高质量铟掺杂氧化镓单晶浮区法生长研究

doi:10.15541/jim20240241

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1384-1390.DOI: 10.15541/jim20240241 CSTR: 32189.14.10.15541/jim20240241

所属专题：【信息功能】透明陶瓷与闪烁晶体（202412）

高质量铟掺杂氧化镓单晶浮区法生长研究

李宪珂(), 张超逸, 黄林, 孙鹏, 刘波, 徐军, 唐慧丽()

同济大学物理科学与工程学院, 先进微结构材料教育部重点实验室, 上海 200092

收稿日期:2024-05-13 修回日期:2024-05-29 出版日期:2024-06-24 网络出版日期:2024-06-24
通讯作者: 唐慧丽, 教授. E-mail: tanghl@tongji.edu.cn
作者简介:李宪珂(1999-), 男, 硕士研究生. E-mail: va142857@163.com
基金资助:
国家自然科学基金(12375181);上海市科技计划项目(23511102302);中央高校基本科研业务费专项基金(22120220626)

High-quality Indium-doped Gallium Oxide Single Crystal Growth by Floating Zone Method

LI Xianke(), ZHANG Chaoyi, HUANG Lin, SUN Peng, LIU Bo, XU Jun, TANG Huili()

MOE Key Laboratory of Advanced Micro-Structured Materials, School of Physics Science and Engineering, Tongji University, Shanghai 200092, China

Received:2024-05-13 Revised:2024-05-29 Published:2024-06-24 Online:2024-06-24
Contact: TANG Huili, professor. E-mail: tanghl@tongji.edu.cn
About author:LI Xianke (1999-), male, Master candidate. E-mail: va142857@163.com
Supported by:
National Natural Science Foundation of China(12375181);Shanghai Science and Technology Plan Project(23511102302);Fundamental Research Funds for the Central Universities(22120220626)

摘要/Abstract

摘要：

β-Ga₂O₃是一种新型超宽带隙半导体材料, 性能出色, 在高功率电子器件和日盲深紫外探测器等领域有着巨大的应用前景。通过掺入In³⁺离子, 可以调节β-Ga₂O₃的带隙宽度和光学性质, 从而进一步拓展其应用范围。本研究以高纯度Ga₂O₃、In₂O₃为原料, 采用光学浮区法制备了β-Ga₂O₃:9%In、β-Ga₂O₃:15%In单晶。生长速度为5 mm/h时, 晶体出现失透现象, 在光学显微镜下观察, 发现晶体中含有大量气泡缺陷, 这些缺陷主要呈条状和球状, 其中条状气泡的长度在50~200 μm范围内, 沿[010]晶体生长方向延伸。通过扫描电子显微镜观察缺陷形貌和元素分布, 发现气泡周围的元素分布均匀, 无杂质元素聚集。结果表明, 缺陷的形成与In₂O₃高温分解有关, 产生的气体未及时排出, 随熔体结晶进入晶体内部形成气泡。优化晶体生长工艺解决了气泡缺陷引起的晶体失透问题, 得到的透明β-Ga₂O₃:9%In单晶摇摆曲线半峰宽可达44 arcsec, 晶体的结晶质量显著提升。本研究为生长高质量β-Ga₂O₃:In体块单晶提供了解决方案, 为深入了解其光电性能奠定了基础。

关键词: 铟掺杂氧化镓, 光学浮区法, 晶体生长, 气泡缺陷

Abstract:

β-Ga₂O₃ is a novel wide bandgap semiconductor material with excellent performance, which has great potential applications in high power electronic devices and deep ultraviolet detectors. By doping with In³⁺ ions, the bandgap and optical properties of β-Ga₂O₃ can be adjusted, further expanding its application range. In this study, β-Ga₂O₃:9%In and β-Ga₂O₃:15%In single crystals are prepared using high-purity Ga₂O₃ and In₂O₃ as raw materials by the optical floating zone method. When the growth rate is 5 mm/h, the crystals exhibit a phenomenon of transparency loss. Observation under an optical microscope reveals the presence of numerous bubble defects in the crystals, which mainly appearing strip-like and spherical shape. Length of the strip-like bubbles ranges from 50 to 200 μm and extends along the [010] crystal direction. Observation under a scanning electron microscope reveals uniform elemental distribution around the bubbles, with no evidence of impurity element accumulation. These findings suggest that the formation of defects is related to the high-temperature decomposition of In₂O₃, where the generated gas is not timely discharged, entering the crystal interior with the crystallization of the melt to form bubbles. After optimizing the crystal growth process, the problem of opacity caused by bubble defects is effectively resolved, resulting in transparent β-Ga₂O₃:9%In single crystal with a full width at half maximum of the rocking curve as low as 44 arcsec and significantly improved crystalline quality. This study provides a solution for growing high-quality β-Ga₂O₃:In bulk single crystal, laying a foundation for a deeper understanding of its optoelectronic properties.

Key words: indium-doped gallium oxide, optical floating zone method, crystal growth, bubble defect

中图分类号:

TQ174

李宪珂, 张超逸, 黄林, 孙鹏, 刘波, 徐军, 唐慧丽. 高质量铟掺杂氧化镓单晶浮区法生长研究[J]. 无机材料学报, 2024, 39(12): 1384-1390.

LI Xianke, ZHANG Chaoyi, HUANG Lin, SUN Peng, LIU Bo, XU Jun, TANG Huili. High-quality Indium-doped Gallium Oxide Single Crystal Growth by Floating Zone Method[J]. Journal of Inorganic Materials, 2024, 39(12): 1384-1390.

图/表 9

图1 β-Ga2O3:In晶体照片

Fig. 1 Images of as-grown β-Ga2O3:In crystals (a) Opaque β-Ga2O3:9%In; (b) Transparent β-Ga2O3:9%In; (c) Transparent β-Ga2O3:15%In

图2 β-Ga2O3: In晶体粉末的XRD图谱

Fig. 2 XRD patterns of β-Ga2O3:In crystal powders (a) XRD patterns in the range of 2θ=10°-90°; (b) XRD diffraction peak of (400) crystal surface at 2θ=30.095°

图3 光学显微镜下失透β-Ga2O3:9%In气泡缺陷形貌

Fig. 3 Optical microscope morphologies of bubble defects in opaque β-Ga2O3:9%In (a) Long strip bubble; (b) Short strip bubble; (c) Spherical bubble; (d) Short strip bubble

图4 失透β-Ga2O3:9%In晶体SEM照片、EDS能谱和对应的元素分布

Fig. 4 SEM image, EDS pattern and corresponding elemental mappings of the opaque β-Ga2O3:9%In crystal (a) SEM image; (b) EDS pattern and elemental contents; (c-e) Elemental mappings of (c) Ga, (d) O and (e) In

图5 光学显微镜下透明β-Ga2O3:9%In晶体形貌

Fig. 5 Transparent β-Ga2O3:9%In crystal morphology under optical microscope

图6 透明β-Ga2O3:9%In晶体SEM照片、EDS能谱和对应的元素分布

Fig. 6 SEM image, EDS pattern and corresponding elemental mappings of transparent β-Ga2O3:9%In crystal (a) SEM image; (b) EDS pattern and elemental contents; (c-e) Elemental mappings of (c) Ga, (d) O and (e) In

表1 透明β-Ga2O3:9%In、β-Ga2O3:15%In晶体的ICP-AES测试结果(%, in mass)

Table 1 ICP-AES testing of transparent β-Ga2O3:9%In and β-Ga2O3:15%In crystals (%, in mass)

Element	β-Ga₂O₃:9%In	β-Ga₂O₃:15%In
In	1.76	1.87
Si	0.01	0.03
Al	0.01	0.01
Fe	0.01	0
Mg	0.02	0.02

图7 UID β-Ga2O3和β-Ga2O3:In晶体的吸收光谱和光学带隙

Fig. 7 Absorption spectra and optical bandgaps of UID β-Ga2O3 and β-Ga2O3:In crystals (a) Absorption spectra of UID β-Ga2O3, opaque β-Ga2O3:9%In, transparent β-Ga2O3:9%In and transparent β-Ga2O3:15%In crystals; (b) Optical bandgap fitting of UID β-Ga2O3, transparent β-Ga2O3:9%In and transparent β-Ga2O3:15%In crystals

图8 失透β-Ga2O3:9%In和透明β-Ga2O3:9%In晶体摇摆曲线

Fig. 8 Rocking curves of (a) opaque β-Ga2O3:9%In and (b) transparent β-Ga2O3:9%In crystals

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高质量铟掺杂氧化镓单晶浮区法生长研究

High-quality Indium-doped Gallium Oxide Single Crystal Growth by Floating Zone Method

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