Nucleation and growth of catalyst-free zinc oxide nanostructures

This paper deals with the investigations on the nucleation and growth of Zinc Oxide (ZnO) nanostructures in a catalyst free synthesis. The ZnO nanostructures have been formed by evaporation of Zn (99.99%) in O2 and Ar atmosphere in single zone furnace under two temperature regions, region A (approximately 1173-1073 K) and region B (approximately 873-773 K). Through application of XRD and TEM techniques, it has been shown that first ZnO is formed which changes to ZnOx through creation of oxygen vacancies. The ZnOx acts as self-catalyst and leads to formation of various nanostructures. Those observed in the present investigation are nanotetrapods (1 D, diameter approximately 70-450 nm, length approximately 2-4.5 approximatelym) nanorods (1 D, diameter approximately 45-95 nm, length approximately 2.5-4.5 microm), nanoflowers(2D, central core diameter approximately 90-185 nm, length of petals/nanorod approximately 1.0-3.5 microm) and nanoparticles (3D, size approximately 0.85-2.5 microm). These nanostructures have been revealed by SEM explorations. Attempts have been made to explain the formation of the various nanostructures in terms of the creation and distribution of the ZnOx, the temperature as well as oxygenation conditions.     

Structural and magnetic properties of Zn1-xcoxO nanorods prepared by microwave irradiation technique

We have successfully synthesized large-scale aggregative flowerlike Zn1-xCo(x)O (0.0 < or = x < or = 0.07) nanostructures, consisting of many branches of nanorods at different orientations with diameter within 100-150 nm (tip diameter approximately 50 nm) and length of approximately 1 microm. The rods were prepared using Zinc nitrate, cobalt nitrate and KOH in 180 Watt microwave radiation for short time interval. The synthesized nanorods were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), field emission transmission electron microscopy (FETEM) and DC magnetization measurements. XRD and TEM results indicate that the novel flowerlike nanostructures are hexagonal with wurtzite structure and Co ions were successfully incorporated into the lattice position of Zn ions in ZnO matrix. The selected area electron diffraction (SAED) pattern reveals that the nanorods are single crystal in nature and preferentially grow along [0 0 1] direction. Magnetic studies show that Zn1-xCo(x)O nanorods exhibit room temperature ferromagnetism. This novel nanostructure could be a promising candidate for a variety of future spintronic applications.     

Rapid growth of nanotubes and nanorods of würtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution

Large quantities of single-crystalline ZnO nanorods and nanotubes have been prepared by the microwave irradiation of a metalorganic complex of zinc, in the presence of a surfactant. The method is simple, fast, and inexpensive (as it uses a domestic microwave oven), and yields pure nanostructures of the hexagonal würtzite phase of ZnO in min, and requires no conventional templating. The ZnO nanotubes formed have a hollow core with inner diameter varying from 140–160 nm and a wall of thickness, 40–50 nm. The length of nanorods and nanotubes varies in the narrow range of 500–600 nm. These nanostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The ZnO nanorods and nanotubes are found by SAED to be single-crystalline. The growth process of ZnO nanorods and nanotubes has been investigated by varying the surfactant concentration and microwave irradiation time. Based on the various results obtained, a tentative and plausible mechanism for the formation of ZnO nanostructures is proposed.     

The effects of addition of citric acid on the morphologies of ZnO nanorods

ZnO nanorods of 25-100 nm in diameter and 0.2-1 μm in length were fabricated through citric acid assisted annealing process. The microstructure of ZnO nanorods was characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and field-emission scanning electron microscopy, respectively. As a result, it was found that ZnO nanorods were single crystalline and pure. The effects of the growth conditions such as addition of citric acid, annealing temperature on the morphologies of ZnO nanostructures have also been investigated. At the given temperature the length decreased but the diameter increased with addition of the mass of citric acid. With the rising of the calcining heat, the shape of ZnO changed from rod to granule for a given amount of citric acid. Finally, the mechanism for citric acid assisted annealing synthesis of the ZnO nanostructure is discussed.     

Growth of well-aligned ZnO nanorods using auge catalyst by vapor phase transportation

Well-aligned ZnO nanorods have been achieved using new alloy (AuGe) catalyst. Zn powder was used as a source material and it was transported in a horizontal tube furnace onto an AuGe deposited Si substrates. The structural and optical properties of ZnO nanorods were characterized by scanning electron microscopy, high resolution X-ray diffraction, and photoluminescence. ZnO nanorods grown at 650 degrees C on 53 nm thick AuGe layer show uniform shape with the length of 8 +/- 0.5 microm and the diameter of 150 +/- 5 nm. Also, the tilting angle of ZnO nanorods (+/- 5.5 degrees) is confirmed by HRXRD. High structural quality of the nanorods is conformed by the photoluminescence measurement. All samples show strong UV emission without considerable deep level emission. However, weak deep level emission appears at high (700 degrees C) temperature due to the increase of oxygen desertion.     

Epitaxial growth of the zinc oxide nanorods, their characterization and in vitro biocompatibility studies

Here, we have synthesized Zinc Oxide (ZnO) nanorods at room temperature using zinc acetate and hexamethylenetetramine as precursors followed by characterization using X-ray diffraction (XRD), fourier transform infra red spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The growth of the synthesized ZnO was found to be very close to its hexagonal nature, which is confirmed by XRD. The nanorods were grown perpendicular to the long-axis and grew along the [001] direction, which is the nature of ZnO growth. The morphology of the synthesized ZnO nanorods was also confirmed by SEM. The size of the nanorod was estimated to be around 20-25?nm in diameter and approximately 50-60?nm in length. Our biocompatibility studies using synthesized ZnO showed no significant dose- or time-dependent increase in the formation of free radicals, accumulation of peroxidative products, antioxidant depletion or loss of cell viability on lung epithelial cells.     

Growth of tungsten oxide nanorods with carbon caps

Hybrid nanostructures consisting of tungsten oxide nanorods with mushroom-shaped carbon caps were grown on electrochemically etched tungsten tips by thermal chemical vapor deposition with methane and argon. These nanorods grow along the radial direction and are very straight and smooth. Electron microscopy revealed a dominant diameter and length of approximately 50 nm and approximately 0.6 microm, respectively. High-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS) revealed the presence of crystalline monoclinic W18O49 in the nanorods, and the cap was entirely amorphous carbon. A plausible growth mechanism involves the reduction of tungsten oxide WO3, present on the tungsten surface, by methane at 900 degrees C.     

A simple microwave-assisted decomposing route for synthesis of ZnO nanorods in the presence of PEG400

In the paper, a simple microwave-assisted decomposing reaction in the presence of PEG400 has been successfully developed to synthesize ZnO nanorods with 10-25 nm of diameter and 60-200 nm of length. The product was analyzed and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and HRTEM. Ultraviolet-visible (UV-vis) absorption peak of ZnO nanorods shows a distinct blue shift from that of the bulk and the Photoluminescence (PL) spectrum exhibits a strong near-band-edge emission at 385 nm. Further experiments have also been designed, and the results show that microwave radiation and surfactant PEG400 all played an important role on the formation of ZnO nanorods.     

水溶液法制备CdSe和ZnSe纳米棒

用水溶液法直接合成了水溶性、发荧光的ZnSe和CdSe纳米棒。ZnSe纳米棒的直径约20～30nm,长度可达60～70nm;CdSe纳米棒的直径约30～60nm,长度可达150～450nm。用X射线衍射仪(XRD)、透射电镜(TEM)、高分辨透射电镜(HR-TEM)、荧光仪等仪器对纳米棒进行了表征。XRD和HRTEM的结果显示纳米棒具有立方结构,结晶度较高。讨论了纳米棒的形成机理以及pH对纳米棒发光强度的影响。合成的纳米棒在水溶液中至少稳定半年,表面被氨基和羧基化,在生物分析中具有广泛的应用前景。     

CO2-mediated synthesis of ZnO nanorods and their application in sensing ethanol vapor

High-purity ZnO nanorods have been synthesized via a two-step route using zinc acetate as a precursor without any surfactant and additive. In this method, ZnCO3 fibers were first formed in the CO2-ethanol solution, which directed the formation of ZnO nanorods by subsequent treatment in KOH aqueous solution. The as-prepared nanorods were fully characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and Fourier transform Infrared spectroscopy. It was found that the as-obtained ZnO nanorods were single crystals with uniform diameter around 150 nm and length of 4 microm. The nanorod crystals were prismatic with hexagonal cross sections, consistent with the wurtzite lattice structure. Moreover, the sensing properties of the as-prepared ZnO nanorods were also investigated. It was demonstrated that they exhibited good performance for detecting ethanol vapor even at 380 and 250 degrees C.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Controlled morphology of ZnO nanostructures by adjusting the zinc foil heating temperature in an air-filled box furnace

By heating zinc foil in an air-filled box furnace, one-dimensional ZnO nanorods, two-dimensional ZnO nanoplates and three-dimensional ZnO nanotetrapods were prepared by adjusting the temperature in the furnace in the ranges of 500–600, 650–750 and 800–900 °C, respectively. The morphologies, structures and emissions of the synthesized ZnO nanostructures were investigated by scanning electron microscopy, X-ray diffractometry, transmission electron microscopy, selected area electron diffraction and photoluminescence spectroscopy. Mechanisms on the control of the morphology and photoluminescence were discussed in terms of the crystal growth habits combined with the temperature-dependent diffusions of zinc and oxygen atoms in the ZnO lattices.     

Zinc oxide nanorod growth on gold islands prepared by microsphere lithography on silicon and quartz

Gold islands, vapor deposited on silicon and quartz by microsphere lithography patterning, are used to nucleate arrays of ZnO nanorods. ZnO is grown on approximately 0.32 microm2 Au islands by carbothermal reduction in a tube furnace. Scanning electron microscopy (SEM) and energy dispersive atomic X-ray spectroscopy (EDS) confirm that the gold effectively controls the sites of nucleation of ZnO. Atomic force microscopy (AFM) shows that approximately 30 nm diameter nanorods grow horizontally, along the surface. Alloy droplets that are characteristic of the vapor-liquid-solid (VLS) mechanism are observed at the tips of the nanorods. The spatial growth direction of VLS catalyzed ZnO nanorods is along the substrate when they nucleate from gold islands on silicon and quartz. The energy of adhesion of the VLS droplet to the surface can account for the horizontal growth.     

室温固相法合成ZnO纳米棒及其光学特性

在氯化钠存在下,以硫酸锌和氢氧化钠为原料,采用一步室温固相法制备了纳米氧化锌.XRD、TEM分析结果表明:所得纳米氧化锌为棒状,直径约10nm左右,长度约100～160nm.利用紫外-可见分光光度计测试了光吸收性能,发现ZnO纳米棒对200～380nm波长范围的光有很强吸收性,在可见光范围内,也有较强的吸收.ZnO纳米棒在550nm左右具有较弱的荧光发光峰且ZnO纳米棒较普通氧化锌发光峰波长发生了明显的红移.     

ZnO纳米四脚状阵列电极染料敏化太阳能电池

采用化学气相沉积(CVD)法制备了不同尺寸的四脚状纳米ZnO和ZnO纳米棒。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)对纳米ZnO的晶型结构和形貌进行表征,研究结果表明CVD法制备的四脚状纳米ZnO具有三维空间结构,其最小平均臂宽约为70nm,臂长约300nm,制备的纳米棒直径约为84nm,长约2μm,且都为六方纤锌矿晶型结构。将ZnO纳米四脚状及纳米棒利用滚涂法在FTO导电玻璃上形成ZnO光阳极,经N719染料敏化后组装成染料敏化太阳能电池,光电性能结果表明,染料敏化小尺寸的四脚状纳米ZnO太阳能电池光电转换效率(η=1.88%)高于染料敏化大尺寸的四脚状纳米ZnO太阳能电池光电转换效率(η=1.18%),远高于染料敏化ZnO纳米棒太阳能电池的光电转换效率(η=0.7%)。     

反应时间对球状及棒状ZnO纳米晶的影响

本实验采用溶液法合成球状及棒状ZnO纳米晶。X射线衍射分析(XRD)显示合成的纳米晶为六方纤锌矿结构ZnO。紫外可见光(UV-vis)光谱和透射电镜(TEM)图表明通过改变反应时间可以控制ZnO纳米棒的长度。随着反应时间从90min延长到360min,纳米棒的长度可以从25nm长大到60nm。同时,纳米晶的室温光致发光谱(PL)具有强烈的近带边发射,在LED和LD等光电器件上有一定的应用前景。     

Effect of ammonia water on the morphology of monoethanolamine-assisted sonochemicaly synthesized ZnO nanostructures

In the present work, ZnO nanostructures were synthesized by monoethanolamine (MEA)-assisted ultrasonic method at low temperature. Structural analysis was carried out by X-ray diffraction (XRD) confirmed the formation of hexagonal wurtzite structure of ZnO. The effect of ammonia water on the molecular structure of MEA, and its effect on the morphology of ZnO nanostructures were monitored by electron microscopy. Scanning electron microscopy (SEM) results suggest that ZnO nanoparticles with 100 nm in diameter were produced in case of MEA-assisted ultrasonic method. However, as ammonia water was added into the reaction system the morphology of ZnO nanoparticles changed into nanorods, flower-like nanostructures and finally microrods. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies showed that as prepared ZnO nanostructures were single crystalline in nature and grew in different directions resulted in the formation of various structures. The growth mechanism of as prepared ZnO nanostructures was discussed in detail. It was proposed that the addition of ammonia water into the reaction system resulted into the formation of ethylene diamine (EDA) which directed the growth of ZnO. The optical property was studied by photoluminescence (PL) spectroscopy showed only UV emission and no defects mediated visible emission.     

Catalyst-free MOCVD growth of ZnO nanorods and their structural characterization

We have synthesized ZnO nanorods on ZnO-coated Si(100) substrates without a metal catalyst by a reaction of a diethylzinc (DEZn) and oxygen (O₂) mixture. By adjusting the argon (Ar)/O₂ gas flow ratio, we have obtained ZnO nanorods of various densities at a temperature of 450°C. The ZnO nanorods had an average diameter of 30–70 nm, and transmission electron microscopy (TEM) showed a single crystalline structure.     

Low-temperature growth of well-aligned ZnO nanorods/nanowires on flexible graphite sheet and their photoluminescence properties

We have grown large-scale well-aligned ZnO nanorods/nanowires on commercial flexible graphite sheet (FGS) at low temperature via chemical vapor deposition method. The products were characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The effects of the growth temperature and oxygen flow rate on the morphology of ZnO nanostructures have been investigated. The growth mechanism of ZnO is found to be a self-catalytic vapor–solid process assisted by the immiscibility of ZnO with graphite. The as-grown ZnO/FGS products show strong green emission and their photoluminescence properties can be tuned by changing growth condition or annealing treatment.     

Size-induced variations in lattice dimension, photoluminescence, and photocatalytic activity of ZnO nanorods

Highly crystalline ZnO nanorods with diameters ranging from 5 to 57 nm were prepared by a seed-mediated solution method. With a diameter reduction, the lattice volume of ZnO nanorods increased and c/a ratio decreased, in apparent contradiction to what was observed in spherical ZnO nanocrystals. All ZnO nanorods showed a strong yellow emission without the UV or green emissions that had been observed for ZnO nanostructures prepared by other methods. For larger diameters, the yellow emission exhibited an abnormal red shift, which was associated with the lattice variations in the nanoscale structure and the resulting band modifications. The size-induced band modifications were also confirmed by the photocatalytic activity of ZnO nanorods, which have an optimum diameter (approximately 30 nm) for the photodegradation of Rhodamine B dye solution.