二维单层MoSi2X4 (X=N, P, As)的电子结构及光学性质研究

doi:10.6023/A21110533

摘要/Abstract

采用平面波超软赝势方法研究了二维单层MoSi₂X₄ (X=N, P, As)的稳定性、电子结构和光学性质. 研究结果显示, 基于单层MoSi₂N₄的两种同分异构体M1和M2所构建的六种晶体结构具有较好的动力学稳定性. 通过能带和有效质量的计算, 单层MoSi₂N₄在MoSi₂X₄ (X=N, P, As)六种晶体结构中显示出最宽的间接带隙和最高的载流子迁移率. 随后带边电位的计算结果表明, 单层MoSi₂N₄带边势分别为M1: –0.368、1.416 V, M2: –0.227、1.837 V, 其结果相较于MoSi₂P₄和MoSi₂As₄导带边电位更负, 价带边电位更正, 是六种晶体结构中最适合用作光催化剂的材料. 同时, 光吸收谱的计算结果显示, 单层MoSi₂N₄的光学吸收表现出明显的各向异性, 在可见光和紫外光波段内具有较强的光吸收能力, 说明其在可见光催化领域有着潜在的应用前景. 这些结果为进一步深入研究二维单层MoSi₂N₄在光催化水解领域的应用提供了理论指导.

关键词: MoSi₂N₄, 电子结构, 光催化, 第一性原理, 光学性质

Two-dimensional systems have served as potential materials in the generation of clean energy and energy storage, which are attributed to their particular advantages in photovoltaic, photocatalytic and electrochemical fields. Recently, the two-dimensional monolayer MoSi₂N₄ has been successfully fabricated. Motivated by these recent experimental results, herein the structural stability, electronic structures and optical properties of monolayer MoSi₂X₄ (X=N, P, As) using the method of plane-wave ultrasoft pseudopotentials were investigated. Six crystal structures were constructed based on the monolayer MoSi₂N₄ isomers M1 and M2. The phonon spectra did not show negative frequency vibration mode in the entire Brillouin region, indicating good dynamic stability. By analyzing the density of states, it can be known that the top of the valence band and the bottom of the conduction band of the six crystal structures are mainly contributed by MoX₂ (X=N, P, As) orbitals. Energy band structures and effective masses show that the monolayer MoSi₂N₄ exhibits the widest indirect band gap and the highest carrier mobility among the six crystal structures. The band edge potentials show that the monolayer MoSi₂N₄ band edge potentials are M1: –0.368, 1.416 V and M2: –0.227, 1.837 V, respectively. Compared with MoSi₂P₄ and MoSi₂As₄, the monolayer MoSi₂N₄ has a more negative potential of the conduction band edge and a more positive potential of the valence band edge, indicating that it is the most suitable material for photocatalysts among the six crystal structures. Meanwhile, the optical absorption spectrum shows that the optical absorption of monolayer MoSi₂N₄ exhibits excellent optical absorption ability in visible and ultraviolet wavelengths, indicating that it has a potential application prospect in the field of visible photocatalysis. The results provide theoretical guidance on the application of monolayer MoSi₂N₄, for further research in the field of photocatalytic hydrolysis.

Key words: MoSi₂N₄, electronic structure, photocatalysis, first-principle, optical property

引用此文

龚雪, 马新国, 万锋达, 段汪洋, 杨小玲, 朱进容. 二维单层MoSi₂X₄ (X=N, P, As)的电子结构及光学性质研究[J]. 化学学报, 2022, 80(4): 510-516.

Xue Gong, Xinguo Ma, Fengda Wan, Wangyang Duan, Xiaoling Yang, Jinrong Zhu. Study on the Electronic Structure and Optical Properties of Two-dimensional Monolayer MoSi₂X₄ (X=N, P, As)[J]. Acta Chimica Sinica, 2022, 80(4): 510-516.

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图/表 9

图1. 二维单层MoSi2X4 (X=N, P, As)两种同分异构体的俯视图和侧视图: (a)构型M1; (b)构型M2, 绿色球为Mo, 红色球为Si, 灰色球为X (X=N, P, As)

Figure 1. The top and side views of two monolayer MoSi2X4 (X=N, P, As) isomers: (a) M1; (b) M2, the green, red and gray balls denote Mo, Si and X (X=N, P, As) atoms, respectively

Structure	Model	a/nm	b/nm	E_g/eV	Bond length/nm		Bond angle/(°)		Cohesive energy/(eV•atom^–1)
Structure	Model	a/nm	b/nm	E_g/eV	l1	l2	θ1	θ2	Cohesive energy/(eV•atom^–1)
MoSi₂N₄	M1	0.290	0.290	1.783	0.209	0.175	73.36	106.61	–5.29
	M1	0.290	0.290	1.783	0.209	0.175	73.36	106.61	–5.29
	M2	0.289	0.289	2.064	0.209	0.175	74.08	107.01	–5.28
	M2	0.289	0.289	2.064	0.209	0.175	74.08	107.01	–5.28
MoSi₂P₄	M1	0.347	0.347	0.657	0.245	0.224	70.44	116.96	–3.30
	M1	0.347	0.347	0.657	0.245	0.225	70.44	116.96	–3.30
	M2	0.346	0.346	0.889	0.245	0.226	70.99	117.34	–3.29
	M2	0.346	0.346	0.889	0.245	0.225	70.99	117.34	–3.29
MoSi₂As₄	M1	0.365	0.366	0.559	0.257	0.236	69.97	117.94	–2.94
	M1	0.365	0.366	0.559	0.257	0.237	69.97	117.94	–2.94
	M2	0.364	0.365	0.709	0.257	0.240	70.26	116.85	–2.93
	M2	0.364	0.365	0.709	0.257	0.238	70.26	116.85	–2.93

表1. 采用GGA-PBE方法对单层MoSi2X4 (X=N, P, As)进行结构优化后的晶格常数、带隙、键长、键角和单点能

Table 1. The calculated crystal parameters, band gap, bond length, bond angle and total energy for monolayer MoSi2X4 (X=N, P, As) optimized with GGA-PBE

图2. 单层MoSi2X4 (X=N, P, As)六种晶体结构的声子谱

Figure 2. Phonon spectra of six crystal structures of monolayer MoSi2X4 (X=N, P, As)

图3. 单层MoSi2X4 (X=N, P, As)六种晶体结构的能带结构(左)和分态密度图(右)

Figure 3. Energy band structures (left) and partial density of states (PDOS) (right) of six crystal structures of monolayer MoSi2X4 (X=N, P, As)

图4. 单层MoSi2X4 (X=N, P, As)六种晶体结构导带底和价带顶的能带曲线(实线), 以及导带底最低位置和价带顶最高位置附近的二次函数拟合曲线(虚线)

Figure 4. The top curves of valence band and the bottom curves (solid line) of conduction band for six crystal structures of monolayer MoSi2X4 (X=N, P, As), and quadratic fitting curves (dash lines) at the bottom point of conduction band and top point of valence band

Structure	Model	$m_{e}^{*}$/m₀	$m_{h}^{*}$/m₀	μ₀/m₀	Work function/eV
MoSi₂N₄	M1	0.461	0.644	0.269	4.766
MoSi₂N₄	M2	0.462	0.798	0.293	4.787
MoSi₂P₄	M1	0.615	0.799	0.348	4.705
MoSi₂P₄	M2	0.702	0.778	0.369	4.805
MoSi₂As₄	M1	0.625	0.606	0.308	4.700
MoSi₂As₄	M2	0.614	0.806	0.349	4.778
MoS₂		0.457	0.779	0.288	5.149

表2. 单层MoSi2X4 (X=N, P, As)六种晶体结构和二维单层MoS2的有效质量和功函数

Table 2. Calculated effective masses and work functions of monolayer MoSi2X4 (X=N, P, As) and MoS2

图5. 单层MoSi2X4 (X=N, P, As)六种晶体结构模型的功函数(红色和蓝色虚线分别代表真空能级E0和费米能级EF)

Figure 5. Calculated work functions for six crystal structures of monolayer MoSi2X4 (X=N, P, As) (the blue and red dashed lines represent the vacuum level E0 and the Fermi level EF, respectively)

图6. 单层MoSi2X4 (X=N, P, As)六种晶体结构的边带位置

Figure 6. The band edge positions of six crystal structures of MoSi2X4 (X=N, P, As)

图7. 单层MoSi2N4构型M1和构型M2的光吸收谱

Figure 7. Calculated optical absorption spectra for (a) MoSi2N4 (M1) and (b) MoSi2N4 (M2)

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二维单层MoSi₂X₄ (X=N, P, As)的电子结构及光学性质研究

Study on the Electronic Structure and Optical Properties of Two-dimensional Monolayer MoSi₂X₄ (X=N, P, As)

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