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

doi:10.6023/A21110533

Abstract

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

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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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Fig. & Tab. 9

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

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

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

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

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

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

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)

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

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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二维单层MoSi2X4 (X=N, P, As)的电子结构及光学性质研究