Cathodoluminescence study of extended defects in hydrothermal ZnO crystals

Understanding the luminescence of ZnO is very important for some applications. In spite of the many studies carried out, there are still some points concerning the origin of some of the luminescence emissions in ZnO crystals that require additional study; in particular, the role of extended defects remains to be a matter of controversy. We present here a cathodoluminescence analysis of the defects generated by Vickers indentation in hydrothermal HTT crystals. Special emphasis was paid to the luminescence band peaking around 3.3 eV. The origin of this band is a matter of controversy, since it has been related to different causes, extended defects being one of the candidates for this emission. The CL images were acquired around crystal defects. It is observed that the 3.3 eV emission is enhanced around the crystal defects; though it is also observed, but weaker, out of the defect regions, which suggests that there exist two luminescence emissions peaking very close to 3.3 eV. The two emissions, one related to structural defects and the other to the LO phonon replica of the free excitonic band, appear very close each other and their relative intensity should determine the shape of the spectrum.     

p型未掺杂富锌ZnO薄膜的形成和性能研究

以高纯ZnO为靶材,氩气为溅射气体,利用射频磁控溅射技术在石英衬底上生长出纤锌矿结构的富锌ZnO薄膜.薄膜沿(002)择优取向生长,厚约为1.2μm,呈现电绝缘特性.将溅射的ZnO薄膜在10-3Pa,510~1 000 K的温度范围等温退火1 h,室温Hall测量结果表明ZnO薄膜的导电性能经历了由绝缘—n型—p型—n型半导体的变化.XPS测试表明ZnO薄膜的Zn/O离子比随退火温度的升高而降低,但一直是富锌ZnO,说明未掺杂的富锌ZnO也可以形成p型导电.p型未掺杂富锌ZnO薄膜的形成可归因于VZn受主浓度可以克服VO和Zni本征施主的补偿效应.     

磁控溅射ZnO薄膜的成核机制及表面形貌演化动力学研究

利用原子力显微镜分析了ZnO薄膜在具有本征氧化层的Si(100)和Si(111)基片上的表面形貌 随沉积时间的演化. 通过对薄膜生长形貌的动力学标度表征，研究了射频反应磁控溅射条件 下，ZnO薄膜的成核过程及生长动力学行为. 研究发现，ZnO在基片表面的成核过程可分为初 期成核阶段、低速率成核阶段和二次成核阶段. 对于Si(100)基片，三个成核阶段的生长指 数分别为β₁=1.04，β₂=0.25±0.01，β₃=0.74；对 于Si(11 关键词： ZnO薄膜 磁控溅射 生长动力学 成核机制     

Preparation and characterization of ZnO nanorods from NaOH solutions with assisted electrical field

ZnO naorods on ZnO-coated seed substrates were fabricated by solution chemical method from Zn(NO₃)₂/NaOH under assisted electrical field. The working mechanism of electrical field was analyzed and the factors affecting the rod growth such as potential, precursor concentration and growth temperature were elucidated. The structural and optical properties are characterized by SEM, TEM, XRD, HRTEM and UV-vis. The results indicated that the nanorods have wurtzite structure without electrical field and are primarily of zincite structure under electrical field; when the electrical field is 1.1-1.3 V, not only the elevation of ion diffusion and adsorption lower the crystallite/solution interfacial energy and then the crystal nucleation barrier by increasing charge intensity, but also the production of H⁺ through oxidation of OH⁻ increases properly the degree of solution supersaturation near the substrate, and thus lowers the activation energy. Both the two processes do favor to rod growth. With increasing precursor concentration in this system, the average diameter and length of ZnO nanorods increase, leading to decreasing of optical transmittance. The maximum rod growth rate at given concentration of Zn²⁺ occurs at a specific temperature.     

高性能ZnO纳米块体材料的制备及其拉曼光谱学特征

利用六面顶高压设备制备了高密度、低脆性、纳米级的ZnO块体材料，用MDI/JADE5 X射线衍射仪(Cu靶)和XL30S-FEG场发射扫描电子显微镜对高压样品的相组成、晶粒尺寸及微观形貌进行了表征.利用E55+FRA106/5傅里叶变换激光拉曼光谱仪通过ZnO块体样品位于50—500cm^-1之内的拉曼光谱, 研究了极性半导体纳米材料的拉曼光谱学特征.发现在极性半导体ZnO纳米块体材料中，没有出现明显的尺寸限制效应. 关键词： ZnO纳米块体 拉曼光谱 尺寸限制效应     

生长温度对磁控溅射ZnO薄膜的结晶特性和光学性能的影响

采用反应射频磁控溅射方法，在Si (100) 基片上制备了具有高c轴择优取向的ZnO薄膜.利用 原子力显微镜、透射电子显微镜、X射线衍射分析、拉曼光谱等表征技术，研究了沉积温度 对ZnO薄膜的表面形貌、晶粒尺度、应力状态等结晶性能的影响；通过沉积温度对透射光谱 和光致荧光光谱的影响，探讨了ZnO薄膜的结晶特性与光学性能之间的关系.研究结果显示， 在室温至500℃的范围内，ZnO薄膜的晶粒尺寸随沉积温度的增加而增加，在沉积温度为500 ℃时达到最大；当沉积温度为750℃时，ZnO薄膜的晶粒尺度有所减小；在室温至750℃的范 围内，薄膜中ZnO晶粒与Si基体之间均存在着相对固定的外延关系；在沉积温度低于500℃时 ，制备的ZnO薄膜处于压应变状态，而750℃时沉积的薄膜表现为张应变状态.沉积温度的不 同导致ZnO薄膜的折射率、消光系数、光学禁带宽度以及光致荧光特性的变化，沉积温度对 紫外光致荧光特性起着决定性的作用.此外，探讨了影响薄膜近紫外光致荧光发射的可能因 素. 关键词： ZnO薄膜 表面形貌 微观结构 光学常数     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

Preparation of nanosized ZnO using α brass

Nanosized ZnOs were synthesized on the surface of α brass coated a film of nickel catalyst at 500-700 °C under atmosphere of O₂ and CH₄ gases. The nanosized ZnOs have shapes including pillar, leaf, sheet and rod, which were determined by the synthesis temperature and the flow rates of O₂ and CH₄ gases. The nanosized ZnOs were characterized by electron microscopy including transmission electron microscope for crystal structure, morphology and high resolution images, both field emission scanning electron microscope and scanning electron microscope for morphology, and energy dispersive X-ray spectroscope equipped in electron microscope for chemical composition. A mechanism was proposed for the growth of nanosized ZnO obtained in this work.     

Kinetics and mechanism of free-surface vaporization of zinc, cadmium and mercury oxides analyzed by the third-law method

On the basis of critical comparison of experimental and theoretical values of the E parameter and investigation of the retardation effect of oxygen on the evaporation rate of ZnO, CdO and HgO, it was concluded that the dissociative evaporation of ZnO and HgO proceeds with releasing of atomic oxygen (O) as a primary product of decomposition. By contrast, the mechanism of dissociative evaporation of CdO corresponds to the equilibrium reaction with releasing of molecular oxygen (O₂) as a primary product of decomposition. As was shown, this difference in mechanisms is not related with interatomic OO distances in these oxides. From the analysis of crystal structure for 12 different oxides, which evaporate with releasing of atomic oxygen, and for 13 compounds, which evaporate with releasing of molecular oxygen, it was revealed that the first mechanism is observed for all oxides with the cubic crystal structure. It was proposed that a decisive role in this difference belongs to a local symmetry in the position of O atoms.     

Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.