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Updated: May 9, 2025

Probe Type II Band Alignment in One-Dimensional Van Der Waals Heterostructures Using First-Principles Calculations
Published on: October 12, 2019
Non-centrosymmetric structures designed rationally via a "dimensionality addition" strategy toward the promising
Shao-Min Pei1,2, Fan Wu1, Ming-Shu Zhang1
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China. bwliu@fjirsm.ac.cn.
Abstract:
Formulating a well-defined strategy for designing non-centrosymmetric (NCS) structures is an urgent requirement but a formidable challenge. Herein, we conducted a comprehensive statistical analysis of tetrahedra-based chalcogenide systems, revealing a significantly high probability for obtaining NCS structures in rigid three-dimensional (3D) systems, where the arrangement of tetrahedral units is minimally influenced by the non-directional spherical coordination of electropositive cations. Based on this premise, a "dimensionality addition" strategy implemented by regulating the A/M ratio (A = electropositive cations and M = tetrahedrally coordinated cations) is established for the first time. Consequently, six 3D NCS salt-inclusion selenides were successfully synthesized, namely, A[A4Cl][In14Se23] (A = K and Rb), A2[A3BaCl][In18Se30] (A = K and Rb), and [K4Cl][AK9-10Cl4][In22Se38] (A = Li and Ba). All these compounds collectively employed separated polycations as "dimension regulators" to facilitate the assembly of [InSe4] tetrahedra into 3D NCS diamond-like frameworks, enabling promising second-harmonic generation (SHG) responses (0.69-2.10 × AgGaS2). This study may serve as an instructive guidance for exploring symmetry-dependent materials.
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