Effect of variable pressure on growth and photoluminescence of ZnO nanostructures

Thin films constituted of equiaxed and one dimensional nanostructures of ZnO via metal-catalyst-free vapor phase were grown using a simplistic thermal evaporation technique under two different pressure conditions approximately of the order of 10(-1) and 10(-3) torr, respectively. ZnO deposited at low vacuum (approximately 10(-1) torr) exhibited the formation of nanograins of variable size between 60 to 180 nm. In contrast the film grown at high vacuum (approximately 10(-3) torr) resulted the nanowired type morphology with a random networking, generally distributed with equiaxed grains of film microstructure. The diameter of maximum number of these nanowires lies between 45 to 65 nm. The films grown at low vacuum has shown almost equal composition of Zn and O while the film grown at high vacuum has shown lower content of O. The nanowires formed under limited O (high vacuum: approximately 10(-3) torr) signifies the role of O vacancies during growth. It has been postulated that presumably under high vacuum deposition, initially formed ZnO transforms to ZnOx (x < 1) through creation of O vacancies due to limited presence of O. Subsequently ZnOx acts as self-catalyst and heterogeneous nuclei are responsible for the formation of nanowired type morphology. The effect of different microstructures has been correlated and discussed to understand the photoluminescence characteristics obtained on these films.     

Synthesis of zinc oxide nanotetrapods and nanorods by thermal evaporation without catalysis

ZnO nanotetrapods and nanorods have been synthesized by a simple thermal evaporation of Zn powder (300 mesh, 99.99% purity) under simultaneous flow of oxygen and argon gases in two-zone furnace in two different temperature regions. These ZnO nanostructures have hexagonal structure, which grow along the [001] direction in the form of nanotetrapods (diameter approximately 60-150 nm, length approximately 1-4 microm) and nanorods (diameter approximately 30-60 nm, length approximately 2-5 microm). The morphologies of these ZnO nanostructures have been investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It has been found that growth parameters like temperature, gas flow rate etc., control the diameter of the nanotetrapods and nanorods. These novel structures of ZnO nanorods and nanotetrapods may be attractive for optical and other nanodevices.     

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.     

Simple solution phase synthesis of 3-D assembly of ZnO nanoneedles and its efficient field emission

Three dimensional (3-D) assemblies of ZnO nanoneedles have been synthesized on silicon substrate by a unique chemical process. Each nanoneedle in the assemblies was hexagonal faceted having [001] growth direction and tip diameter approximately 20 nm. The growth of 3-D assemblies was governed by the initial nuclei formation, followed by their aggregation and subsequently nanoneedle formation from each nucleus. Room temperature photoluminescence (PL) spectrum of the assemblies showed two prominent peaks, one narrow peak in the ultraviolet region (385 nm) and another broad peak in the visible region (440 nm-600 nm). The 3-D assemblies of ZnO nanoneedles showed very good field emission property with turn-on voltages 390 V, 530 V and 680 V for the anode-emitter distances of 100 microm, 200 microm and 300 microm respectively. The turn-on voltages showed a linear relationship with the anode-emitter distance. Field enhancement factor (beta) for the nanostructure was calculated to be 2873. The high beta value and the low turn-on field are attributed to the sharp needle like structure and their interesting three dimensional assemblies.     

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.     

Synthesis and characterization of one-dimensional MgO nanostructures

Magnesium oxide (MgO) nanowire arrays, nanoribbons, two- and three-dimensional network like nanostructures were prepared by the simple thermal evaporation of Mg powder with and without using catalyst at a relatively low temperature. The non-catalytic approaches favor the formation of network like nanoforms whereas the catalytic approaches favors the formation of one-dimensional nanowire arrays and quasi one-dimensional nanoribbons depending on the temperature and vapor concentrations of the growth site. The diameter and length of the MgO network like columns varied within 40-50 nm and approximately 200 nm respectively. The MgO nanowires produced by the catalytic approach had diameter within 20-30 nm and length approximately 2 microm. Whereas the widths of the nanoribbons varied within 50-100 nm and their length were of the order of a few hundred micrometers. The nanoforms were single crystalline and cubic in phase. The products were characterized by the X-ray diffraction study, energy dispersive analysis of X-ray study, scanning and transmission electron microscopy, and photoluminescence measurements to explore the structural, compositional, morphological, and physical properties of the MgO nanoforms.     

Fabrication of vertical ZnO nanowires on silicon (100) with epitaxial ZnO buffer layer

Vertical ZnO nanowires were successfully grown on epitaxial ZnO (002) buffer layer/Si (100) substrate. The nanowire growth process was controlled by surface morphology and orientation of the epitaxial ZnO buffer layer, which was deposited by radio-frequency (rf) sputtering. The copper catalyzed the vapor-liquid-solid growth of ZnO nanowires with diameter of approximately 30 nm and length of approximately 5.0 microm. The perfect wurtzite epitaxial structure (HCP structure) of the ZnO (0002) nanowires synthesized on ZnO (002) buffer layer/Si (100) substrate results in excellent optical characteristics such as strong UV emission at 380 nm with potential use in nano-optical and nano-electronic devices.     

Synthesis and characterization of Cu nanotubes and nanothreads by electrical arc evaporation

We report the formation and characterization of copper nanostructures, nanotubules and nanothreads, which were obtained by electrical arc evaporation of Cu electrodes under varied conditions of He ambience. Electrical arc evaporation was done with approximately 10 V and (approximately 50-100 A) DC current. The current was used in a pulse mode. The evaporated material was condensed on a formvar-coated Cu grid mounted on a liquid N2-cooled specimen holder. Transmission electron microscopy was employed to characterize the condensed materials. These investigations revealed that the condensed materials consisted of the mentioned nanostructures. Nanotubes and nanothreads are formed for a He pressure in the chamber corresponding to approximately 140 and approximately 500 torr, respectively. Extensive electron microscopic investigations showed that the diameter of the nanotubes varied from approximately 5 nm to approximately 50 nm and their length from 2 microns to 3 microns.     

Self-assembly hierarchical micro/nanostructures of leaf-like polyaniline with 1D nanorods on 2D foliage surface

A novel 2D leaf-like polyaniline with special hierarchical micro/nanostructures, a length of about 3 μm, width of about 2.3 μm and thickness of about 120 nm, has been successfully synthesized in the presence of poly (acrylic acid-co-maleic acid) sodium salt (PAA/MA-SS), which is self-assembled from 2D square nanoplate and 1D nanorods. Its surface consists of highly cross-linked nanorods of approximately 100 nm in length and 30 nm in diameter. In order to investigate the formation mechanism of such 2D leaf-like polyaniline, some micro/nanostructures of polyaniline are synthesized at different polymerization times and the results show that the polyaniline microleaves originate from square nanoplates, which then self-assemble into leaf-like micro/nanostructures with nanorods on the surface.     

The shape control of ZnO based nanostructures

Tetrapod-shape ZnO nanostructures are formed on Si substrates by vapor phase transportation method. The effects of two important growth parameters, growth temperature and VI/II ratio, are investigated. The growth temperature is varied in the range from 600 degrees C to 900 degrees C to control the vapor pressure of group II-element and the formation process of nanostructures. VI/II ratio was changed by adjusting the flux of carrier gas which affects indirectly the supplying rate of group VI-element. From the scanning electron microscopy (SEM), systematic variation of shape including cluster, rod, wire and tetrapod was observed. ZnO tetrapods, formed at 800 degrees C under the carrier gas flux of 0.5 cc/mm2 min, show considerably uniform shape with 100 nm thick and 1-1.5 microm long legs. Also stoichiometric composition (O/Zn - 1) was observed without any second phase structures. While, the decrease of growth temperature and the increase of carrier gas flux, results in the irregular shaped nanostructures with non-stoichiometric composition. The excellent luminescence properties, strong excitonic UV emission at 3.25 eV without deep level emission, indicate that the high crystalline quality tetrapod structures can be formed at the optimized growth conditions.     

Characterizations of Ga-doped ZnO nanowires depending on growth temperature and target-substrate distance in hot-walled pulsed laser deposition

Using a hot-walled pulsed laser deposition (HW-PLD), nanowires (NWs) comprising 3 weight% Ga-doped ZnO (3GZO) have been successfully grown on a sapphire substrate. The structural and optical properties of 3GZO nanostructures have also been systematically investigated with respect to the target-substrate (T-S) distance and the growth temperature. The morphology transformations of nanostructures such as nano-horns, NWs, and clusters are strongly affected by growth temperatures due to different thermal energy. Also, the morphologies of nanostructures--including length, diameter, and density--are strongly affected by the T-S distance, illustrating a close correlation between the growth kinetics and the position in the plume formed by the particles from the GZO target. Also, the exciton that is bound to the neutral donor (D(0)X) peak of the 3GZO nanostructures is found at the low temperature PL spectra, indicating successful Ga-doping into ZnO NWs.     

Controlled self-assembly of organic nanowires and platelets using dipolar and hydrogen-bonding interactions

Synergistic dipole-dipole and hydrogen-bonding interactions are used to assemble nanostructured materials. Precipitation of a hydrogen-bonding donor-acceptor molecule 8-[[p-[bis(ethyl)amino]phenyl]azo]-isobutylflavin (ABFL) yields nanowires approximately 50-150 nm in diameter and lengths of several millimeters. Precipitation of the non-hydrogen-bonding analog, methylated ABFL (MABFL), generates micrometer-sized hexagonal platelets that are 5-10 microm in length, 1-5 microm in width, and 0.1-0.5 microm thick. The structural similarity of the two molecules allows intermediate morphologies to be formed via co-precipitation. Doping experiments demonstrate efficient control over nanowire length and diameter due to the disruption of the hydrogen bonding within the nanowires.     

Crabwise ZnO nanowires: growth and field emission properties

Crabwise ZnO nanowires with an average length of 5 microm and an average diameter of 30 nm were selectively grown on ZnO:Ga/glass templates. Cathodoluminescence measurement indicated that the crystal quality of the crabwise ZnO nanowires was good. With an applied voltage of 120 V, the crabwise ZnO nanowire field emitters gave an emission current of 0.1 mA/cm2. Moreover, the field enhancement factor, beta, of the crabwise ZnO nanowires was approximately 980.     

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.     

Influence of process variables on growth of ZnO nanowires by cathodic electrodeposition on zinc substrate

Influence of the deposition duration and electrolyte concentration on the structural and morphological features of the ZnO thin films, grown by cathodic electrodeposition on zinc substrate followed by annealing in air at 400 °C, have been investigated. The surface morphology of the as-synthesized films shows two distinct features, presence of ‘2-dimensional nanosheets’ on the area near the electrolyte-air interface and ‘granular’ nanostructures, below the interface region. However, upon annealing, the formation of ZnO nanowires, possessing length of several microns and diameter less than 20 nm, on the entire substrate is observed. The X-ray and selected area electron diffraction patterns clearly confirm the polycrystalline nature of the ZnO nanowires.     

Morphology controlled synthesis of ZnO nanostructures by varying pH

ZnO nanostructures have been synthesized in a controlled manner by varying the pH of the precursor solution using hydrothermal technique. The morphological changes of the prepared ZnO nanostructures have been investigated in the range of pH 5–10. Radial hexagonal rod-like shape is formed at lower pH values of 5 and 6 whereas, flower-like shape is obtained for higher pH values of 9 and 10. Flake-like structure is observed at moderate pH of 8. The prepared ZnO nanostructures have been characterized using X-ray diffraction technique (XRD), energy dispersive X-ray analysis, scanning electron microscope and FTIR spectroscopy. XRD results show that the prepared ZnO nanostructures exhibit hexagonal wurtzite structure. The growth mechanism suggests that the supersaturation of the precursor results in various nucleation habits, which induce the formation of ZnO nanostructures with different morphologies. UV–Vis spectroscopy and photoluminescence were applied to study the optical properties. The photoluminescence spectrum demonstrated two emission bands, a near band edge emission in the UV region and a strong deep band emission in the visible region. The change in pH from 5 to 10 results in band gap variations of 3.47–3.97 eV and blue-shift in the peak emission of visible PL from 560 to 460 nm.     

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.     

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.     

Single layer polycrystalline ZnO-Al2O3 nanocomposite thin films: optical and electrical properties

Nanometric size dependent optical absorption coefficients, dispersive nature of the dielectric constants and ac conductivity are observed for the single layer ZnOx(Al2O3)1-x (x = 0.20 and 0.50) nanocomposites thin films. The sol-gel prepared thin films with thickness approximately 119 nm, contains randomly dispersed ZnO nanocrystallites in the A2O3, matrix. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) revealed homogeneous distributions of the nanoparticles in the matrix. The shifting and broadening of the optical absorption peaks to the lower wavelength region at higher annealing temperatures was analyzed in order to relate the particle-particle interactions and the sizes of the dispersed nanoparticles in the matrix. AC impedance spectroscopy in the frequency range of 500 Hz to 5 MHz was measured at room temperature (300 K), 325 K, 395 K, and 450 K. The dielectric relaxations in each case were found to be of Cole-Cole type. The semicircular pattern of the ac capacitance in the complex plane showed contributions from the grain and grain boundary subject to concentration of ZnO in the matrix. The appearance of the negative capacitance at higher frequency was also analyzed.     

Hydrogen peroxide-assisted hydrothermal synthesis of hierarchical CuO flower-like nanostructures

Hierarchical CuO nanostructures were synthesized through a hydrogen peroxide-assisted hydrothermal route in which Cu(OH)₂ was the copper source. The CuO nanostructures were composed of numerous nanobelts that radiated from the center of the nanostructure and formed a flower-like shape with a diameter of 5-10 μm. The nanobelts had lengths of 2.5-5 μm and widths of 150-200 nm. The H₂O₂ concentration directly influenced the product morphology. As the concentration of H₂O₂ increased, the length and width of the nanobelts increased and the quantity of the nanobelts decreased. The possible formation mechanism of hierarchical CuO flower-like nanostructures was presented.