通过硫代调控Ga、In、Tl磷酸盐光学性质的第一性原理研究

doi:10.16553/j.cnki.issn1000-985x.2024.0193

摘要/Abstract

摘要： 本文基于第一性原理对磷酸盐与硫代磷酸盐家族中的GaPO₄、InPO₄、TlPO₄、GaPS₄、InPS₄和Tl₃PS₄进行系统的对比研究,探究[PO₄]^3-基团和[PS₄]^3-基团之间的联系与区别。能带计算结果表明,TlPO₄带隙最小(E_g=0.788 eV),InPO₄、GaPS₄、InPS₄和Tl₃PS₄带隙较大,分别为2.604、2.352、2.360和2.393 eV,而GaPO₄带隙最大(E_g=4.487 eV),发现[PS₄]^3-基团化合物能带结构更加容易预测与调控。态密度计算结果表明,GaPO₄、InPO₄与TlPO₄价带顶均由O-2p轨道贡献,导带底均由阳离子的s轨道及O-2p轨道共同贡献,GaPS₄、InPS₄与Tl₃PS₄在价带顶处均由S原子的p轨道贡献,而在导带部分[PS₄]^3-基团化合物的P原子的p轨道表现更加活跃。通过分析介电函数发现,[PO₄]^3-基团化合物和[PS₄]^3-基团化合物的峰值均随阳离子尺寸增大发生红移,且含[PS₄]^3-基团的化合物具有比含[PO₄]^3-基团化合物更高的静态介电常数。双折射计算结果表明,GaPO₄、InPO₄、TlPO₄、GaPS₄、InPS₄和Tl₃PS₄在波长1 064 nm处的双折射率分别为0.017、0.049、0.057、0.247、0.022和0.038,其中GaPS₄双折射率最大(0.247),这是由于其内部P—S键与Ga原子对能量较敏感。差分电荷密度与布居分析结果表明,六种化合物的光学效应与能带结构主要受到[PO₄]^3-与[PS₄]^3-基团影响。弹性模量分析表明磷酸盐化合物的弹性性质要高于硫代磷酸盐,并且发现In的化合物具有更高的力学稳定性和刚性。

关键词: 第一性原理, 密度泛函理论, 磷酸盐晶体, 硫代磷酸盐晶体, 电子结构, 光学性质, 力学性质

Abstract: In this work, we present a comprehensive first-principles investigation to compare the phosphates GaPO₄, InPO₄, TlPO₄, and the thiophosphates GaPS₄, InPS₄, Tl₃PS₄, focusing on the [PO₄]^3- and [PS₄]^3- groups. Band structure calculations disclose that TlPO₄ possesses the smallest bandgap (E_g=0.788 eV), whereas InPO₄, GaPS₄, InPS₄ and Tl₃PS₄ exhibit larger bandgaps of 2.604, 2.352, 2.360 and 2.393 eV, respectively. GaPO₄ stands out with its notably large bandgap, which is 4.487 eV. The band structure of the [PS₄]^3- compounds is notably more predictable and adjustable. Density of states analyses indicate that in GaPO₄, InPO₄ and TlPO₄, the valence band maximum is primarily attributed to O-2p orbitals, while the conduction band minimum is a result of both the cation's s orbital and O-2p orbitals. Conversely, in GaPS₄, InPS₄ and Tl₃PS₄, the valence band maximum is dominated by the p orbitals of sulfur atoms, with the porbitals of phosphorus atoms in the [PS₄]^3- groups showing increase activity in the conduction band. The dielectric function analysis reveals that the peak values for both [PO₄]^3- and [PS₄]^3- compounds experience a redshift with the enlargement of the cation size, with the [PS₄]^3- compounds exhibiting a larger static dielectric constant compared to their [PO₄]^3- counterparts. Birefringence calculations at 1 064 nm show that GaPS₄ has the highest birefringence value (0.247), attributed to the sensitivity of its internal P—S bonds and Ga atoms to energy changes. The other compounds exhibit birefringence values of 0.017 (GaPO₄), 0.049 (InPO₄), 0.057 (TlPO₄), 0.022 (InPS₄), and 0.038 (Tl₃PS₄). Differential charge density and population analysis suggest that the optical effects and band structures of these six compounds are predominantly influenced by the [PO₄]^3- and [PS₄]^3- groups. Elastic modulus analysis concludes that the phosphates exhibit superior elastic properties over the thiophosphates, with indium-containing compounds showing enhanced mechanical stability and rigidity.

Key words: first-principle, density functional theory, phosphate crystal, thiophosphate crystal, electronic structure, optical property, mechanical property

中图分类号:

TB34
O469

丁家福, 和志豪, 王云杰, 苏欣. 通过硫代调控Ga、In、Tl磷酸盐光学性质的第一性原理研究[J]. 人工晶体学报, 2025, 54(1): 95-106.

DING Jiafu, HE Zhihao, WANG Yunjie, SU Xin. First-Principles Study on the Regulation of Optical Properties of Gallium, Indium, and Thallium Phosphates Through Sulfur Substitution[J]. Journal of Synthetic Crystals, 2025, 54(1): 95-106.

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