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Published on: July 18, 2025
Regulating Second-Harmonic Generation by van der Waals Interactions in Two-dimensional Lead Halide Perovskite
Wen-Juan Wei1,2,3, Xing-Xing Jiang4, Li-Yuan Dong2
1School of Materials Science and Engineering; TKL of Metal and Molecule-Based Material Chemistry , Nankai University , Tianjin 300350 , China.
Abstract:
The flexible organic amine cations on the interfaces of two-dimensional (2D) hybrid organic-inorganic perovskite nanosheets could form relaxed structures, which would lead to exotic optoelectronic properties but are hard to understand. Here, the unusual interfacial relaxation of nanosheets exfoliated from an orthorhombic 2D lead halide perovskite, [(C6H5CH2NH3)2]PbCl4, is interrogated via ultrafast second-harmonic generation (SHG) spectroscopy. The in-plane SHG intensity anisotropy of these nanosheets is found to decrease with reducing layer thickness. Combined first-principles calculations and Monte Carlo simulations reveal that the induced second-order polarization arises primarily from the (C6H5CH2NH3)+ cations; and these organic amine cations form significantly reorganized conformations with decreasing nanosheet thickness due to weakened van der Waals interactions. Because the orientations of organic components at the interface determine their electric properties and specifically the dipolar susceptibility, the resulting structure leads to striking changes in the SHG properties.
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