First-Principles Study on Electronic Structure and Magnetic Properties of Transition Metal-Doped β -Ga2O3

doi:10.16553/j.cnki.issn1000-985x.2025.0208

Abstract

Abstract: In this paper， the first-principles calculation method was adopted to systematically investigate the effects of Ga vacancies and 3d transition metal elements Ti， V， Cr， Mn， Fe， Co， Ni and Cu doping on the geometric structure， electronic structure， stability and magnetic properties of β-Ga₂O₃.The calculation results show that both Ga vacancies and doped atoms cause local distortions of different degrees in the geometric structure of β-Ga₂O₃， but do not destroy the overall symmetry of β-Ga₂O₃ structure. The formation energy calculation results indicate that β-Ga₂O₃ systems containing Ga vacancies or doped atoms are all stable and are more likely to be formed in an oxygen-rich environment. More importantly， the ground states of the β-Ga₂O₃ systems containing Ga vacancies and Ti， V， Cr， Mn， Fe， Ni and Cu doping are magnetic， with magnetic moments of 2.51， 0.67， 0.12， 3.00， 2.05， 1.00， 1.00 and 1.92 μ_B， respectively. Based on the analysis， it can be concluded that the magnetic moment distribution in β-Ga₂O₃ systems containing Ga vacancies or doped with Ti， V， Cr， Mn， Fe， Ni， and Cu is associated with the hybridization between the vacancy/dopant atom and its neighboring oxygen atoms. In transition metal-doped β-Ga₂O₃ systems， the magnetic moments primarily originate from the contribution of 3d transition metal dopants.

Key words: β-Ga₂O₃; transition metal doping; first-principle; density functional theory; magnetic property; electronic structure

CLC Number:

O469

WANG Yanjie, LI Bao, SONG Junhui, HE Xingcan, WANG Chao, YANG Fan, YAN Xingzhen, CHI Yaodan, YANG Xiaotian. First-Principles Study on Electronic Structure and Magnetic Properties of Transition Metal-Doped β -Ga₂O₃[J]. Journal of Synthetic Crystals, 2026, 55(3): 452-460.

Figures/Tables 8

Fig.1 β-Ga2O3 structure diagram. （a） Schematic diagram of transition metal element X doping at octahedral Ga sites；（b） schematic diagram of octahedral centered on the doped atom X

Fig.2 β-Ga2O3 electronic structure diagram. （a） Band diagram of β-Ga2O3；（b） total density and orbital-specific density diagrams of β-Ga2O3

Table 1 Bond lengths dX-Oy of dopant atoms and surrounding O atoms in Ga31O48X system， average bond length AX-O， octahedral volume VX. Where X = Ti， V， Cr， Mn， Fe， Co， Ni， Cu； y = 1， 2， 3， 4， 5， 6

System	d_X-O1/Å	d_X-O2/Å	d_X-O3/Å	d_X-O4/Å	d_X-O5/Å	d_X-O6/Å	A_X-O/Å	V_X/Å³
Ga₂O₃	1.94	2.02	1.98	2.08	2.08	1.98	2.01	10.67
Ga₃₁O₄₈Ti	1.93	2.05	1.96	2.09	2.09	1.96	2.01	10.59
Ga₃₁O₄₈V	1.91	2.02	1.96	2.06	2.06	1.96	2.00	10.30
Ga₃₁O₄₈Cr	1.94	2.00	1.96	2.03	2.03	1.96	1.99	10.24
Ga₃₁O₄₈Mn	1.90	1.95	1.94	2.01	2.01	1.94	1.96	9.81
Ga₃₁O₄₈Fe	1.89	1.95	1.94	2.00	2.00	1.94	1.95	9.65
Ga₃₁O₄₈Co	1.91	1.92	1.94	1.96	1.96	1.94	1.94	9.54
Ga₃₁O₄₈Ni	1.91	1.94	1.97	2.01	2.01	1.97	1.97	9.99
Ga₃₁O₄₈Cu	1.94	2.00	1.99	2.04	2.04	1.99	2.00	10.46

Fig.3 Differential charge density map of β-Ga2O3 system. （a） Ga2O3；（b） Ga31O48；（c）~（j） Ga31O48X （X=Ti， V， Cr， Mn， Fe， Co， Ni， Cu） system

Table 2 Band gap， magnetic moment， formation energy （Ef（D）） under Ga-rich and O-rich conditions， spin polarized state and non-spin polarized state energy difference（ΔEspin） of Ga31O48 and Ga31O48X （X = Ti， V， Cr， Mn， Fe， Co， Ni， Cu） system

System	Band gap/eV	Magnetic moment/μ_B	E_f（D）/eV		ΔE_spin/meV
System	Band gap/eV	Magnetic moment/μ_B	O-rich	Ga-rich	ΔE_spin/meV
Ga₃₁O₄₈	0.04×10^-1	2.51	3.79	7.62	-0.34
Ga₃₁O₄₈Ti	0.01	0.67	-5.01	-1.18	-0.13
Ga₃₁O₄₈V	0.03	-0.12	-2.89	0.95	-0.40
Ga₃₁O₄₈Cr	0.81	3.00	-2.96	0.87	-1.82
Ga₃₁O₄₈Mn	0.09	2.05	-1.80	2.03	-0.97
Ga₃₁O₄₈Fe	0.53	1.00	-0.63	3.20	-0.37
Ga₃₁O₄₈Co	1.36	0.09	-0.16	3.67	0
Ga₃₁O₄₈Ni	0.01	-1.00	0.92	4.75	-0.17
Ga₃₁O₄₈Cu	0.39	1.92	1.94	5.78	-0.33

Fig.4 Spin density distribution map of Ga31O48 and Ga31O48X （X = Ti， V， Cr， Mn， Fe， Co， Ni， Cu） systems. The yellow and blue contour lines represent the spin density with spin up and spin down， respectively， the red and green spheres represent the O and Ga atoms， and the blue represents the doped atoms

Fig.5 Total density of states and orbital density of states of Ga31O48 and Ga31O48X （X = Ti， V， Cr， Mn， Fe， Co， Ni， Cu） systems

Fig.6 Band diagrams of Ga31O48 and Ga31O48 X （X = Ti， V， Cr， Mn， Fe， Co， Ni， Cu） systems. The green dotted line represents the Fermi level

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First-Principles Study on Electronic Structure and Magnetic Properties of Transition Metal-Doped β -Ga₂O₃

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