybrid indium/antimony halide perovskites and studied their electronic properties.…”