Ru Fan, Xia Jing, Li Xuanze, Wang Yifan, Hua Ze, Shao Ruiwen, Wang Xuecong, Lee Chun-Sing, Meng Xiang-Min
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
Analysis & Testing Center, Beijing Institute of Technology, Beijing, 102488, P. R. China.
Nanoscale. 2021 Jul 8;13(26):11525-11533. doi: 10.1039/d1nr02613e.
II-VI semiconductor heterojunctions show huge potential for application in nanodevice fabrication due to their type-II alignments owing to the better spatial separation of electrons and holes. However, the hetero-epitaxial growth of high-quality heterostructures is still a challenge, especially for materials with large lattice mismatch. In this work, well-aligned single-crystalline ZnO/ZnS core/shell nanorod arrays were obtained by introducing an Al2O3 buffer layer. It is interesting that the nature of the ZnS layer varies with the thickness of the Al2O3 layer. When Al2O3 is less than 2 nm, the interaction between the substrate and epilayer is strong enough to penetrate through the buffer layer, enabling the growth of ZnS on Al2O3-coated ZnO nanorod arrays. On the basis of detailed characterization, a rational growth mechanism of the core/shell heterostructure is proposed, in which the Al2O3 interlayer can eliminate voids due to the Kirkendall effect around the interface and accommodate a misfit dislocation between the inner ZnO and outer ZnS, resulting in more sufficient strain relaxation in the epitaxy. In addition, cathodoluminescence measurements demonstrate that the optical properties of the ZnO/ZnS heterostructure could be effectively improved by taking advantage of the thin Al2O3. The I-V curves characterized by PeakForce tunneling atomic force microscopy reveal that the heterostructure shows a typical rectifying behavior and good photoresponse to ultraviolet light. These findings may provide a reasonable and effective strategy for the growth of highly lattice-mismatched heterostructure arrays buffered by the Al2O3 layer, broadening the options for fabricating heterojunctions and promoting their applications in optoelectronic devices.
II-VI族半导体异质结由于其II型能带排列,电子和空穴具有更好的空间分离,在纳米器件制造中显示出巨大的应用潜力。然而,高质量异质结构的异质外延生长仍然是一个挑战,特别是对于晶格失配较大的材料。在这项工作中,通过引入Al2O3缓冲层获得了排列良好的单晶ZnO/ZnS核壳纳米棒阵列。有趣的是,ZnS层的性质随Al2O3层的厚度而变化。当Al2O3小于2nm时,衬底与外延层之间的相互作用足够强,能够穿透缓冲层,使得ZnS在涂覆有Al2O3的ZnO纳米棒阵列上生长。在详细表征的基础上,提出了核壳异质结构的合理生长机制,其中Al2O3中间层可以消除由于界面处柯肯达尔效应产生的空隙,并容纳内部ZnO和外部ZnS之间的失配位错,从而在外延中实现更充分的应变弛豫。此外,阴极发光测量表明,利用薄Al2O3可以有效改善ZnO/ZnS异质结构的光学性质。通过峰值力隧穿原子力显微镜表征的I-V曲线表明,该异质结构表现出典型的整流行为和对紫外光良好的光响应。这些发现可能为生长由Al2O3层缓冲的高度晶格失配异质结构阵列提供一种合理有效的策略,拓宽制造异质结的选择,并促进其在光电器件中的应用。