Growth and optical properties of large-sized Co2+: ZnGa2O4 single crystal

Zhengyuan Li; Jiaqi Wei; Yiyuan Liu; Huihui Li; Yang Li; Zhitai Jia; Xutang Tao; Wenxiang Mu

doi:10.1088/1674-4926/25010017

J. Semicond. > In Press

ARTICLES

Growth and optical properties of large-sized Co²⁺: ZnGa₂O₄ single crystal

Zhengyuan Li¹, Jiaqi Wei², Yiyuan Liu¹, Huihui Li¹, Yang Li¹, Zhitai Jia¹, Xutang Tao¹ and Wenxiang Mu^1,

+ Author Affiliations

Corresponding author: Wenxiang Mu, mwx@sdu.edu.cn

DOI: 10.1088/1674-4926/25010017CSTR: 32376.14.1674-4926.25010017

Abstract: The transition of cobalt ions located at tetrahedral sites will produce strong absorption in the visible and near-infrared regions, and is expected to work in a passively Q-switched solid-state laser at the eye-safe wavelength of 1.5 µm. In this study, Co²⁺ ions were introduced into the wide bandgap semiconductor material ZnGa₂O₄, and large-sized and high-quality Co²⁺-doped ZnGa₂O₄ crystals with a volume of about 20 cm³ were grown using the vertical gradient freeze(VGF) method. Crystal structure and optical properties were analyzed using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and absorption spectroscopy. XRD results show that the Co²⁺-doped ZnGa₂O₄ crystal has a pure spinel phase without impurity phases and the rocking curve full width at half maximum (FWHM) is only 58 arcsec. The concentration of Co²⁺ in Co²⁺-doped ZnGa₂O₄ crystals was determined to be 0.2 at.% by the energy dispersive X-ray spectroscopy. The optical band gap of Co²⁺-doped ZnGa₂O₄ crystals is 4.44 eV. The optical absorption spectrum for Co²⁺-doped ZnGa₂O₄ reveals a prominent visible absorption band within 550−670 nm and a wide absorption band spanning from 1100 to 1700 nm. This suggests that the Co²⁺ ions have substituted the Zn²⁺ ions, which are typically tetrahedrally coordinated, within the lattice structure of ZnGa₂O₄. The visible region's absorption peak and the near-infrared broad absorption band are ascribed to the ⁴A₂(⁴F) → ⁴T₁(⁴P) and⁴A₂(⁴F) →⁴T₁(⁴F) transitions, respectively. The optimal ground state absorption cross section was determined to be 3.07 × 10⁻¹⁹ cm² in ZnGa₂O₄, a value that is comparatively large within the context of similar materials. This finding suggests that ZnGa₂O₄ is a promising candidate for use in near-infrared passive Q-switched solid-state lasers.

Key words: ZnGa₂O₄, bulk single crystals, cobalt doping, absorption, ultra-wide bandgap semiconductors

References

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Fig. 1. (Color online) (a) Photograph of VGF-grown ZnGa₂O₄ bulk crystal and wafer. (b) Powder XRD pattern of the Co²⁺-doped ZnGa₂O₄ crystal. (c) Laue diffraction pattern of the (111) plane Co²⁺-doped ZnGa₂O₄ crystal wafer. (d) X-ray rocking curve for (111) diffraction of the Co²⁺-doped ZnGa₂O₄ crystal wafer.

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Fig. 2. (Color online) (a) gallium (Ga 2p), (b) oxygen (O 1s) and (c) zinc (Zn 2p) are the XPS spectra of the Co²⁺-doped ZnGa₂O₄ crystal.

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Fig. 3. (Color online) (a) The Co²⁺-doped ZnGa₂O₄ wafer for optical testing. (b) The band gap width of Co²⁺-doped ZnGa₂O₄ crystal. (c) The measured absorption spectrum of the Co²⁺-doped ZnGa₂O₄ wafer in the visible region. (d) The measured absorption spectrum of the Co²⁺-doped ZnGa₂O₄ wafer in the near-infrared region.

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Table 1. The elemental composition of different elements in the Co²⁺-doped ZnGa₂O₄ sample.

Elements	Zn	Ga	O	Co
Co²⁺: ZnGa₂O₄ sample	13.63 ± 0.15 at.%	28.38 ± 0.20 at.%	57.78 ± 0.25 at.%	0.2 ± 0.05 at.%

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Table 2. Ground state absorption cross sections (σ_gas) of Co²⁺ doped spinel materials prepared by different methods.

Material	Co²⁺ concentration (at.%)	σ_gas (10⁻¹⁹ cm²)	Reference
Co²⁺: MgAl₂O₄ ceramics	0.05	2.9	[61]
Co²⁺: MgAl₂O₄ single crystal	0.8	3.5	[6]
Co²⁺: MgAl₂O₄ ceramics	0.05	2.55	[62]
Co²⁺: ZnGa₂O₄ single crystal	0.2	3.07	This work

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Received: 13 January 2025 Revised: 08 February 2025 Online: Accepted Manuscript: 20 February 2025Uncorrected proof: 03 April 2025

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Zhengyuan Li, Jiaqi Wei, Yiyuan Liu, Huihui Li, Yang Li, Zhitai Jia, Xutang Tao, Wenxiang Mu. Growth and optical properties of large-sized Co2+: ZnGa2O4 single crystal[J]. Journal of Semiconductors, 2025, In Press. doi: 10.1088/1674-4926/25010017 ****Z Y Li, J Q Wei, Y Y Liu, H H Li, Y Li, Z T Jia, X T Tao, and W X Mu, Growth and optical properties of large-sized Co2+: ZnGa2O4 single crystal[J]. J. Semicond., 2025, 46(7), 072501 doi: 10.1088/1674-4926/25010017

Citation:

Zhengyuan Li, Jiaqi Wei, Yiyuan Liu, Huihui Li, Yang Li, Zhitai Jia, Xutang Tao, Wenxiang Mu. Growth and optical properties of large-sized Co²⁺: ZnGa₂O₄ single crystal[J]. Journal of Semiconductors, 2025, In Press. doi: 10.1088/1674-4926/25010017 ****

Z Y Li, J Q Wei, Y Y Liu, H H Li, Y Li, Z T Jia, X T Tao, and W X Mu, Growth and optical properties of large-sized Co²⁺: ZnGa₂O₄ single crystal[J]. J. Semicond., 2025, 46(7), 072501 doi: 10.1088/1674-4926/25010017

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Growth and optical properties of large-sized Co²⁺: ZnGa₂O₄ single crystal

DOI: 10.1088/1674-4926/25010017

CSTR: 32376.14.1674-4926.25010017

1.
State Key Laboratory of Crystal Materials, Institute of Novel Semiconductors, Institute of Crystal Materials, Shandong University, Jinan 250100, China
2.
State Key Laboratory for Mesoscopic Physics and Frontiers Science Center for Nano-optoelectronics, School of Physics, Peking University, Beijing 100871, China

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Zhengyuan Li got his BS degree from Shandong University in 2020. Now he is a PhD student at Shandong University under the supervision of Prof. Zhitai Jia. His research focuses on the crystal growth and investigation of properties of ultrawide-bandgap semiconductor material of β-Ga₂O₃ and ZnGa₂O₄
Wenxiang Mu got his BS degree in 2013 and PhD degree in 2018 at Shandong University. Now he is an associate professor at institute of novel semiconductors of Shandong University. His research interests include crystal growth, substrate processing, performance optimization and device design based on ultrawide-bandgap semiconductor material of β-Ga₂O₃
Corresponding author: mwx@sdu.edu.cn
Received Date: 2025-01-13
Revised Date: 2025-02-08

Available Online: 2025-02-20

Abstract

Abstract

The transition of cobalt ions located at tetrahedral sites will produce strong absorption in the visible and near-infrared regions, and is expected to work in a passively Q-switched solid-state laser at the eye-safe wavelength of 1.5 µm. In this study, Co²⁺ ions were introduced into the wide bandgap semiconductor material ZnGa₂O₄, and large-sized and high-quality Co²⁺-doped ZnGa₂O₄ crystals with a volume of about 20 cm³ were grown using the vertical gradient freeze(VGF) method. Crystal structure and optical properties were analyzed using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and absorption spectroscopy. XRD results show that the Co²⁺-doped ZnGa₂O₄ crystal has a pure spinel phase without impurity phases and the rocking curve full width at half maximum (FWHM) is only 58 arcsec. The concentration of Co²⁺ in Co²⁺-doped ZnGa₂O₄ crystals was determined to be 0.2 at.% by the energy dispersive X-ray spectroscopy. The optical band gap of Co²⁺-doped ZnGa₂O₄ crystals is 4.44 eV. The optical absorption spectrum for Co²⁺-doped ZnGa₂O₄ reveals a prominent visible absorption band within 550−670 nm and a wide absorption band spanning from 1100 to 1700 nm. This suggests that the Co²⁺ ions have substituted the Zn²⁺ ions, which are typically tetrahedrally coordinated, within the lattice structure of ZnGa₂O₄. The visible region's absorption peak and the near-infrared broad absorption band are ascribed to the ⁴A₂(⁴F) → ⁴T₁(⁴P) and⁴A₂(⁴F) →⁴T₁(⁴F) transitions, respectively. The optimal ground state absorption cross section was determined to be 3.07 × 10⁻¹⁹ cm² in ZnGa₂O₄, a value that is comparatively large within the context of similar materials. This finding suggests that ZnGa₂O₄ is a promising candidate for use in near-infrared passive Q-switched solid-state lasers.
- ZnGa₂O₄,
- bulk single crystals,
- cobalt doping,
- absorption,
- ultra-wide bandgap semiconductors

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