Organic–inorganic
hybrid Pb-halide perovskites
have attracted
tremendous interest due to their potential application in photovoltaic
and optoelectronic fields. However, the toxicity and poor stability
of Pb-halide perovskites have become key bottlenecks toward their
future commercialization and industrialization. Therefore, in this
work, two novel hybrid lead-free perovskite nonlinear optical (NLO)
crystals (2-AMP)2BiX7·H2O (X
= Cl, Br) with high stability were successfully synthesized. Both
the crystals belong to the orthorhombic P212121 space group, displaying a zero-dimensional
perovskite structure. The thermal, environmental, and solvent atmospheric
stabilities were comprehensively investigated, with high thermal stability
up to 170 °C and high environmental and high solvent atmospheric
stability observed for (2-AMP)2BiBr7·H2O. First-principles calculations were carried out to study
the relationship of the structure and properties. A large birefringence
of 0.1368@1064 nm was determined for (2-AMP)2BiBr7·H2O, which was derived from the strong aeolotropic
conjugated π-electron distribution of planar 2-aminomethylpyridium.
A second-harmonic generation (SHG) effect that was 0.25 and 0.32 times
that of KH2PO4 (KDP) was measured for (2-AMP)2BiCl7·H2O and (2-AMP)2BiBr7·H2O, respectively, and the stronger
SHG response of bromide was attributed to the larger distortions of
{BiBr6} octahedrons. This work may offer new guidance for
exploration of low toxicity and high stability of perovskite NLO materials.
Introducing electronegative species into organic constituents was considered to be one effective strategy for adjusting crystal symmetry and designing new nonlinear optical (NLO) materials. By substitution of C4 in piperidine (C 5 H 11 N) with electronegative oxygen, organic morpholine (C 4 H 9 NO) was easily obtained. Therefore, to design NLO crystals, we focused on combinations of stereochemically active lone-pair (SCALP) cation (Pb 2+ )-based chloride and bromide with morpholine molecules. In this work, two lead halide hybrid perovskite (C 4 H 10 NO)PbX 3 (X = Cl, Br, abbreviated as MPbCl 3 and MPbBr 3 , respectively) single crystals with moderate nonlinear optical properties were synthesized by a slow evaporation method. The two title crystals belong to orthorhombic space group P2 1 2 1 2 1 with one-dimensional (1D) chainlike perovskite structures. Theoretical calculations revealed that the second harmonic generation (SHG) responses mainly originate from distorted {PbX 6 } octahedrons of the inorganic framework. Remarkably, moderate phase-matching SHG effects of about 0.70 and 0.81 times KH 2 PO 4 , large birefringences of 0.098 and 0.111 at 1064 nm, and large laser damage thresholds (LDTs) of 19.94 and 46.82 MW/cm 2 were estimated for MPbCl 3 and MPbBr 3 , respectively. This work provides a novel strategy for new purpose-designed hybrid NLO crystals by adjustment and modulation of chemical modification.
By combination of stereochemically active lone-pair d10 metal Cd2+ with halogen anions was identified as an effective method to obtain enhanced nonlinear optical (NLO) materials. In this work, hybrid lead-free perovskite...
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