Point defects: key issues for II-oxides wide-bandgap semiconductors development

Xie Xiu-Hua; Li Bing-Hui; Zhang Zhen-Zhong; Liu Lei; Liu Ke-Wei; Shan Chong-Xin; Shen De-Zhen

doi:10.7498/aps.68.20191043

Abstract

II-oxides wide-bandgap semiconductor, including the beryllium oxide (BeO), magnesium oxide (MgO), zinc oxide (ZnO), have large exciton binding energy (ZnO 60 meV, MgO 80 meV), high optical gain (ZnO 300 cm^–1) and wide tunable band gap (3.37 eV ZnO, MgO 7.8 eV, BeO 10.6 eV), which are the advantages of achieving low-threshold laser devices in the ultraviolet wavelength. It is also one of the important candidates to replace the traditional gas arc lamp (such as mercury lamp, deuterium lamp, excimer lamp, xenon lamp etc.) as the source of deep ultraviolet and even vacuum ultraviolet. Although, during the past decades, the ZnO-based pn homojunction devices have made great progress in the near-UV electroluminescence, but as the band gap broadens, the acceptor (or donor) ionization energy becomes higher (On the order of hundreds meV), which causing the room temperature equivalent thermal energy (26 meV) cannot make the impurities ionizing effectively. In addition, the self-compensation effect in the doping process further weakens the carrier yield. These above drawbacks have become the bottleneck that hinders II-oxides wide-bandgap semiconductor from achieving ultraviolet laser devices and expanding to shorter wavelengths, and are also a common problem faced by other wide-bandgap semiconductor materials. The regulation of the electrical and luminescent properties of materials often depends on the control of critical defect states. The rich point defects and their combination types make the II-oxides wide-bandgap semiconductors an important platform for studying defect physics. For the identification and characterization of specific point defects, it is expected to discover and further construct shallower defect states, which will provide a basis for the regulation of electrical performance. In this paper, recent research results of II-oxides wide-bandgap semiconductors will be described from three aspects: high-quality epitaxial growth, impurity and point defects, p-type doping and ultraviolet electroluminescence. Through the overview of related research works, II-oxides wide-bandgap semiconductors are clarified as deep ultraviolet light sources materials. Meanwhile, indicates that the key to the regulation of electrical performance in the future lies in the regulation of point defects.

Keywords:

Authors and contacts

1.
State Key Laboratory of Luinescence and Applications, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033, China
2.
Zhengzhou University, School of Physics and Engineering, Zhengzhou 450001, China

Corresponding author: Shen De-Zhen, shendz@ciomp.ac.cn

Funds: Project supported by the National Key Scientific Instrument and Equipment Development Project of China (Grant No. 11727902) and the Excellent Young Scientists Fund of Jilin Province, China (Grant No. 20190103042JH).

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图 1 ZnO外延生长过程中缓冲层的RHEED线条图像演变过程　(a)氧等离子体处理后的蓝宝石(0001)表面; (b) 二维成核阶段的MgO缓冲层表面; (c) MgO缓冲层开始三维成岛状生长; (d) 薄层低温ZnO缓冲层生长在MgO上; (e) 退火后的ZnO缓冲层表现出平整二维表面^[9]

Figure 1. Evolution of RHEED line image of buffer layer during epitaxial growth of ZnO: (a) Oxygen plasma treated sapphire (0001) surface; (b) MgO buffer layer surface in two-dimensional nucleation stage; (c) the MgO buffer layer begins to grow into three-dimensional islands; (d) thin layer low temperature ZnO buffer layer grown on MgO; (e) annealed ZnO buffer layer exhibits a flat two-dimensional surface^[9]

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图 2 ZnO在c面蓝宝石上的原子排列示意图　(a)厚度为1 nm的MgO缓冲层; (b)厚度大于3 nm的MgO缓冲层^[14]

Figure 2. Schematic diagram of atomic arrangement of ZnO on c-sapphire: (a) MgO buffer layer with a thickness of 1 nm; (b) MgO buffer layer with a thickness greater than 3 nm^[14]

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图 3 ZnO与GaN异质界面的STEM图像, 通过Zn束流保护, 获得了清晰陡峭的界面, 保证了外延层的Zn极性均一^[17]

Figure 3. The STEM image of the hetero interface between ZnO and GaN, and it is protected by Zn beam, which obtains a clear and sharp interface and ensures uniformity of Zn polarity in the epitaxial layer^[17]

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图 4 N掺杂MgZnO薄膜原子力图像, 粗糙度为0.72 nm^[29]

Figure 4. Atomic force image of N-doped MgZnO film with roughness of 0.72 nm^[29]

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图 5 II族氧化物半导体带隙与晶格常数关系

Figure 5. Relationship between band gap and lattice constant of group II oxide semiconductors.

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图 6 (a), (b)二维电子气系统中应变层应力类型与压电极化方向; (c) BeMgZnO体系下应变类型随组分比例的变化情况^[56]

Figure 6. (a), (b) Strain stress type and piezoelectric polarization direction in two-dimensional electron gas system; (c) variation of strain type with composition ratio in BeMgZnO system^[56]

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图 7 ZnO薄膜中杂质浓度的深度分布情况　(a)非故意掺杂层中Si, Mo, Ta, Al的分布情况; (b)氮掺杂层中C, B, N, Cl, F的分布情况; (c) 施主型杂质元素经抑制后的纵向分布情况^[79]

Figure 7. Depth distribution of impurity concentration in ZnO thin films: (a) Distribution of Si, Mo, Ta and Al in unintentionally doped layers; (b) longitudinal distribution of donor-type impurity elements after suppression^[79]

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图 8 ZnO单晶衬底上外延层中杂质元素的SIMS数据^[80]

Figure 8. SIMS data of impurity elements in epitaxial layers on ZnO single crystal substrates^[80]

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图 9 极性面ZnO单晶衬底在氧环境下经1150 ℃退火1h前后, 杂质种类及含量变化情况^[23]

Figure 9. Changes in impurity types and contents of O-polar ZnO single crystal substrate after annealing at 1150 ℃ for 1 hour in an oxygen atmosphere^[23]

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图 10 (a)稀盐酸刻蚀后的ZnO单晶Zn极性表面; (b)稀盐酸刻蚀前后, Si元素的深度分布^[81,82]

Figure 10. (a) Zn polar surface of ZnO single crystal after being etched by dilute hydrochloric acid; (b) depth distribution of Si element before and after being etched dilute hydrochloric acid^[81,82]

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图 11 沿极性表面外延时, Zn极性与O极性表面极化电荷分布情况以及利用光生非平衡载流子构建Zn极性表面层富电子环境^[17]

Figure 11. Zn polar and O polar surface polarized charge distribution along epitaxial surface and Zn polar surface layer rich electronic environment using photogenerated unbalanced carriers^[17]

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图 12 Zn极性表面(2 × 2) + V_Zn重构的STM图像及结构示意图^[105]

Figure 12. STM image and structure diagram of Zn polar surface (2 × 2) + V_Zn reconstruction^[105]

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