First-Principles Calculation Study on Metal-Doped β -Ga2O3 for Photocatalysis

doi:10.16553/j.cnki.issn1000-985x.xb2026.0024

Abstract

Abstract: Aiming at the problem of narrow response spectrum of β-Ga₂O₃ in photocatalysis caused by high carrier recombination rate and wide band gap，the influence mechanisms of metal Zn，Cd，and Hg doping on the electronic structure，optical properties，and catalytic stability of β-Ga₂O₃ were investigated via first-principles calculation in this study. The results show that all three metal-doped systems all meet the energy level matching conditions for photocatalytic water splitting. Among them，the electron-hole relative effective mass ratio （ $m e *$ / $m h *$ ） of the Zn-doped system is higher than those of the Cd- and Hg-doped systems，which is more conducive to the spatial separation and migration of photogenerated carriers. Formation energy calculations show that Zn doping preferentially occupies Ga（1） lattice sites under oxygen-rich conditions，and its formation energy is much lower than those of Cd- and Hg-doped systems，indicating that Zn-doped β-Ga₂O₃ has the optimal structural stability. Optical absorption spectrum analysis shows that the optical absorption capacity of the material presents anisotropy，and the optical absorption coefficient along the ［001］ crystal direction is significantly higher than those along the ［100］ and ［010］ directions. Zn，Cd，and Hg doping greatly improve the optical absorption capacity of β-Ga₂O₃ in the infrared region. In summary，among the three metal doping，Zn doping can be used as the preferred impurity. This result provides a theoretical reference for the design of high-efficiency photocatalysts.

Key words: first-principle; β-Ga₂O₃; metal doping; photocatalysis; optical absorption coefficient; semiconductor material

CLC Number:

O644.1

ZHANG Ye, YANG Fengdie, LIU Lanxuan, ZHANG Qimiao, YAO Mingyuan, WANG Chaofan, MIAO Ruixia, HOU Yinlong. First-Principles Calculation Study on Metal-Doped β -Ga₂O₃ for Photocatalysis[J]. Journal of Synthetic Crystals, 2026, 55(6): 940-948.

Figures/Tables 10

Fig.1 Intrinsic β-Ga2O3 crystal structure schematic，small spheres represent O atoms，large spheres represent Ga atoms，numbers 1 and 2 represent Ga （1） and Ga （2） sites，respectively

Fig.2 Doping formation energy of Zn-，Hg-，and Cd-doped β-Ga2O3

Fig.3 Band structures of intrinsic and doped β-Ga2O3. （a） Intrinsic；（b） Zn-doped；（c） Hg-doped；（d） Cd-doped

Table 1 VBM，CBM extremum and band gap of different β -Ga2O3 systems

	Intrinsic β-Ga₂O₃	Zn@β-Ga₂O₃	Hg@β-Ga₂O₃	Cd@β-Ga₂O₃
CBM/eV	1.655	2.003	2.059	2.013
VBM/eV	-0.280	0.124	0.086	0.163
E_g/eV	1.935	1.879	1.973	1.850

Fig.4 PDOS diagrams of intrinsic and doped β-Ga2O3. （a） Intrinsic；（b） Zn-doped；（c） Hg-doped；（d） Cd-doped

Table 2 Mulliken electronegativity of each element

X（Ga）/eV	X（O）/eV	X（Zn）/eV	X（Hg）/eV	X（Cd）/eV
3.180	7.539	4.390	4.695	4.145

Table 3 Scissors operator correction values and band edge positions for each doped element

Material	$E g (P B E) / e V$	$E g' (A d j u s t e d) / e V$	$E C B (N H E) / e V$	$E V B (N H E) / e V$
Intrinsic β-Ga₂O₃	1.935	4.800	-1.562	3.237
Zn@β-Ga₂O₃	1.879	4.743	-1.491	3.252
Hg@β-Ga₂O₃	1.973	4.837	-1.529	3.308
Cd@β-Ga₂O₃	1.850	4.715	-1.484	3.230

Table 3 Scissors operator correction values and band edge positions for each doped element

Material	$E g (P B E) / e V$	$E g' (A d j u s t e d) / e V$	$E C B (N H E) / e V$	$E V B (N H E) / e V$
Intrinsic β-Ga₂O₃	1.935	4.800	-1.562	3.237
Zn@β-Ga₂O₃	1.879	4.743	-1.491	3.252
Hg@β-Ga₂O₃	1.973	4.837	-1.529	3.308
Cd@β-Ga₂O₃	1.850	4.715	-1.484	3.230

Fig.5 Band edge positions of intrinsic and doped β-Ga2O3

Table 4 Relative effective masses and relative effective mass ratios of photoexcited electrons and holes in intrinsic，Zn-，Hg-，and Cd-doped β -Ga2O3 systems

Material	$m e *$	$m h *$	$D$
Intrinsic β-Ga₂O₃	0.490	3.457	7.055
Zn@β-Ga₂O₃	0.501	28.454	56.794
Hg@β-Ga₂O₃	0.533	19.540	36.660
Cd@β-Ga₂O₃	0.508	28.453	56.010

Table 4 Relative effective masses and relative effective mass ratios of photoexcited electrons and holes in intrinsic，Zn-，Hg-，and Cd-doped β -Ga2O3 systems

Material	$m e *$	$m h *$	$D$
Intrinsic β-Ga₂O₃	0.490	3.457	7.055
Zn@β-Ga₂O₃	0.501	28.454	56.794
Hg@β-Ga₂O₃	0.533	19.540	36.660
Cd@β-Ga₂O₃	0.508	28.453	56.010

Fig.6 Optical absorption coefficient along different crystal orientations for various doping. （a）［100］；（b）［010］；（c）［001］

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First-Principles Calculation Study on Metal-Doped β -Ga₂O₃ for Photocatalysis

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