Vertically aligned nanocrystalline Cu–ZnO thin films for photoelectrochemical splitting of water

Cu-incorporated nanocrystalline ZnO thin films were deposited on glass substrate by sol–gel. To a solution of zinc acetate 2-hydrate in dimethyl formamide, calculated quantities of copper acetate were added. The clear solution, obtained after 2 h of continuous stirring, was coated on ITO plates. Pre-annealing at 250 °C was followed by sintering at 400, 500, and 600 °C. XRD analysis revealed dominant evolution of hexagonal ZnO with a possible simultaneous growth of meta-stable cubic ZnO. AFM and SEM analysis indicated preferential growth of nanocrystallites along c-axis. Optical characterization led to two prominent absorption thresholds in the UV region; one matching with the band gap of bulk ZnO and the second at slightly higher energy, suggesting quantum confinement effect in nanocrystallites. Cu incorporation influenced the two band gap energies differently. Photoelectrochemical splitting of water using 1% at. Cu–ZnO film sintered at 600 °C resulted in 141% gain in photocurrent at zero bias.     

Studies on ac response of zinc oxide pellets

The ac responses of the ZnO pellets have been studied by ac measurements (impedance, capacitance and phase angle) over the temperature range 300–435 K. The ac conductivity of the ZnO pellets is observed to be proportional to ω ^s , where ω is the angular frequency and the exponent s is a temperature- and frequency-dependent parameter. Based on the existing theories of ac conduction, it has been concluded that for low frequency region (20 Hz–2 kHz), the dominant conduction mechanism in the ZnO pellets is multihopping at all temperatures, whereas for high frequency region (500 kHz–2 MHz), the small polaron tunneling model is the dominant mechanism in the pellets. Activation energies for ac conduction processes are estimated to be in the range of 0.028–0.277 eV which are found to vary with the frequency of the ac signal. These results are found to be consistent with the hopping model. The ac capacitance and the dielectric loss tangent are found to be dependent on both frequency and temperature. Such dependences have been explained taking into account the equivalent circuit model comprising a frequency-independent capacitive element in parallel with a temperature-dependent resistive element, both in series with a low value resistance. Impedance spectroscopy studies show single semicircular arcs in the complex impedance spectra at all temperatures in the range 300–435 K, with their centres lying below the real axis at a particular angle of depression indicating a multirelaxation behaviour in the pellets.     

Effect of annealing temperature on electrical and nano-structural properties of sol–gel derived ZnO thin films

Zinc oxide (ZnO) thin films have been prepared on silicon substrates by sol–gel spin coating technique with spinning speed of 3,000 rpm. The films were annealed at different temperatures from 200 to 500 °C and found that ZnO films exhibit different nanostructures at different annealing temperatures. The X-ray diffraction (XRD) results showed that the ZnO films convert from amorphous to polycrystalline phase after annealing at 400 °C. The metal oxide semiconductor (MOS) capacitors were fabricated using ZnO films deposited on pre-cleaned silicon (100) substrates and electrical properties such as current versus voltage (I–V) and capacitance versus voltage (C–V) characteristics were studied. The electrical resistivity decreased with increasing annealing temperature. The oxide capacitance was measured at different annealing temperatures and different signal frequencies. The dielectric constant and the loss factor (tanδ) were increased with increase of annealing temperature.     

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.     

Growth of aligned arrays of ZnO nanorods by low temperature solution method on Si surface

We report growth of ZnO nanorods by low temperature (<100°C) solution growth method. The substrates (Si, glass and fused Quartz) were seeded by pre-coating with ZnO nanoparticles (4–7 nm diameter) prepared by chemical precipitation route. Nanorods were grown on the seeded substrate in aqueous solution of Zinc Nitrate and Hexamethylenetetramine (HMT). The growth process lasts for up to 8 h and at the maximum time of growth, the nanorods have a width of ∼230–250 nm and length of ∼1.5–1.6 μm. The growth process after some initial growth (<2 h) preserves the aspect ratio and leads to about 90% texturing along the (002) direction. The growth of the nanorods was studied with time and observed growth data suggests a two-stage growth process. The nanorods have a well-defined hexagonal morphology and have a Wurtzite structure. The nanorods were characterized by different techniques and have a band gap of 3.25 eV.     

Fabrication and growth mechanism of hexagonal zinc oxide nanorods via solution process

This article presents, the fabrication of perfectly hexagonal zinc oxide nanorods performed via solution process using zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetramine (HMT) at various concentrations of i.e. 1 × 10⁻³ to 10 × 10⁻² M in 50 mL distilled water and refluxed at 100 °C for 1 h. We used HMT because it acts as a template for the nucleation and growth of zinc oxide nanorods, and it also works as a surfactant for the zinc oxide structures. The X-ray diffraction patterns clearly reveal that the grown product is pure zinc oxide. The diameters and lengths of the synthesized nanorods lie in the range of 200–800 nm and 2–4 μm, respectively as observed from the field emission scanning electron microscopy (FESEM). The morphological observation was also confirmed by the transmission electron microscopy (TEM) and clearly consistent with the FESEM observations. The chemical composition was analyzed by the FTIR spectroscopy, and it shows the ZnO band at 405 cm⁻¹. On the basis of these observations, the growth mechanism of ZnO nanostructures was also proposed.     

Analysis of growth parameters for hydrothermal synthesis of ZnO nanoparticles through a statistical experimental design method

Nanocrystalline ZnO particles were synthesized from an aqueous solution composed of zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and urea (H₂NCONH₂). A precipitating precursor, basic zinc carbonate (Zn₅(CO₃)₂(OH)₆), was first formed by hydrothermally treating the solution at 120 °C for 2–4 h. Nanocrystalline ZnO particles were then obtained by calcining the precursors at 350–650 °C for 0.5–2 h. The synthesis products were characterized using thermogravimetry–differential scanning calorimetry–mass spectrometry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. Based on the experimental results, a possible reaction mechanism for the ZnO formation was proposed. The effects of experimental parameters (namely, the hydrothermal treatment time, the calcination time, and the calcination temperature) on the characteristics of the resulting ZnO products (i.e., the crystalline size and the photoluminescence properties) were analyzed by the Taguchi method to attain the optimum synthesis conditions. By using the appropriate parameters derived from this method, we verified that the optimized synthesis provided a yield of ~70% and that the resulting ZnO particles possessed the characteristics of a ~25 nm crystalline size and a satisfactory photoluminescence property.     

Low-temperature crystallization of oriented ZnO film using seed layers prepared by sol–gel method

Transparent zinc oxide (ZnO) films were coated on seed layers prepared by the sol–gel method by chemical solution deposition method. Firstly, seed layers were prepared from zinc acetate and monoethanolamine, 2-methoxyethanol by the sol–gel method on a silicon substrate or a slide glass. Next, the substrate coated with a seed layer was immersed in zinc nitride solution with hexamethylenetetramine, and ZnO films were obtained. The transmittance of the ZnO films depended on the morphology and crystallinity of the seed layers. When the seed layer were dried on a hot plate, the seed layer had flat surface and transparent ZnO film could be obtained on the seed layers dried at temperatures above 200 °C. When the seed layer was prepared from zinc acetate dihydrate dried in a petri dish, the seed layer were smooth without cracks and the transparent ZnO films were obtained at temperature below 100 °C.     

Microstructural analysis and paramagnetic to ferromagnetic phase transition of chemically synthesized nanoparticles of Tb-doped ZnO

Tb³⁺-doped zinc oxide was prepared by the co-precipitation method. The as-dried sample was annealed at 80, 300, 500, 700, and 1000 °C. Rietveld analysis of the X-ray diffraction patterns of the samples annealed up to 300 °C showed that all the Tb³⁺ ions were entered in the ZnO lattice. But a fraction of Tb³⁺ ions could not enter in the ZnO lattice above 300 °C and this fraction increases with the increase of annealing temperature. The crystallite size and the internal strain due to substitution of bigger size R-ions in the ZnO lattice of the samples were estimated by using the Hall–Williamson plot. Results extracted from high resolution transmission electron microscopy are in agreement with those obtained from the XRD analysis. Magnetic susceptibility (χ) in the range of 300–14 K and magnetization as a function of magnetic field in the range of 300–5 K of the sample annealed at 80 °C were measured by Faraday and SQUID magnetometers, respectively. Values of χ in the paramagnetic region were analyzed by invoking the crystal field interaction of the Tb³⁺ ions with its diamagnetic neighbors. Paramagnetic to ferromagnetic phase transition has been observed at low temperature and the saturation magnetization measured at 5 K is quite high compared to the pristine sample.     

Synthesis and microstructure of vertically aligned ZnO nanowires grown by high-pressure-assisted pulsed-laser deposition

The microstructure and growth behavior for vertically aligned Zinc oxide (ZnO) nanowires, synthesized on a ZnO thin film template by pulsed-laser deposition (PLD), is reported. The nanowire growth proceeds without any metal catalyst for nucleation, although an epitaxial ZnO thin film template is necessary in order to achieve uniform alignment. Nanowire growth at argon or oxygen background pressures of 500-mTorr results in nanowire diameters as small as 50–90 nm, with diameters largely determined by growth pressure and temperature. Room temperature photoluminescence show both near-band-edge and deep-level emission. The deep-level emission is believed caused by oxygen vancancies formed during growth.     

Synthesis of ZnO rods by a simple chemical solution deposition method

ZnO short rods with large yield have been synthesized by a simple chemical solution deposition method at a low temperature of 80°C. Polymethyl methacrylate was used as the structure-directing agent in the formation of the rod-like ZnO crystals. X-ray powder diffraction and field emission scanning electron microscopy were used to characterize the obtained product. The results showed that the as-prepared ZnO crystals were rod-like, which have fairly uniform diameter of around 0.5 ∼ 2 μm and length of 4 ∼ 6 μm. A possible formation mechanism of the ZnO rods has been considered.     

Optical and electrical properties of aluminum-doped zinc oxide nanoparticles

Aluminum-doped zinc oxide nanopowders were prepared using a surfactant assisted complex sol–gel method, and were characterized using inductively coupled plasma, X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and UV–Vis spectroscopy. Al was effectively doped into the ZnO matrix with concentrations up to 6.00 atomic ratio percents (at.%). X-ray diffraction results revealed that all of the nanoparticles had a pure hexagonal wurtzite structure free of any impurities when annealing temperature was below 1273 K. The optical band gap of the nanopowders, which was affected by the Al-doping concentration, reached a maximum of 3.43 eV when ZnO was doped with 4.00 at.% Al. The effect of post-annealing temperature and vacuum conditions on the resistivities of the Al-doped ZnO nanoparticles was also investigated. And the lowest volume resistivity (1.2 Ω cm) was achieved by annealing the Al-doped ZnO nanoparticles in a vacuum at 1173 K for 2 h.     

Facile preparation of Ag/ZnO nanoparticles via photoreduction

Ag/ZnO nanoparticles can be obtained via photocatalytic reduction of silver nitrate at ZnO nanorods when a solution of AgNO₃ and nanorods ZnO suspended in ethyleneglycol is exposed to daylight. The mean size of the deposited sphere like Ag particles is about 5 nm. However, some of the particles can be as large as 20 nm. The ZnO nanorods were pre-prepared by basic precipitation from zinc acetate di-hydrate in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide. They are about 50–300 nm in length and 10–50 nm in width. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray powder diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) were used to characterize the resulting Ag/ZnO nanocomposites.     

Power and gas pressure effects on properties of amorphous In–Ga–ZnO films by magnetron sputtering

Amorphous In–Ga–ZnO thin films were deposited on quartz glass substrate at room temperature utilizing radio frequency magnetron sputtering technique. Sputtering power and oxygen flow rate effects on the physical properties of the In–Ga–ZnO films were systematically investigated. It is shown the film deposition rate and the conductivity of the In–Ga–ZnO films increased with the sputtering power. The as-grown In–Ga–ZnO films deposited at 500 W exhibited the Hall mobility of 17.7 cm²/Vs. Average optical transmittance of the In–Ga–ZnO films is greater than 80% in the visible wavelength. The extracted optical band gap of the In–Ga–ZnO films increased from 3.06 to 3.46 eV with increasing the sputtering power. The electrical properties of the In–Ga–ZnO films are greatly dependent on the O₂/Ar gas flow ratio and post-growth annealing process. Increasing oxygen flow rate converted the In–Ga–ZnO films from semiconducting to semi-insulating, but the resistivity of the films was significantly reduced after being annealed in vacuum. Both the as-grown and annealed In–Ga–ZnO films show n-type electrical conductivity.     

Investigation of microhardness and thermo-electrical properties in the Sn–Cu hypereutectic alloy

Sn–3 wt% Cu hypereutectic alloy was directionally solidified upward with different growth rates (2.24–133.33 μm/s) at a constant temperature gradient (4.24 K/mm) and with different temperature gradients (4.24–8.09 K/mm) at a constant growth rate (7.64 μm/s) in the Bridgman-type growth apparatus. The measurements of microhardness of directionally solidified samples were obtained by using a microhardness test device. The dependence of microhardness HV on the growth rate (V) and temperature gradient (G) were analyzed. According to these results, it has been found that with the increasing the values of V and G the value of HV increases. Variations of electrical resistivity (ρ) and electrical conductivity (σ) for casting samples with the temperature in the range of 300–500 K were also measured by using a standard dc four-point probe technique. The variation of Lorenz coefficient with the temperature for Sn–3 wt% Cu hypereutectic alloy was determined by using the measured values of electrical and thermal conductivities. The enthalpy of fusion for same alloy was determined by means of differential scanning calorimeter from heating trace during the transformation from eutectic liquid to eutectic solid.     

Physiochemical characterizations of electrospun (ZnO–GeO<Subscript>2</Subscript>) nanofibers and their optical properties

In this study, nanofiber mats consisting of two potential metal oxides were produced by electrospinning technique. An aqueous solution of zinc acetate dihydrate and germanium isopropoxide was mixed with polyvinyl alcohol solution to prepare a sol–gel that was electrospun at 20 kV. The obtained nanofiber mats were dried under a vacuum at 80 °C for 24 h and then calcined in air at different temperatures and soaking times. Physiochemical characterizations have affirmed that nanofibers composed of zinc oxide-germanium dioxide (ZnO–GeO₂) can be prepared by calcination at different temperatures. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and the Brunauer–Emmett–Teller (BET) technique were employed to characterize the as-spun nanofibers and the calcined product. The specific surface area of the calcined product decreased with increases in temperature. X-ray powder diffractometery (XRD) analysis was used to study the chemical composition and the crystallographic structure. The optical properties of the as-prepared ZnO–GeO₂ nanofibers were also studied.     

Investigation of the effect of solidification processing parameters on the rod spacings and variation of microhardness with the rod spacing in the Sn–Cu hypereutectic alloy

Sn–3 wt% Cu hypereutectic alloy was prepared in a graphite crucible under the vacuum atmosphere. The samples were directionally solidified upwards under argon atmosphere with different temperature gradients (G = 4.24–8.09 K/mm) at a constant growth rate (V = 7.64 μm/s) and with different growth rates (V = 2.24–133.33 μm/s) at a constant temperature gradient (G = 4.24 K/mm) by using a Bridgman type directional solidification apparatus. The microstructure of directional solidified Sn–3 wt% Cu alloy seems to be rod eutectic structure. The influence of the growth rate (V) and temperature gradient (G) on the rod spacing (λ) and undercooling (ΔT) were analysed. The values of λ²V, λ²G, ΔTλ, ΔTV^−0.5 and ΔTG^−0.5 were determined by using the Jackson–Hunt eutectic theory. The dependence of microhardness (HV) on the rod spacing (λ) was analyzed. According to present results, it has been found that the value of HV increases with the increasing the value of λ.     

Photoresponse of n -ZnO/ p -Si heterojunction towards ultraviolet/visible lights: thickness dependent behavior

A series of n-ZnO/p-Si thin film heterojunctions have been fabricated by a low cost sol–gel technique for different ZnO film thicknesses and the dark as well as photo current–voltage (I–V) characteristics have been investigated in details. The heterojunction with ZnO thickness of 0.46 μm shows the best diode characteristics in terms of rectification ratio, I _F/I _R = 5.7 × 10³ at 5 V and reverse leakage current density, J _R = 7.6 × 10⁻⁵ A cm⁻² at −5 V. From the photo I–V curves and wavelength dependent photocurrent of the heterojunctions, it is found that the junction with 0.46 μm ZnO thickness shows the highest sensitivity towards both UV and visible lights.     

Fluorescent dye encapsulated ZnO particles with cell-specific toxicity for potential use in biomedical applications

Fluorescein isothiocyanate (FITC)-encapsulated SiO₂ core-shell particles with a nanoscale ZnO finishing layer have been synthesized for the first time as multifunctional “smart” nanostructures. Detailed characterization studies confirmed the formation of an outer ZnO layer on the SiO₂–FITC core. These ~200 nm sized particles showed promise toward cell imaging and cellular uptake studies using the bacterium Escherichia coli and Jurkat cancer cells, respectively. The FITC encapsulated ZnO particles demonstrated excellent selectivity in preferentially killing Jurkat cancer cells with minimal toxicity to normal primary immune cells (18% and 75% viability remaining, respectively, after exposure to 60 μg/ml) and inhibited the growth of both gram-positive and gram-negative bacteria at concentrations ≥250–500 μg/ml (for Staphylococcus aureus and Escherichia coli, respectively). These results indicate that the novel FITC encapsulated multifunctional particles with nanoscale ZnO surface layer can be used as smart nanostructures for particle tracking, cell imaging, antibacterial treatments and cancer therapy.     

Fabrication of ZnO tetrapods on silicon substrate by thermal evaporation

Large-scale ZnO tetrapods have been fabricated on silicon substrate by a simple thermal evaporation method at 700 °C without vapor transportation and characterized by FESEM, XRD, Micro-Raman, and PL, respectively. FESEM images indicate that the length of tetrapod arm is about 3–4 μm, and the diameter of the tip is about 50 nm. XRD and Raman spectrum reveal that ZnO tetrapods are highly pure hexagonal wurtzite structure. The PL spectrum indicates that the ZnO tetrapods have strong green emission at 510 nm.