Rapid preparation, characterization, and photoluminescence of ZnO films by a novel chemical method

A novel and simple chemical route was developed for the deposition of ZnO film from aqueous solution, integrating the merits of successive ionic layer adsorption and reaction and chemical bath deposition. ZnO thin films on glass and Si(1 0 0) substrates were deposited with the precursor of zinc-ammonia complex. As-deposited ZnO film exhibits good crystallinity with the hexagonal wurtzite crystalline structure and the preferential orientation along (0 0 2) plane. With a dense and continuous appearance, the film is composed of ZnO particles in even size of 200-300 nm. Under the excitation of 340 nm, strong and sharp near band gap emission (∼391 nm) dominates the photoluminescence spectra with several weak emission peaks related to the deep level (∼450-500 nm). In addition, the mechanism for the deposition process of ZnO from aqueous solution was preliminarily discussed.     

Effect of crystallite size of zinc oxide on the mechanical,thermal and flow properties of polypropylene/zinc oxide nanocomposites

ZnO nanoparticles were prepared using zinc chloride and sodium hydroxide in chitosan medium. Prepared ZnO (NZO) and commercial ZnO (CZO) was characterized by scanning electron microscopic and X-ray diffraction studies. PP/ZnO nanocomposites were prepared using 0–5 wt% of zinc oxide by melt mixing. It was then compression moulded into films. Transparency of the composite films were improved by reducing the crystallite size of ZnO. Melt flow index studies revealed that NZO increased the flow characteristics of PP while CZO decreased. X-ray diffraction studies indicated α-form of isotactic polypropylene. An increase in mechanical properties, dynamic mechanical properties and thermal stability of the composites were observed by the addition of ZnO. Uniform dispersion of the ZnO was observed in the scanning electron micrographs of the tensile fractured surface of composites.     

Large-scale synthesis of hexagonal cone-shaped ZnO nanoparticles with a simple route and their application to photocatalytic degradation

We report the large-scale synthesis of hexagonal cone-shaped ZnO nanoparticles by the esterification between zinc acetate and alcohol. The morphology of the ZnO nanoparticles was investigated by transmission electron microscopy, selected area electron diffraction and scanning electron microscopy measurements. The synthesized ZnO nanoparticles are single-crystalline with hexagonal phase and show a strong UV emission at −378 nm due to the excellent crystallinity of particles. A possible formation mechanism of the hexagonal cone-shape structure is proposed. Furthermore, the as-prepared ZnO particles exhibit high photocatalytic activity for the photocatalytic degradation of Rhodamine B, indicating that the ZnO nanostructure is promising as a semiconductor photocatalyst.     

Preparation of aluminum doped zinc oxide films and the study of their microstructure, electrical and optical properties

Aluminum doped zinc oxide (AZO) polycrystalline thin films were prepared by sol-gel dip-coating process on optical glass substrates. Zinc acetate solutions of 0.5 M in isopropanol stabilized by diethanolamine and doped with a concentrated solution of aluminum nitrate in ethanol were used. The content of aluminum in the sol was varied from 1 to 3 at.%. Crystalline ZnO thin films were obtained following an annealing process at temperatures between 300 °C and 500 °C for 1 h. The coatings have been characterized by X-ray diffraction, UV-Visible spectrophotometry, scanning electron microscopy, and electrical resistance measurement. The ZnO:Al thin films are transparent (∼ 90%) in near ultraviolet and visible regions. With the annealing temperature increasing from 300 °C to 500 °C, the film was oriented more preferentially along the (0 0 2) direction, the grain size of the film increased, the transmittance also became higher and the electrical resistivity decreased. The X-ray diffraction analysis revealed single-phase ZnO hexagonal wurtzite structure. The best conductors were obtained for the AZO films containing 1 at.% of Al, annealed at 500 °C, 780 nm film thickness.     

Electromechanical response of semiconducting carbon–polyimide nanocomposite thin films

Electromechanically responsive polymer nanocomposite thin films can provide embedded microscale sensing elements for unobtrusive monitoring of strain, torque and pressure particularly for composite structures. Thin nanocomposite carbon–polyimide films with thicknesses up to 90 μm were produced with carbon contents that yield semiconducting behaviour attributable to distance dependent electron hopping between isolated nanoparticles. The tensile modulus and the strain at break indicated minimum interaction between polymer and nanoparticle surfaces. A decreasing storage modulus with increasing temperature indicated increasing free volume inducing polymer chain motions.     

Low temperature solution synthesis and characterization of ZnO nano-flowers

Synthesis of flower-shaped ZnO nanostructures composed of hexagonal ZnO nanorods was achieved by the solution process using zinc acetate dihydrate and sodium hydroxide at very low temperature of 90 °C in 30 min. The individual nanorods are of hexagonal shape with sharp tip, and base diameter of about 300-350 nm. Detailed structural characterizations demonstrate that the synthesized products are single crystalline with the wurtzite hexagonal phase, grown along the [0 0 0 1] direction. The IR spectrum shows the standard peak of zinc oxide at 523 cm⁻¹. Raman scattering exhibits a sharp and strong E₂ mode at 437 cm⁻¹ which further confirms the good crystallinity and wurtzite hexagonal phase of the grown nanostructures. The photoelectron spectroscopic measurement shows the presence of Zn, O, C, zinc acetate and Na. The binding energy ca. 1021.2 eV (Zn 2p_3/2) and 1044.3 eV (Zn 2p_1/2), are found very close to the standard bulk ZnO binding energy values. The O 1s peak is found centered at 531.4 eV with a shoulder at 529.8 eV. Room-temperature photoluminescence (PL) demonstrate a strong and dominated peak at 381 nm with a suppressed and broad green emission at 515 nm, suggests that the flower-shaped ZnO nanostructures have good optical properties with very less structural defects.     

Thermal mismatch induced disorder of beta-eucryptite and its effect on thermal expansion of beta-eucryptite/Al composites

In this paper, beta-eucryptite/Al composites with different volume fraction of beta-eucryptite particles (Euc/Al) were prepared by spark plasma sintering process. The microstructures of the composites were studied by transmission electron microscope. The phase compositions and thermal physical properties of the composites were analyzed by X-ray diffraction and thermal dilatometer. The change of peaks intensity ratio of beta-eucryptite (2 0 0) to beta-eucryptite (2 0 2) plane after 12 months of aging in room condition and at elevated temperature (40–300 °C) was used to characterize the disorder of beta-eucryptite, which was due to the high thermal mismatch stress in the composite. The results indicate that the disorder of beta-eucryptite can recover when the thermal mismatch stress in beta-eucryptite is released after 12 months of aging or at elevated temperature. Both compressive stress and tensile stress could induce the disorder of eucryptite (2 0 0) plane. The relationships among CTE behavior of the composite, the phase transformation of beta-eucryptite and the thermal mismatch stress were discussed.     

The growth of nanoscale ZnO films by pulsed-spray evaporation chemical vapor deposition and their structural, electric and optical properties

Great interest in nanoscale thin films (sub-100 nm) has been stimulated by the developing demands of functional devices. In this paper, nanoscale zinc oxide (ZnO) thin films were deposited on glass substrates at 300 °C by pulsed-spray evaporation chemical vapor deposition. Scanning electron micrographs indicate uniform surface morphologies composed of nanometer-sized spherical particles. The growth kinetics and growth mode are studied and the relationship between the film thickness and the electric properties with respect to the growth mode is interpreted. X-ray diffraction shows that all ZnO films grown by this process were crystallized in a hexagonal structure and highly oriented with their c-axes perpendicular to the plane of the substrate. Optical measurements show transparencies above 85% in the visible spectral range for all films. The absorbance in the UV spectral range respects well the Beer-Lambert law, enabling an accurate optical thickness measurement, and the absorption coefficient was measured for a selected wavelength. The measured band gap energies exhibit an almost constant value of 3.41 eV for all films with different thicknesses, which attributed to the thickness-independent crystallite size.     

Solution precursor plasma deposition of nanostructured ZnO coatings

Zinc oxide (ZnO) is a wide band gap semiconducting material that has various applications including optical, electronic, biomedical and corrosion protection. It is usually synthesized via processing routes, such as vapor deposition techniques, sol-gel, spray pyrolysis and thermal spray of pre-synthesized ZnO powders. Cheaper and faster synthesis techniques are of technological importance due to increased demand in alternative energy applications. Here, we report synthesis of nanostructured ZnO coatings directly from a solution precursor in a single step using plasma spray technique. Nanostructured ZnO coatings were deposited from the solution precursor prepared using zinc acetate and water/isopropanol. An axial liquid atomizer was employed in a DC plasma spray torch to create fine droplets of precursor for faster thermal treatment in the plasma plume to form ZnO. Microstructures of coatings revealed ultrafine particulate agglomerates. X-ray diffraction confirmed polycrystalline nature and hexagonal Wurtzite crystal structure of the coatings. Transmission electron microscopy studies showed fine grains in the range of 10-40 nm. Observed optical transmittance (∼65-80%) and reflectivity (∼65-70%) in the visible spectrum, and electrical resistivity (48.5-50.1 mΩ cm) of ZnO coatings are attributed to ultrafine particulate morphology of the coatings.     

Synthesis of PbS/poly (vinyl-pyrrolidone) nanocomposite

A simple solution growth method for synthesis of nanocomposite of PbS nanoparticles in poly(vinyl-pyrrolidone) (PVP) polymer is described. The nanocomposite is prepared from methanolic solution of lead acetate (PbAc), thiourea (TU) and PVP at room temperature (∼27 °C). Optical absorption spectrum of PbS/PVP nanocomposite solution shows strong absorption from 300 to 650 nm with significant bands at 400 and 590 nm which is characteristic of nanoscale PbS. Spin-coated nanocomposite films on glass have an absorption edge at ∼650 nm with band gap of 2.55 eV. Fourier transform infrared (FTIR) spectroscopy of PbS/PVP nanocomposite and PVP shows strong chemical bond between PbS nanoparticles and host PVP polymer. The transmission electron microscope (TEM) images reveal that 5-10 nm PbS particles are evenly embedded in PVP polymer. The formation of PbS is confirmed by selective area electron diffraction (SAED) of a typical nanoparticle.     

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.     

Applicability of liquid-liquid interface reaction technique for the preparation of zinc sulfide nano particulate thin films

Thin films of zinc sulfide are prepared by the liquid-liquid interface reaction technique. Cubic and hexagonal mixed phase is observed from electron diffraction (ED) of the film showing a spot pattern with faint rings in the background. The optical absorption edge shows a blue shift with respect to bulk indicating the nano nature of the film material. Transmission electron microscopy confirms the nanostructure of the film with particle size in the range 2-9 nm, with peak maxima between 3-5 nm consistent with the particle size suggested by optical absorption studies.     

Physical and sensing properties of ZnO:F:Al thin films deposited by sol-gel

Fluorine and aluminum-doped zinc oxide thin films, ZnO:F:Al, were prepared on soda-lime glass substrates by the sol-gel method and repeated dip-coating. The effect of the solution ageing and film thickness on the physical characteristics of the films was studied. Two ageing times, namely, two and seven days, and three different thicknesses, in the order of 220, 330, and 520 nm, were the main variables used in this work. As-deposited ZnO:F:Al films showed a high electrical resistivity, however after a vacuum thermal treatment, it was registered a significant decrease. Structural, optical, and morphological characterizations were carried out in vacuum-annealed films. The X-ray diffraction (XRD) patterns revealed that both as-deposited and vacuum-annealed ZnO:F:Al thin films were polycrystalline with a hexagonal wurtzite-type structure with a well-defined (002) diffraction peak, irrespective of the ageing time of the starting solution. The (002) peak shows a proportional increase with the thickness magnitude. An average crystallite size of about 20 nm was estimated using the well-known Scherrer's formula. From the surface morphological study it was observed that the grain size is almost independent of the ageing time of the starting solution, and the film thickness. Films presented an average optical transmittance in the visible range (400-700 nm) in the order of 90%, as well as a band gap of 3.3 eV. The gas-sensing properties of ZnO:F:Al thin films in an atmosphere containing different concentrations of carbon monoxide, and at different operation temperatures were probed. The highest sensitivity registered was of the order of 93%.     

Solvothermal synthesis of nanorods of ZnO, N-doped ZnO and CdO

ZnO nanorods with diameters in the 80-800 nm range are readily synthesized by the reaction of zinc acetate, ethanol and ethylenediamine under solvothermal conditions. The best products are obtained at 330 °C with a slow heating rate. Addition of the surfactant Triton^®-X 100 gave nanorods of uniform (300 nm) diameter. By adding a small amount of liquid NH₃ to the reaction mixture, N-doped ZnO nanorods, with distinct spectroscopic features are obtained. CdO nanorods of 80 nm diameter have been prepared under solvothermal conditions using a mixture of cadmium cupferronate, ethylenediamine and ethanol at 330 °C. Similarly, Zn_1−xCd_xO nanorods of a 70 nm diameter are obtained under solvothermal conditions starting with a mixture of zinc acetate, cadmium cupferronate, ethanol and ethylenediamine.     

Effect of boron doping on optical properties of sol-gel based nanostructured zinc oxide films on glass

Boron doped zinc oxide thin films (∼80 nm) were deposited onto pure silica glass by sol-gel dip coating technique from the precursor sol/solution of 4.0 wt.% equivalent oxide content. The boron concentration was varied from 0 to 2 at.% w.r.t. Zn using crystalline boric acid. The nanostructured feature of the films was visualized by FESEM images and the largest cluster size of ZnO was found in 1 at.% boron doped film (B1ZO). The presence of mixed crystal phases with hexagonal as major phase was identified from XRD reflections of the films. Particle size, optical band gap, visible specular reflection, room temperature photoluminescence (PL) emissions (3.24-2.28 eV), infra-red (IR) and Raman active longitudinal optical (LO) phonon vibration were found to be dependent on dopant concentration. For the first time, we report the room temperature fine structured PL emissions as phonon replicas originated from the LO phonon (both IR and Raman active) in 1 at.% boron doped zinc oxide film.     

The effect of annealing on Al-doped ZnO films deposited by RF magnetron sputtering method for transparent electrodes

In this study, transparent conducting Al-doped zinc oxide (AZO) films with a thickness of 150 nm were prepared on Corning glass substrates by the RF magnetron sputtering with using a ZnO:Al (Al₂O₃: 2 wt.%) target at room temperature. This study investigated the effects of the post-annealing temperature and the annealing ambient on the structural, electrical and optical properties of the AZO films. The films were annealed at temperatures ranging from 300 to 500 °C in steps of 100 °C by using rapid thermal annealing equipment in oxygen. The thicknesses of the films were observed by field emission scanning electron microscopy (FE-SEM); their grain size was calculated from the X-ray diffraction (XRD) spectra using the Scherrer equation. XRD measurements showed the AZO films to be crystallized with strong (002) orientation as substrate temperature increases over 300 °C. Their electrical properties were investigated by using the Hall measurement and their transmittance was measured by UV-vis spectrometry. The AZO film annealed at the 500 °C in oxygen showed an electrical resistivity of 2.24 × 10^− 3 Ω cm and a very high transmittance of 93.5% which were decreased about one order and increased about 9.4%, respectively, compared with as-deposited AZO film.     

Synthesis, characterization and optical properties of sheet-like ZnO

Sheet-like ZnO with regular hexagon shape and uniform diameter has been successfully synthesized through a two-step method without any metal catalyst. First, the sheet-like ZnO precursor was synthesized in a weak alkaline carbamide environment with stirring in a constant temperature water-bath by the homogeneous precipitation method, then sheet-like ZnO was obtained by calcining at 600 °C for 2 h. The structures and optical properties of sheet-like ZnO have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and UV-vis-NIR spectrophotometer. The results reveal that the product is highly crystalline with hexagonal wurtzite phase and has appearance of hexagon at (0 0 0 1) plane. The HRTEM images confirm that the individual sheet-like ZnO is single crystal. The PL spectrum exhibits a narrow ultraviolet emission at 397 nm and a broad visible emission centering at 502 nm. The band gap of sheet-like ZnO is about 3.15 eV.     

Pulsed laser deposition and photoluminescence measurements of ZnO thin films on flexible polyimide substrates

In order to assess the potential of zinc oxide (ZnO) in flexible electronics applications, we created continuous ZnO films on polymeric substrates for evaluation of structural and optical properties. Specifically, we have used pulsed laser deposition to deposit ZnO films with thickness of several microns on flexible free-standing polyimide substrates. A KrF excimer laser (248 nm) operated at fluences of 3.0-6.2 J/cm² was used. ZnO films were deposited at temperatures between room temperature and 300 °C under O₂ atmosphere at a pressure of 50 Pa. Good flexibility characterizes the obtained layers and X-ray diffraction measurements show that films present all reflections of hexagonal ZnO. We discuss luminescence measurements on the films in relation to the complex interface phenomena expected in our samples.     

Mn-doped ZnO transparent conducting films deposited by DC magnetron sputtering

Mn-doped zinc oxide (ZnO:Mn) thin films with low resistivity and relatively high transparency were firstly prepared on glass substrate by direct current (DC) magnetron sputtering at room temperature. Influence of film thickness on the properties of ZnO:Mn films was investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. As the thickness increases from 144 to 479 nm, the crystallite size increases while the electrical resistivity decreases. However, as the thickness increases from 479 to 783 nm, the crystallite size decreases and the electrical resistivity increases. When film thickness is 479 nm, the deposited films have the lowest resistivity of 2.1 × 10^− 4 Ω cm and a relatively high transmittance of above 84% in the visible range.     

Preparation and ethanol sensing properties of the superstructure SnO2/ZnO composite via alcohol-assisted hydrothermal route

Self-assembled superstructure of SnO₂/ZnO composite was synthesized by using alcohol-assisted hydrothermal method gas sensing properties of the material were investigated by using a static test system. The structure and morphology of the products were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscope (FE-SEM). The diameter of the SnO₂ nanorods was about 40 nm with a length of about 300 nm, SnO₂ nanorods and ZnO nanosheets interconnect each other to form a superstructure. The gas sensing properties of superstructure SnO₂/ZnO composite with different content of ZnO were investigated. Furthermore, the superstructure SnO₂/ZnO composite sensor is characterized at different operating temperatures and its long-term stability in response to ethanol vapor is tested over a period of 3 months.