From BPS4 to AB3P2S10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement

Yi Huang; Dongdong Chu; Yihan Yun; Wenlong Xie; Guangmao Li; Yong Zhang

doi:10.1039/d3dt01337e

From BPS₄ to AB₃P₂S₁₀ (A = Na, K): cations inducing dimension reduction and bandgap enlargement

Dalton Trans. 2023 Jun 13;52(23):7792-7796. doi: 10.1039/d3dt01337e.

Authors

Yi Huang¹, Dongdong Chu^{2

3}, Yihan Yun^{2

3}, Wenlong Xie², Guangmao Li^{2

3}, Yong Zhang^{1

4}

Affiliations

¹ School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China. yongzhang@hit.edu.cn.
² CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS, 40-1 South Beijing Road, Urumqi 830011, China. ligm@ms.xjb.ac.cn.
³ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
⁴ School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China.

PMID: 37272654
DOI: 10.1039/d3dt01337e

Abstract

Regulating the crystal structure by cations is one of the most effective methods to adjust the performances of optical materials and enrich the structural chemistry of solid-state inorganic crystals. In this work, only boron-thiophosphate BPS₄ (BPS) was used as the template. By introducing alkali metal ions, Na⁺ and K⁺, the synthesis, structural revolution, and bandgap adjustment were studied. Namely, the first quaternary boron-thiophosphates, AB₃P₂S₁₀ (A = Na, K) (ABPS) were obtained, whose anion skeleton decreased to zero dimension from one dimension (1D) in BPS. In addition, the bandgap showed obvious improvement from 3.30 (BPS) to 3.42 and 3.49 eV (ABPS). Structural studies and theoretical analyses indicated that the insert of cations separates the infinite chains to [B₃P₂S₁₀] clusters, localizes the electrons around the S^2- in [BS₄] and [PS₄] groups, and widens the bandgaps. This work could enrich the structural chemistry of boron-thiophosphates and reveal that ionic bonds can modulate the covalent skeleton and show the effect on the optical properties.