Spin coating of transparent zinc oxide films using novel precursor

The coating of transparent ZnO films using zinc 2-ethylhexanoate [Zn(OOCH(C₂H₅)C₄H₉)₂] as a novel metal organic monomer is reported. Zinc 2-ethylhexanoate is liquid at room temperature and can be spin-coated on a flat substrate without precipitation of ZnO under ambient condition. The spin-coated films were heated at different temperatures to remove unwanted organic materials from the surface. It was found that transparent ZnO films could be produced on glass substrates at low heating temperature (~400 °C). The ZnO films produced using the new monomer were free of cracks and defects. Also the ZnO films produced using the new monomer have excellent optical transmittance, mechanical properties and small surface roughness. The surface morphology and degree of crystallinity of the films coated by the new monomer were compared with these properties of ZnO films produced using zinc acetate-based sol–gels. The results clearly indicate that the novel monomer is a potential precursor for coating transparent ZnO films at low temperatures.     

The influence of surfactants on the roughness of titania sol–gel films

Substrate dipping in a composite sol–gel solution was used to prepare both smooth and rough thin films of titanium dioxide (TiO₂) on commercial fiberglass. The deposition of a composite film was done in a beaker using a solution of titanium (IV) isopropoxide as the sol–gel precursor and cetyltrimethyl ammonium bromide as the surfactant. In order to establish a correlation between experimental conditions and the titanium oxide produced, as well as the film quality, the calcined samples were characterized using Raman spectroscopy, UV–vis spectrophotometry, scanning electron microscopy and atomic force microscopy. One of the most important results is that a 61-nm TiO₂ film was obtained with a short immersion of fiberglass into the sol–gel without surfactant. In other cases, the deposited film consisted of a titanium precursor gel encapsulating micelles of surfactant. The gel films were converted to only the anatase phase by calcining them at 500 °C. The resulting films were crystalline and exhibited a uniform surface topography. In the present paper, it was found that the TiO₂ films prepared from the sol–gel with a surfactant showed a granular microstructure, and are composed of irregular particles between 1.5 and 3 μm. Smooth TiO₂ films could have useful optical and corrosion-protective properties and, on other hand, roughness on the TiO₂ films can enhance the inherent photocatalytic activity.     

Thickness dependency of sol-gel derived ZnO thin films on gas sensing behaviors

ZnO thin films were fabricated by a sol-gel method using Zn(CH₃COO)₂·2H₂O as starting material in order to prepare an acetone gas sensor. A homogeneous and stable solution was prepared by dissolving the zinc acetate in a solution of ethanol and monoethanolamine. The sol-gel solution is coated on alumina substrates with various thicknesses by spin coating technique and heat treated to grow crystalline ZnO thin films. The effect of thickness on physical and electrical properties of as deposited ZnO thin films has been studied. The as deposited ZnO thin films were characterized by X-ray diffraction spectroscopy, field emission scanning electron microscopy and atomic force microscopy. The root mean square surface roughness factors increase with thickness of the films and found 3.9, 6.6, 9.0, and 11.28 nm for 80-, 220-, 450- and 620-nm-thin films respectively. The activation energies of the films are calculated from the resistance temperature characteristics. The sensitivities of the ZnO films towards the acetone gas were determined at an operating temperature of 200 °C. The sensitivity towards acetone vapor is strongly depending on surface morphology of the ZnO thin films.     

Effect of solution concentration on surface morphology and photocatalytic activity of ZnO thin films synthesized by hydrothermal methods

ZnO thin films were synthesized via hydrothermal method on silicon substrate at various solution concentrations. The thin films were characterized by X-ray diffraction, field-emission scanning electron microscope and UV–Vis spectrophotometer. The results show that the thin films are polycrystalline with wurtzite hexagonal structure. The T _c values of (101) surface of the thin film increase from 0.929 to 1.840 at first, and then decrease to 0.779 with increasing solution concentration. The preferential orientation along the (101) crystal surface can be controlled by changing the solution concentration. Solution concentration has a significant effect on surface morphology of the thin films. The optical band gap of the thin films decreases, when the solution concentration of zinc nitrate hexahydrate increases from 0.01 to 0.06 mol/L and then increases when the solution concentration of zinc nitrate hexahydrate further increases to 0.08 mol/L. Photocatalytic activity of the thin films on degradation of methyl orange under UV light irradiation was studied in detail. The ZnO thin film with many cracks prepared from 0.01 mol/L shows the higher photocatalytic activity but the tower-like ZnO thin film prepared from 0.08 mol/L reveals the lower photocatalytic activity. Therefore, the photocatalytic activity of the thin films are mainly relate to surface morphology and crystallographic orientation.     

ZnO films and nanorod/shell arrays electrodeposited on PET-ITO electrodes

In this work, ZnO films, nanorod and nanorod/shell arrays were synthesized on the surface of PET-ITO electrodes by electrochemical methods. ZnO films with high optical transmittance were prepared from a zinc nitrate solution using a pulsed current technique with a reduced pulse time (3 s). The X-ray diffraction pattern of ZnO film deposited on PET-ITO electrode showed that it has a polycrystalline structure with preferred orientations in the directions [0 0 2] and [1 0 3]. ZnO nanorods were synthesized on electrochemical seeded substrate in an aqueous solution containing zinc nitrate and hexamethylenetetramine. In order to increase the stability of PET-ITO electrode to electrochemical and chemical stresses during ZnO nanorods deposition the surface of the electrode was treated with a 17 wt% NH₄F aqueous solution. Electrochemical stability of PET-ITO electrode was evaluated in a solution containing nitrate ions and hexamethylenetetramine. ZnO nanorod/shell arrays were fabricated using eosin Y as nanostructuring agent. Photoluminescence spectra of ZnO nanorod and ZnO nanorod/shell arrays prepared on the surface of PET-ITO electrode were discussed comparatively. By employing the 1.5 μm-length ZnO nanorod/shell array covered with a Cu₂O film a photovoltaic device was fabricated on the PET-ITO substrate.     

Realization of nonpolar a-plane ZnO films on r-plane sapphire substrates using a simple single-source chemical vapor deposition

Nonpolar (112?0) ZnO thin films (a-plane ZnO) have been grown on (11?02) sapphire substrates (r-plane sapphire) by a simple atmospheric pressure single-source chemical vapor deposition (SSCVD) approach. The crystallinity, surface morphology and optical property of the films were investigated using high-resolution X-ray diffraction (HRXRD), scanning electron microscope (SEM) and transmission spectrum, respectively. XRD results revealed that the ZnO films were grown on the substrates epitaxially along (112?0) orientation, and the epitaxial relationship between the ZnO films and the substrates was determined to be (112?0)ZnO∥(11?02) Al2O3, and [1?101]ZnO∥[022?1]Al₂O₃. The SEM image exhibited that the a-plane ZnO films showed a high density of well-aligned ZnO sheets with rectangular structure. The transmission spectrum showed that the ZnO films were highly transparent in the visible region.     

Synthesis and characterization of (CuO)x(ZnO)1 − x composite thin films with tunable optical and electrical properties

Mixed (CuO)_x(ZnO)_1 − x composite films have been prepared on glass substrates by a sol-gel spin coating method using copper acetate hydrate and zinc acetate dihydrate as precursors. The surface morphology and crystal structure of the films were investigated by field emission scanning electron microscopy and x-ray diffraction, respectively. It was observed that the crystal structure changed from wurtzite (ZnO) to monoclinic (CuO) as the Cu content increased from 0% to 100% in the films. UV-Vis absorption and photoluminescence measurements indicated that the optical properties can be tuned continuously from pure ZnO to pure CuO as the Cu content was increased, following the expected trends for a transition from ZnO to CuO. The resistivity of the films decreased by three orders of magnitude as Cu increased from 0% to 100%. These semiconducting composite oxides with tunable optical and electrical properties have potential applications in electronics and optoelectronics.     

Growth of ZnO thin films at low temperature by plasma-enhanced atomic layer deposition using H2O and O2 plasma oxidants

Zinc oxide (ZnO) thin films were grown at 70 °C by plasma-enhanced atomic layer deposition using H₂O and O₂ plasmas. Plasma oxidants were used in order to improve the ZnO crystallinity and optoelectronic properties, avoiding high-temperature synthesis. The deposition parameters were optimized to achieve saturation in each reaction step. X-ray photoelectron spectroscopy (XPS) reveals high purity of the obtained ZnO films. X-ray diffraction (XRD) measurements indicate that the grown layers are polycrystalline and that the H₂O plasma synthesis leads to better crystallinity than the O₂ plasma as inferred from the intensity of the (100) and (002) peaks. The films are with high optical transmission, ~90%, as inferred from UV–visible (UV–Vis) transmittance measurements, and optical band gaps of 3.22 and 3.23 eV for H₂O and O₂ plasma, respectively. Atomic force microscopy (AFM) indicates that the films are smooth, with an average roughness of ~?0.22 nm. The growth rate was found to be in the range of 1.2–1.4 Å/cycle. The XPS, XRD, UV–Vis, and AFM results prove the possibility to obtain high-quality ZnO films by O₂ and H₂O plasma processes at 70 °C with chemical, structural, and optical properties promising for flexible electronics. ZnO films were successfully deposited on polyethylene terephthalate substrates using the optimal conditions for H₂O plasma process. No damage of the film surface or substrate was observed.

     

Fabrication and characterization of highly c-axial oriented ZnO films by chemical solution deposition

Highly c-axial oriented ZnO thin films were successfully fabricated on glass substrates at a very low pre-heating temperature by chemical solution deposition using polyvinyl alcohol (PVA) as the solvent. Effect of deposition parameters on the crystalline of ZnO films was investigated including atmosphere, pre-treating temperature and annealing temperature. It was found that all the samples were c-axial oriented regardless of growth conditions, attributing to the dominating mechanism of the PVA-Zn network. In addition, the optical properties of ZnO films were correlated with the surface morphology.     

Analysis of Li-related defects in ZnO thin films influenced by annealing ambient

Li-doped ZnO thin films were grown on quartz substrates by radio frequency magnetron sputtering and in situ annealing under O₂ or Ar ambient. Li-related defects in ZnO films strongly depend on the annealing ambient. AFM and XRD indicated that ZnO films possessed a good crystallinity with c-axis orientation, uniform thickness and dense surface. Electrical and optical properties demonstrated that, an amount of Li_Zn defect had existed in ZnO annealed under O₂ambient and an amount of Li_i(o) defect had existed in ZnO annealed under Ar ambient. First-principle calculations were performed to calculate formation energies of Li-doped ZnO in order to explain the formation mechanism of Li-related defects in ZnO.     

Fabrication of copper oxide thin films by the drop chemical deposition technique

Copper oxide thin films were deposited by the drop chemical deposition technique using an aqueous solution containing CuSO₄ and Na₂SO₃. The deposited films were cubic crystalline structure and had O/Cu ratio of ～0.77 with a very small amount of sulfur. The surface morphology of the films appeared compact without any crack. In the optical transmission measurement, a clear absorption edge was observed near 800 nm wavelength. Photo-electrochemical measurement confirmed the p-type conductivity and photosensitivity of the films. Cu_xO-based heterojunctions with ZnO were fabricated, and rectification properties and weak photovoltaic effects were observed.     

Characterization of mesoporous ZnO:SiO2 films obtained by the sol-gel method

ZnO:SiO₂ films are intensively investigated for optical and electronic applications. Additionally, porous ZnO:SiO₂ films are of great interest as catalyst and gas-sensing materials. The sol-gel method is an efficient and low-cost process for the deposition of meso- and microporous silica-based films. The present paper studies the effect of the withdrawal speed on the microstructure and optical properties of mesoporous ZnO:SiO₂ films obtained by the sol-gel method. The morphology of the films was investigated by atomic force microscopy and the overall structure was studied by X-ray diffraction. The structure and size of the zinc oxide nanoparticles embedded in the silica matrix were investigated in more detail by transmission electron microscopy. These techniques showed ZnO:SiO₂ films with crack-free mesoporous morphology and highly efficient embedding of ZnO nanoparticles with (100) preferred orientation. Furthermore, the optical transmittance (in the visible and near infrared regions) and the optical band gap value were observed to vary with withdrawal speed. It is shown that ZnO:SiO₂ nanocomposites films which possess ZnO particles exhibiting a (100) orientation, with possible special applications in non-linear optics, could be prepared by the low-temperature crystallization sol-gel method.     

Enhanced magnetic properties of chemical solution deposited BiFeO3 thin film with ZnO buffer layer

Magnetic properties of BiFeO₃ films deposited on Si substrates with and without ZnO buffer layer have been studied in this work. We adopted the chemical solution deposition method for the deposition of BiFeO₃ as well as ZnO films. The x-ray diffraction measurements on the deposited films confirm the formation of crystalline phase of BiFeO₃ and ZnO films, while our electron microscopy measurements help to understand the morphology of few micrometers thick films. It is found that the deposited ZnO film exhibit a hexagonal particulate surface morphology, whereas BiFeO₃ film fully covers the ZnO surface. Our magnetic measurements reveal that the magnetization of BiFeO₃ has increased by more than ten times in BiFeO₃/ZnO/Si film compared to BiFeO₃/Si film, indicating the major role played by ZnO buffer layer in enhancing the magnetic properties of BiFeO₃, a technologically important multiferroic material.     

Comparative study of zinc oxide and aluminum doped zinc oxide transparent thin films grown by direct current magnetron sputtering

Pure and aluminum (Al) doped zinc oxide (ZnO and ZAO) thin films have been grown using direct current (dc) magnetron sputtering from pure metallic Zn and ceramic ZnO targets, as well as from Al-doped metallic ZnAl2at.% and ceramic ZnAl2at.%O targets at room temperature (RT). The effects of target composition on the film's surface topology, crystallinity, and optical transmission have been investigated for various oxygen partial pressures in the sputtering atmosphere. It has been shown that Al-doped ZnO films sputtered from either metallic or ceramic targets exhibit different surface morphology than the undoped ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (002). More significantly, Al-doping leads to a larger increase of the optical transmission and energy gap (E_g) of the metallic than of the ceramic target prepared films.     

ZnO/Al2O3 coatings for the photoprotection of polycarbonate

ZnO and ZnO/Al₂O₃ thin films were deposited by r.f. magnetron sputtering on polycarbonate (PC) films in order to protect this polymer against photodegradation. The composition, structure and optical properties of the ceramic coatings were characterised. CO₂-plasma treatments were applied to PC in order to improve the coating adhesion. The PC surface energy was characterised by wettability measurements and the chemical bonds were analysed by XPS.It was found that ZnO coatings improve the stability of PC to UV radiations and that an intermediate alumina coating inhibits the photocatalytic oxidation of PC at the PC/ZnO interface. Additionally an external alumina coating brings a high hardness to the coating.     

Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering

Zn-doped TiO₂ films were prepared by means of pulsed DC reactive magnetron sputtering method using Ti and Zn mixed target. The deposition condition was optimized to produce uniform and transparent TiO₂ films. Titanium was in the Ti⁴⁺ oxidation state in all Zn-doped TiO₂ films. The zinc oxide deposited on the substrate was in the fully oxidized state of ZnO. Increase of zinc concentration inhibited the crystal growth in the TiO₂ films. The surface morphology gradually changed from crystalline to amorphous along with the increase of doped zinc concentration. The optical transmittances of these films decreased only slightly with increasing zinc concentration due to very similar band edges of ZnO and anatase TiO₂. The doped ZnO had weak influence on light absorption of the TiO₂ films. When zinc concentration was very low (<1 at%), the photocatalytic activities of the doped films had nearly no difference from that of pure TiO₂ film. Photocatalytic activities decreased obviously in the films containing high amount of zinc oxide.     

Optical characterization of ZnO thin films deposited by Sol-gel method

In this paper, ZnO thin film is deposited on Pt/TiO₂/SiO₂/Si substrate using the sol-gel method and the effect of annealing temperature on the structural morphology and optical properties of ZnO thin films is investigated. The ZnO thin films are crystallized by the heat treatment at over 400°C. The ZnO thin film annealed at 600°C exhibits the greatest c-axis orientation and the Full-Width-Half-Maximum (FWHM) of X-ray peak is 0.4360°. A dense ZnO thin film is deposited by the growth of uniform grains with the increase of annealing temperature but when the annealing temperature increases to 700°C, the surface morphology of ZnO thin film becomes worse by the aggregation of ZnO particles. In the results of surface morphology of ZnO thin film using atomic force microscope (AFM), the surface roughness of ZnO thin film annealed at 600°C is smallest, that is, approximately 1.048 nm. For the PL characteristics of ZnO thin film, it is observed that ZnO thin film annealed at 600°C exhibits the greatest UV (ultraviolet) exciton emission at approximately 378 nm, and the smallest visible emission at approximately 510 nm among ZnO thin films annealed at various temperatures. It is deduced that ZnO thin film annealed at 600°C is formed most stoichiometrically, since the visible emission at approximately 510 nm comes from either oxygen vacancies or impurities.     

Simple way for preparation of ZnO films by surfactant mediated spray pyrolysis

Nanocrystalline porous ZnO films are deposited onto alumina foil substrates by polyvinyl alcohol (PVA) modified spray pyrolysis. Water and ethanol–water mixture were used for preparation of the sols. The effect of polyvinyl alcohol on the morphological and photocatalytical properties of ZnO films was studied. It was found that the polyvinyl alcohol plays important role in formation of porous films structure with ganglia like morphology. Relatively compact granular morphology was observed for the ZnO samples, grown without organic surfactant. The X-ray diffraction patterns revealed the formation of phase-pure ZnO thin films. The FTIR spectra and DTA-TG analyses of the precursor mixtures: Zn(CH₃COOH)₂·2H₂O and Zn(NO₃)₂·6H₂0 with PVA revealed that ZnO is formed before the final decomposition of the polymer at 350 °C.     

Enhanced visible light response of ZnO porous thin film by post-annealing treatment

ZnO thin films were synthesized by a facile electrodeposition method in the aqueous solution. Porous ZnO thin films with wurtzite structure could be achieved by mean of annealing treatment. The growth mechanism of the porous ZnO thin film was discussed. The intensity of the E ₂ mode in the ZnO thin film, which represents crystalline quality of the thin film increases with the increasing of annealing temperature. Optical properties indicate that annealing temperature has strong effect on the optical band gap value and defect concentrations. Both the green and yellow emissions corresponding to respective oxygen vacancies and oxygen interstitials can be identified. The results show that ZnO annealed at 400 °C exhibits a significant photocurrent density enhancement which is about 18 times larger than that of the as-deposited ZnO thin films. The mechanism of the enhanced photoresponse for the ZnO thin film has been discussed in detail.     

High quality ZnO films deposited by radio-frequency magnetron sputtering using layer by layer growth method

Three-layered ZnO films were deposited on Si substrates by radio-frequency magnetron sputtering using layer by layer growth method. The Raman scattering confocal analysis confirms that ZnO film quality is improving at increasing the number of ZnO layers at film deposition.Applied method of deposition was used to realize homoepitaxial growth of ZnO films on c-Al₂O₃, Si, SiN_x/Si, glass and ITO/glass substrates. In order to improve the film quality we increased the number of deposition stages up to 5. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmittance measurements were used to testify the quality of grown five-layered ZnO films. XRD results showed that all five-layered ZnO films have (002) texture. The second order diffraction peak (004) on XRD spectra additionally testifies to the high quality of all five-layered ZnO films. SEM results demonstrated that no defects such as cracks and dislocations caused by interruption of deposition ZnO films were observed. Transmittance measurement results showed that ZnO films deposited on transparent substrates have abrupt absorption edge and high optical transmission in the visible region of the spectrum.