温度对ZnO/Al2O3(0001)界面的吸附、扩散及生长初期模式的影响

构建了一个ZnO沉积在α-Al₂O₃(0001)表面生长初期的模型，采用基于密度泛函理论的平面波超软赝势法进行了动力学模拟.发现在400，600和800℃的条件下界面原子有不同的扩散能力，因此温度对ZnO/α-Al₂O₃(0001)表面界面结构以及ZnO薄膜生长初期模式有决定性的影响.在整个ZnO吸附生长过程中，O原子的扩散系数大于Zn原子的扩散系数，O原子的层间扩散对薄膜的均匀生长起着重要作用.进一步从理论计算上证实了ZnO在蓝宝石(0001)上两种生长模式的存在，400℃左右生长模式主要是Zn螺旋扭曲生长，具有Zn六角平面对称特征，且有利于Zn原子位于最外表面.600℃左右呈现为比较规则的层状生长，且有利于O原子位于最外表面.模拟观察到在ZnO薄膜临近Al₂O₃基片表面处，Zn的空位缺陷明显多于O的空位缺陷. 关键词： 扩散 薄膜生长 2O₃(0001)')" href="#">α-Al₂O₃(0001) ZnO     

ZnO纳米线薄膜的合成参数、表面形貌和接触角关系研究

水浴法合成ZnO纳米线薄膜的工艺参数直接影响其表面形貌, 并使其接触角及润湿性能发生变化. 本文仿真分析了轮廓算数平均偏差、偏斜度、峭度、相关长度等特征参数对随机粗糙表面特性的影响规律; 改变生长时间、种子层溶液和生长液的浓度, 批量制备了表面形貌不同的ZnO纳米线薄膜; 提出了取样长度的确定方法, 并基于扫描电镜图像和Matlab图像处理算子对ZnO纳米线薄膜表面形貌的特征参数进行了提取; 将表面形貌高度和水平方向的特征参数引入Wenzel模型, 分析了合成参数、表面形貌特征参数与接触角的影响关系. 结果表明, 合成参数变化时, 选择取样长度5.0 μm为宜; 生长液浓度大于0.125 mol/L时, ZnO纳米线之间发生重结晶, 并呈现疏水性; 改变种子层溶液浓度和生长时间, 均得到超亲水表面. 上述结论可用于不同氧化酶、细胞等在ZnO纳米线薄膜上的有效吸附及相应传感器测试性能的进一步提高. 关键词： ZnO纳米线 水浴合成 表面形貌 接触角     

Growth,structure, and cathodoluminescence of Dy-doped ZnO nanowires

Dy-doped ZnO nanowires have been prepared using high-temperature and high-pressure pulsed-laser deposition. The morphology, structure, and composition of the as-prepared nanostructures are characterized by field emission scanning electron microscopy, X-ray diffraction, Raman scattering spectrometry, X-ray photoelectron spectrometry, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The alloying droplets are located at the top of the as-prepared Dy-doped ZnO nanowires, which means that the growth of the Dy-doped ZnO nanowires is a typical vapor-liquid-solid process. The luminescence properties of Dy-doped ZnO nanowires are characterized by cathodoluminescence spectra and photoluminescence spectra at low temperature (8 K). Two peaks at 481 and 583 nm, respectively, are identified to be from the doped Dy³⁺ ions in the CL spectra of Dy-doped ZnO nanowires.     

纳米ZnO生长及性质分析

利用低压金属有机化学气相沉积(LP-MOCVD)技术,在表面含有ZnO颗粒作为催化剂的Si(111)衬底上制备了ZnO纳米柱阵列。采用X射线衍射(XRD)、喇曼光谱(Raman)、扫描电子显微镜(SEM)、光致发光(PL)谱分析了样品的晶体结构质量、表面性质和光学性质。结果表明,生长出来的纳米ZnO具有较好的c轴择优取向性。发现氧分压对ZnO纳米柱的生长有重要影响:当氧分压较低时,生长基于VLS机制;当氧分压较高时,生长基于VS机制;通过对N2O流量的控制可实现对ZnO纳米材料的可控生长。     

Characteristics of ZnO epilayer on the post-annealed buffer layer on GaN/sapphire substrate by pulsed laser deposition

We employed epi-GaN substrates for ZnO film growth, and studied the deposition and post-annealing effects. ZnO films were grown by pulsed laser deposition (PLD) method. The as-grown films were annealed for one hour under atmospheric pressure air. ZnO morphologies after annealing were investigated and the post-annealed ZnO films grown at T _g =700^oC have very smooth surfaces and the rms with roughness is about 0.5 nm. Finally, ZnO post-annealed buffer layer was inserted between ZnO epilayer and GaN/sapphire substrates. It is confirmed by AFM that growth temperature of 700^oC helps the films grow in step-flow growth mode. It is observed by cathode luminescence spectrum that the ZnO film grown at 700^oC has very low visible luminescence, indicating the decrease of the deep level defects. It is also revealed by Hall measurements that carrier concentration is decreased by increasing the growth temperatures. It is suggested that low temperature buffer layer growth and post-annealing technique can be used to fabricate ZnO hetero-epitaxy.     

Nanointegration of ZnO with Si and SiC

The study is dedicated to some aspects of the controlled heteroepitaxial growth of nanoscaled ZnO structures and an investigation of their general and dimension mediated properties. ZnO nanostructures were synthesized by optimized MOCVD process via two growth approaches: (i) catalyst free self-organized growth of ZnO on Si substrates and (ii) ZnO heteroepitaxy on p-type hexagonal 4H-SiC substrates. The SiC substrate was prepared by sublimation epitaxy and served as a template for the ZnO epitaxial growth. The epitaxial growth of n-ZnO on p-SiC resulted in a regular matrix of well-faceted hexagonally shaped ZnO single crystals. The achievement of ZnO integration with Si encompasses controlled growth of vertically oriented nanosized ZnO pillars. The grown structures were characterized by transmission electron microscopy and microphotoluminescence. Low concentration of native defects due to a stoichiometry balance, advanced optical emission, (excitonic type near-band-edge emission and negligible defect related luminescence) and continuous interfaces (epitaxial relationship ZnO_[0 0 0 1]/SiC_[0 0 0 1]) are evidenced. The ZnO nanopillars were further probed as field emitters: the grown structures exhibits advanced field emission properties, which are explained in term of dimensionality and spatial uniformity of the nanopillars. The present results contribute to understanding and resolving growth and device related issues of ZnO as a functional nanostructured material.     

Synthesis and photoluminescence,field emission properties of stalactite-like ZnS-ZnO composite nanostructures

Wurtzite stalactite-like quasi-one-dimensional ZnS nanoarrays with ZnO protuberances were synthesized through a thermal evaporation route. The structure and morphology of the samples are studied and the growth mechanism is discussed. X-ray diffraction (XRD) results show both the ZnS stem and the ZnO protuberances have wurtzite structure and show preferred [001] oriented growth. The photoluminescence and field emission properties have also been investigated. Room temperature photoluminescence result shows it has a strong green light emission, which has potential application for green light emitter. Experimental results also show that the stalactite arrays have a good field emission property, with turn-on field of 11.4 V/μm, and threshold field of 16 V/μm. The ZnO protuberances on the ZnS stem might enhance the field emission notably. PACS 81.05.Dz; 81.07.Bc; 81.16.-c; 78.60.Hk; 85.45.Db     

Facilitating epitaxial growth of ZnO films on patterned GaN layers: A solution-concentration-induced successive lateral growth mechanism

The hydrothermal epitaxy of ZnO films on a patterned GaN layer with a honeycomb etching hole array is demonstrated. Through m-planes of the GaN layer exposed on the vertical walls of the etching holes, highly crystalline ZnO films via multiple lateral growth stages can be realized. It is found that higher concentrations of zinc nitrate hexahydrate (ZNH) and hexamethylenetetramine (HMT) in hydrothermal solution yield a larger number of ZnO molecules to speed up ZnO growth during the initial stage of hydrothermal growth, also create secondary crystals and initialize further lateral growth stages to bridge neighboring ZnO prisms after smooth surfaces formed on the m-plane of a ZnO prism. A successive lateral growth mechanism that strongly depends on ZNH and HMT concentrations in the hydrothermal solution is proposed and discussed.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Synthesis, effect of capping agents, structural, optical and photoluminescence properties of ZnO nanoparticles

Zinc oxide nanoparticles were synthesized using chemical method in alcohol base. During synthesis three capping agents, i.e. triethanolamine (TEA), oleic acid and thioglycerol, were used and the effect of concentrations was analyzed for their effectiveness in limiting the particle growth. Thermal stability of ZnO nanoparticles prepared using TEA, oleic acid and thioglycerol capping agents, was studied using thermogravimetric analyzer (TGA). ZnO nanoparticles capped with TEA showed maximum weight loss. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for structural and morphological characterization of ZnO nanoparticles. Particle size was evaluated using effective mass approximation method from UV-vis spectroscopy and Scherrer's formula from XRD patterns. XRD analysis revealed single crystal ZnO nanoparticles of size 12-20 nm in case of TEA capping. TEA, oleic acid and thioglycerol capped synthesized ZnO nanoparticles were investigated at room temperature photoluminescence for three excitation wavelengths i.e. 304, 322 and 325 nm, showing strong peaks at about 471 nm when excited at 322 and 325 nm whereas strong peak was observed at 411 for 304 nm excitation.     

热氧化法制备ZnO纳米晶体、纳米线

以高纯Zn块为源材料,通过热氧化法制备了纳米ZnO薄膜。在950℃的温度和一定的压力条件下,通过改变生长时间,分别制备了ZnO纳米晶体、纳米纤维和纳米线。应用扫描电镜观察发现,在恒温生长条件下,纳米ZnO具有定向生长的趋势。随生长时间的延长,纳米晶体定向生长为纳米纤维,最后生长为超长的纳米线。     

Growth and optical study of ZnO nanorods

ZnO nanorods were grown by a simple near room temperature, chemical solution method on ZnO-seeded silicon substrates. Study of the ZnO nanorods over different growth times by electron microscopy methods revealed that the resulting ZnO nanorods were single crystalline with a highly preferential growth perpendicular to the substrate and a very good c-axis alignment. The size of the nanorods increased with increasing growth time. The growth mechanism is briefly discussed. Post-annealing in oxygen slightly improved the surface roughness of the ZnO nanorods. Photoluminescence experiments at 1.6 K revealed a major emission peak of the nanorods at around 3.36 eV which is attributed to the band edge transition of ZnO, while defect-related emission is relatively weak.     

ZnO three-dimensional hedgehog-like nanostructure: synthesis,growth mechanism and optical enhancement

The 3D hedgehog-like ZnO nanostructures were synthesized on Si substrate through chemical vapor deposition process. The morphology and structure of the products were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, as well as transmission electron microscopy. The ZnO 3D hedgehog-like architectures were found to consist of a central nucleus and multiple side-growing nanowires with diameter of 100–250 nm and length up to 10 µm. The growth mechanism of the hedgehog-like ZnO nanostructures was studied. It revealed a three-step process during the entire growth. Finally, room temperature photoluminescence spectra of ZnO 3D nanostructures showed that the center excitation would render much stronger PL emission intensity. Furthermore, simulation results indicated that the enhanced emission came from light-trapping-induced excitation light field enhancement.     

Liquid phase epitaxial growth and optical property of flower-like ZnO nanosheets on Zinc foil

Large scale flower-like ZnO nanosheets have been synthesized on Zinc foil by a simple hydrothermal method. Their morphology and microstructures were characterized and analyzed by X-ray spectroscopy (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM). The as-synthesized flower-like nanosheets are hexagonal phase single crystal with 200-300 nm in width, 50 nm in thickness. The growth process follows the liquid phase epitaxial growth mechanism. In this approach, the ZnO buffer is used as substrate for the growth of flower-like ZnO nanosheets. The growth direction of the nanosheets is the preferential [0 0 0 1] growth direction of ZnO. The photoluminescence spectrum of the sample exhibits only a sharp and strong UV emission centered at 386 nm, which indicates that the flower-like ZnO nanosheets on Zn foil are of good optical property.     

Growth mechanism studies of ZnO nanowire arrays via hydrothermal method

Well-controlled ZnO nanowire arrays have been synthesized using the hydrothermal method, a low temperature and low cost synthesis method. The process consists of two steps: the ZnO buffer layer deposition on the substrate by spin-coating and the growth of the ZnO nanowire array on the seed layer. We demonstrated that the microstructure and the morphology of the ZnO nanowire arrays can be significantly influenced by the main parameters of the hydrothermal method, such as pH value of the aqueous solution, growth time, and solution temperature during the ZnO nanowire growth. Scanning electron microscopy observations showed that the well oriented and homogeneous ZnO nanowire arrays can be obtained with the optimized synthesis parameters. Both x-ray diffraction spectra and high-resolution transmission electron microscopy (HRTEM) observations revealed a preferred orientation of ZnO nanowires toward the c-axis of the hexagonal Wurtzite structure, and HRTEM images also showed an excellent monocrystallinity of the as-grown ZnO nanowires. For a deposition temperature of 90 °C, two growth stages have been identified during the growth process with the rates of 10 and 3 nm/min, respectively, at the beginning and the end of the nanowire growth. The ZnO nanowires obtained with the optimized growth parameters owning a high aspect ratio about 20. We noticed that the starting temperature of seed layer can seriously influence the nanowire growth morphology; two possible growth mechanisms have been proposed for the seed layer dipped in the solution at room temperature and at a high temperature, respectively.     

Thermo-electrochemical selective growth of ZnO nanorods on any noble metal electrodes

Selective growth of ZnO nanorods has been successfully performed on the patterned Au/Ti metal electrode regions on a glass substrate by using a seeded thermo-electrochemical method in an acidic growth solution. The selective growth mechanism of the thermo-electrochemical method was proposed by using a series of chemical reactions for the first time. The thermo-electrochemical selective ZnO growth was performed on the cathode electrode at a temperature below 90 °C. A ZnO seed layer was precoated and selectively etched away from the non-metal regions in order to create the patterned selective nucleation sites on which the precursors are transferred and crystallized into ZnO nanorods. Both the dimensions and the placements of the ZnO nanorods have been simultaneously controlled. Energy dispersive X-ray spectrometry showed that the selectively grown ZnO nanorods consist of only Zn and O, indicating that the selectively grown ZnO nanorods are pure and contamination free. XRD and electron diffraction patterns revealed that the obtained ZnO nanorods have a wurtzite single-crystal structure.     

Synthesis,structural and ellipsometric evaluation of oxygen-deficient and nearly stoichiometric zinc oxide and indium oxide nanowires/nanoparticles

Oxygen-deficient (OD) and nearly stoichiometric (NST) ZnO and In₂O₃ nanowires/nanoparticles were synthesized by chemical vapor deposition on Au-coated silicon substrates. The OD ZnO and OD In₂O₃ nanowires were synthesized at 750 and 950°C, respectively, using Ar flow at ambient pressure. A mixture of flowing Ar and O₂ was used for synthesizing NST ZnO nanowires and NST In₂O₃ nanoparticles. Growth of OD ZnO nanowires and NST In₂O₃ nanoparticles was found to be via a vapor–solid (VS) mechanism and the growth of NST ZnO nanowires was via a vapor–liquid–solid mechanism (VLS). However, it was uncertain whether the growth of OD In₂O₃ nanowires was via a VS or VLS mechanism. The optical constants, thickness and surface roughness of the prepared nanostructured films were determined by spectroscopic ellipsometry measurements. A three-layered model was used to fit the calculated data to the experimental ellipsometric spectra. The refractive index of OD ZnO, NST ZnO nanowires and NST In₂O₃ nanoparticles films displayed normal dispersion behavior. The calculated optical band gap values for OD ZnO, NST ZnO, OD In₂O₃ nanowires and NST In₂O₃ nanoparticles films were 3.03, 3.55, 2.81 and 3.52?eV, respectively.     

生长温度对MOCVD外延ZnO纳米结构的影响

为了探究生长温度对外延ZnO纳米结构的影响,得到ZnO纳米结构可控生长的生长温度条件。利用金属有机化学气相沉积（MOCVD）方法,设计并获得了不同生长温度的ZnO外延样品,并对所有样品进行了表面形貌、光学特性、电学特性表征和结晶质量表征。实验结果表明:600℃生长的ZnO纳米柱横向尺寸最小,为65 nm左右,其光学特性也相对较好,晶体衍射峰的半峰宽最小,为0.165°,晶粒尺寸最大,为47.6 nm;电学性质相对最优的为640℃生长的ZnO样品,霍尔迁移率高达23.5 cm²/（V·s）。通过结果分析发现,生长温度能影响外延ZnO的生长模式,从而影响ZnO的形貌、光学、电学和晶体质量等特性。     

Effects of growth duration on the structural and optical properties of ZnO nanorods grown on seed-layer ZnO/polyethylene terephthalate substrates

Well-aligned single crystalline zinc oxide (ZnO) nanorods were successfully grown, by hydrothermal synthesis at a low temperature, on flexible polyethylene terephthalate (PET) substrates with a seed layer. Photoluminescence (PL), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) measurements were used to analyze the optical and structural properties of ZnO nanorods grown for various durations from 0.5 h to 10 h. Regular and well-aligned ZnO nanorods with diameters ranging from 62 nm to 127 nm and lengths from 0.3 μm to 1.65 μm were formed after almost 5 h of growth. The growth rate of ZnO grown on PET substrates is lower than that grown on Si (1 0 0) substrates. Enlarged TEM images show that the tips of the ZnO nanorods grown for 6 h have a round shape, whereas the tips grown for 10 h are sharpened. The crystal properties of ZnO nanorods can be tuned by using the growth duration as a growth condition. The XRD and PL results indicate that the structural and optical properties of the ZnO nanorods are most improved after 5 h and 6 h of growth, respectively.     

Vapour phase transport growth of ZnO layers and nanostructures

We have developed a novel advanced VPT set-up. ZnO layers and nanorods were grown employing a specially designed horizontal vapour transport system with elemental sources at relatively low temperatures without catalysis. We employed 6N elemental Zn carried by nitrogen and 99.995% oxygen as reactants. Sapphire, SiC, bulk ZnO and ZnO epitaxial layers were implemented as substrates for ZnO growth. Growth temperatures ranged from 500 to 900 C. Reactor pressures were from 5 mbar to atmospheric pressure. We employed x-ray diffractometry, optical microscopy, scanning electron microscopy and atomic force microscopy to investigate the obtained ZnO samples and the influence of different growth parameters on the ZnO homo- and heteroepitaxial growth and to optimise the set of growth parameters either for both epitaxial layers and nanostructures. We also show that the quality of the VPT grown ZnO epitaxial layers on sapphire can be even higher (evaluated from FWHM of the XRD rocking curves) than the MBE grown ones used as epiwafers for VPT growth. High quality ZnO layers with extremely narrow FWHM of the (0002) rocking curve of 38″ are fabricated employing our VPT approach.