Growth of hierarchical based ZnO micro/nanostructured films and their tunable wettability behavior

Hierarchical zinc oxide (ZnO) micro/nanostructured thin films were grown onto as-prepared and different annealed ZnO seed layer films by a simple two step chemical process. A cost effective successive ionic layer adsorption and reaction (SILAR) method was employed to grow the seed layer films at optimal temperature (80 °C) and secondly, different hierarchical based ZnO structured thin films were deposited over the seed layered films by chemical bath deposition (CBD). The influence of seed layer on the structural, surface morphological, optical and wettability behavior of the ZnO thin films were systematically investigated. The XRD analysis confirms the high crystalline nature of both the seed layer and corresponding ZnO micro/nanostructured films with a perfect hexagonal structure oriented along (0 0 2) direction. The surface morphology revels a complex and orientated hierarchical based ZnO structured films with diverse shapes from plates to hexagonal rod-like crystal to tube-like structure and even much more complex needle-like shapes during secondary nucleation, by changing the seed layer conditions. The water contact angle (WCA) measurements on hierarchical ZnO structured films are completely examined to study its surface wettability behavior for its suitability in future self-cleaning application. Photoluminescence (PL) spectra of the ZnO structured film exhibit UV and visible emissions in the range of 420-500 nm. The present approach demonstrates its potential for low-temperature, large-scale, controlled synthesis of crystalline hierarchical ZnO nanostructures films.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Diagnostic study of the roughness surface effect of zirconium on the third-order nonlinear-optical properties of thin films based on zinc oxide nanomaterials

Zinc oxide (ZnO) and zirconium doped zinc oxide (ZnO:Zr) thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 500 °C using zinc and zirconium chlorides as precursors. Effects of zirconium doping agent and surface roughness on the nonlinear optical properties were investigated in detail using atomic force microscopy (AFM) and third harmonic generation (THG) technique. The best value of nonlinear optical susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.12 × 10⁻¹² (esu) of the studied films was found for the 3% doped sample.     

Low-temperature deposition of transparent conducting ZnO:Zr films on PET substrates by DC magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were firstly deposited on polyethylene terephthalate (PET) substrates with ZnO buffer layers by DC magnetron sputtering at room temperature. Dependence of physical properties of ZnO:Zr films on deposition pressure was systematically studied. All the deposited films were polycrystalline and (1 0 0) oriented. When deposition pressure increases from 1 to 2.5 Pa, the crystallinity of the films improves and the resistivity decreases. While deposition pressure increases from 2.5 to 3.5 Pa, the crystallinity of the films deteriorates and the resistivity increases. The lowest resistivity of 1.8 × 10⁻³ Ω cm was obtained for the films deposited at the optimum deposition pressure of 2.5 Pa. All the films present a high transmittance of above 86% in the wavelength range of the visible spectrum.     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

Improvement in crystalline quality and surface smoothness of ZnO film by multi-step deposition process

The effect of multi-step deposition process on the crystalline quality and surface smoothness of ZnO film was investigated. ZnO films were composed of multi-layers, in which each layer was deposited at different temperatures. The maximum intensity and the smallest FWHM of (0 0 2) diffraction peak in XRD spectrum were observed for the multi-layered ZnO film of which each layer was deposited at progressively higher temperatures. In addition, the smoothest film surface was also observed for the ZnO film deposited through multi-step process in which deposition temperatures gradually increase. On the other hand, the large difference between the deposition temperatures in multi-step process did not result in the significant improvement of the crystalline quality of ZnO film. The ZnO film prepared by using multi-step process had high transmittance over 70% in visible region and the optical band gap of 3.22 eV.     

Correlation between the structural and optical properties of Co doped ZnO thin films prepared at different film thickness

Cobalt doped zinc oxide (ZnO:Co) thin films were deposited on glass substrates by ultrasonic spray technique decomposition of Zinc acetate dihydrate and cobalt acetate tetrahydrate in an ethanol solution with film thickness. All films are polycrystalline with a hexagonal wurtzite-type structure with a preferential orientation according to the direction (0 0 2), with the maximum crystallite size was found of 59.42 nm at 569 nm. The average transmittance of all films is about 65–95% measured by UV–vis analyzer. The band gap energy increased from 3.08 to 3.32 eV with increasing the film thickness from 192 to 569 nm. The increase of the electrical conductivity with increases in the film thickness to maximum value of 9.27 (Ω cm)⁻¹ can be explained by the increase in carrier concentration and displacement of the electrons of the films. The correlation between the band gap and crystal structure suggests that the band gap energy of Co doped ZnO is influenced by the crystallite size and the mean strain.     

Optical and electrical properties of nanocrystal zinc oxide films prepared by dc magnetron sputtering at different sputtering pressures

The nanocrystal thin films of zinc oxide doped by Al (ZnO:Al) were deposited by dc reactive magnetron sputtering on the glass substrates, in the pressure range of 33-51 Pa. From the X-ray diffraction patterns, the nanocrystalline structure of ZnO:Al films and the grain size were determined. The optical transmission spectra depend from the sputtering pressure, but their average value was 90% in the range from 33 Pa to 47 Pa. Also, the sputtering pressure changes the optical band gap of ZnO:Al films, which is highest for films deposited at 37 Pa, 40 Pa and 47 Pa. The obtained films at room temperature have a sheet resistance of 190 Ω/cm² which increases with time, but the films annealed at temperature of 400 °C have constant resistance. The surface morphology of the films was studied by Scanning electron microscopy. XPS spectra showed that the peak of O1s of the as-deposited films is smaller than the peak of the annealed ZnO:Al films.     

Auger electron/X-ray photoelectron and cathodoluminescent spectroscopic studies of pulsed laser ablated SrAl2O4:Eu,Dy thin films

Auger electron/X-ray photoelectron and cathodoluminescent (CL) spectroscopic studies were conducted on pulsed laser deposited SrAl₂O₄:Eu²⁺,Dy³⁺ thin films and the correlation between the surface chemical reactions and the decrease in the CL intensity was determined. The Auger electron and the CL data were collected simultaneously in a vacuum chamber either maintained at base pressure or backfilled with oxygen gas. The data were collected when the films were irradiated for 14 h with 2 keV electrons. The CL emission peak attributed to the 4f⁶5d¹ → 4f⁷ transitions was observed at ∼521 nm and the CL intensity of the peaks degraded at different rates in different vacuum conditions. X-ray photoelectron spectroscopy (XPS) data collected from degraded films suggest that strontium oxide (SrO) and aliminium oxide (Al₂O₃) were formed on the surface of the film as a result of electron stimulated surface chemical reaction (ESSCR).     

Electrodeposition of zinc oxide/tetrasulfonated copper phthalocyanine hybrid thin film for dye-sensitized solar cell application

Hybrid film of zinc oxide (ZnO) and tetrasulfonated copper phthalocyanine (TSPcCu) was grown on an indium tin oxide (ITO) glass by one-step cathodic electrodeposition from aqueous mixtures of Zn(NO₃)₂, TSPcCu and KCl. The addition of TSPcCu strongly influences the morphology and crystallographic orientation of the ZnO. The nanosheets stack of ZnO leads to a porous surface structure which is advantageous to further adsorb organic dyes. The photovoltaic properties were investigated by assembling the DSSC device based on both the only ZnO film and the ZnO/TSPcCu hybrid films. Photoelectrochemical analysis revealed that the optimized DSSC device with TSPcCu represented a more than three-fold improvement in power conversion efficiency than the device without TSPcCu. The DSSC based on ZnO/TSPcCu hybrid films demonstrates an open circuit voltage of 0.308 V, a short circuit current of 90 μA cm⁻², a fill factor of 0.26, and a power conversion efficiency of 0.14%.     

Deposition of nanostructured crystalline and corrosion resistant alumina film on bell metal at low temperature by rf magnetron sputtering

Aluminium oxide films deposited by rf magnetron sputtering for protective coatings have been investigated. The alumina films are found to exhibit grainy surface microstructure. The grain size, structure and density depend on different system parameters such as argon and/or oxygen flow rate and applied rf power etc. The effect of transition of the discharge from metallic to reactive mode on the surface characteristics of the alumina film is studied. X-ray diffractometry reveals that in poisoned mode of sputtering and under optimized power and pressure, crystalline alumina film can be grown. Different system conditions are optimized for corrosion resistant aluminium oxide films with good adhesion properties. Nanostructured alumina film is obtained at lower pressure (8 × 10⁻⁴ to 9 × 10⁻⁴ Torr) by rf reactive magnetron sputtering.     

Electrostatic spray deposited zinc oxide films for gas sensor applications

In this work, thin films of zinc oxide (ZnO) for gas-sensor applications were deposited on platinum coated alumina substrate, using electrostatic spray deposition (ESD) technique. As precursor solution zinc acetate in ethanol was used. Scanning electron microscopy (SEM) evaluation showed a porous and homogeneous film morphology and the energy dispersive X-ray analysis (EDX) confirmed the composition of the films with no presence of other impurities. The microstructure studied with X-ray diffraction (XRD) and Raman spectroscopy indicated that the ZnO oxide films are crystallized in a hexagonal wurtzite phase. The films showed good sensitivity to 1 ppm nitrogen dioxide (NO₂) at 300 °C while a much lower sensitivity to 12 ppm hydrogen sulphide (H₂S).     

Effect of substrate temperature on properties of multilayer thin film based on ZnO and Mo-doped indium oxide

Zinc oxide/molybdenum-doped indium oxide/zinc oxide (ZnO/IMO/ZnO) multilayer thin films are grown using pulsed laser deposition technique. The effect of substrate temperature on structural, optical, and electrical properties of multilayer films is studied. It is observed that films grown at high substrate temperature are oriented along (0 0 2) and (2 2 2) direction for ZnO and IMO respectively. The crystallinity of these films increases with increase in substrate temperature. It is also seen that conductivity, carrier concentration, and mobility increase with increase in temperature. The multilayer film grown at 500 °C has low resistivity (7.67 × 10⁻⁵ Ω cm), high carrier concentration (3.90 × 10²⁰ cm⁻³), and high mobility (209 cm²/Vs).     

Synthesis and characterization of Ni-doped ZnO: A transparent magnetic semiconductor

We report synthesis of a transparent magnetic semiconductor by incorporating Ni in zinc oxide (ZnO) matrix. ZnO and nickel-doped zinc oxide (ZnO:Ni) thin films (∼60 nm) are prepared by fast atom beam (FAB) sputtering. Both undoped and doped films show the presence of ZnO phase only. The Ni concentration (in at%) as determined by energy dispersive X-ray (EDX) technique is ∼12±2%. Magnetisation measurement using a SQUID magnetometer shows that the Ni-doped films are ferromagnetic, having coercivity (H_c) values 192, 310 and 100 Oe and saturation magnetization (M_s) values of 6.22, 5.32 and 4.73 emu/g at 5, 15 and 300 K, respectively. The Ni-doped film is transparent (>80%) across visible wavelength range. Resistivity of the ZnO:Ni film is ∼2.5×10⁻³ Ω cm, which is almost two orders of magnitude lower than the resistivity (∼4.5×10⁻¹ Ω cm) of its undoped counterpart. Impurity d-band splitting is considered to be the cause of increase in conductivity. Interaction between free charges generated by doping and localized d spins of Ni is discussed as the reason for ferromagnetism in the ZnO:Ni film.     

Characteristics of filtered vacuum arc deposited ZnO-SnO2 thin films on room temperature substrates

ZnO, SnO₂ and zinc stannate thin films were deposited using filtered vacuum arc deposition (FVAD) system on commercial microscope glass and UV fused silica substrates (UVFS) at room temperature (RT). The structural and morphological analyses were performed using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM), respectively. XRD patterns of ZnO films deposited at RT had strongly c-axis orientation, whereas SnO₂ and zinc stannate films had amorphous structure as they did not have any defined patterns. Average crystalline size and surface grain size of ZnO films were ∼16 nm, as determined from diffraction line broadening and AFM images, respectively. Optical constants in the 250-1100 nm wavelength range were determined by variable angle spectroscopic ellipsometry and transmission measurements. The transmission of the deposited films in the VIS was 80-90%, affected by interference. The refractive indices and the extinction coefficients of deposited ZnO, SnO₂ and zinc stannate films were in the range 1.87-2.15 and 0.02-0.04, depending on wavelengths and deposition parameters. The optical band gap (E_g) was determined by the dependence of the absorption coefficient on the photon energy at short wavelengths. Its values for ZnO, SnO₂ and zinc stannate were in the range 3.25-3.30 eV, 3.60-3.98 eV and 3.43-3.52 eV, respectively, depending on the deposition pressure.     

Structural and electrical properties of zinc oxides thin films prepared by thermal oxidation

We report on zinc oxide (ZnO) thin films (d = 55-120 nm) prepared by thermal oxidation, at 623 K, of metallic zinc films, using a flash-heating method. Zinc films were deposited in vacuum by quasi-closed volume technique onto unheated glass substrates in two arrangements: horizontal and vertical positions relative to incident vapour. Depending on the preparation conditions, both quasi-amorphous and (0 0 2) textured polycrystalline ZnO films were obtained. The surface morphologies were characterized by atomic force microscopy and scanning electron microscopy. By in situ electrical measurements during two heating-cooling cycles up to a temperature of 673 K, an irreversible decrease of electrical conductivity of as flash-oxidized Zn films was revealed. The influence of deposition arrangement and oxidation conditions on the structural, morphological and electrical properties of the ZnO films is discussed.     

Effects of seed layer on the structure and property of zinc oxide thin films electrochemically deposited on ITO-coated glass

ZnO films with different morphologies were deposited on the ITO-coated glass substrate from zinc nitrate aqueous solution at 65 °C by a seed-layer assisted electrochemical deposition route. The seed layers were pre-deposited galvanostatically at different current densities (i_sl) ranging from −1.30 to −3.0 mA/cm², and the subsequent ZnO films had been done using the potentiostatic technique at the cathode potential of −1.0 V. Densities of nucleation centers in the seed layers varied with increasing the current density, and the ZnO films on them showed variable morphologies and optical properties. The uniform and compact nanocrystalline ZnO film with (0 0 2) preferential orientation was obtained on seed layer that was deposited under the current density (i_sl) of −1.68 mA/cm², which exhibited good optical performances.     

Low temperature synthesis wide optical band gap Al and (Al, Na) co-doped ZnO thin films

Al-doped ZnO (AZO) and (Al, Na) co-doped ZnO (ANZO) thin films were prepared via sol-gel technique with an annealing process at temperatures between 450 and 550 °C for 60 min in air ambient, and their structural and optical properties have been investigated. The deposited films exhibited hexagonal zinc oxide structure except annealing at 450 °C. For the 500 °C-annealed samples, the surface morphology was analyzed via scanning electron microscopy, Photoluminescence (PL) of different Na content ANZO thin films showed that there were very obvious violet and blue emission bands between 400 and 500 nm, and intensity of which were enhanced with Na content increasing. Transparency of the films was improved along with increasing Na content. The result of UV indicated the absorb bands appeared obviously red shift with Na doping into ZnO, the optical gaps of all films far beyond 3.37 eV of pure ZnO, and gradually decreased with Na content increasing, this is very virtual for improving photoelectricity performance of transparent conduct oxide (TCO) film. The possible origins responsible for structure and optical properties also had been discussed.     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

Laser energy density, structure and properties of pulsed-laser deposited zinc oxide films

Zinc oxide thin films were deposited on soda lime glass substrates by pulsed laser deposition in an oxygen-reactive atmosphere at 20 Pa and a constant substrate temperature at 300 °C. A pulsed KrF excimer laser, operated at 248 nm with pulse duration 10 ns, was used to ablate the ceramic zinc oxide target. The structure, the optical and electrical properties of the as-deposited films were studied in dependence of the laser energy density in the 1.2-2.8 J/cm² range, with the aid of X-ray Diffraction, Atomic Force Microscope, Transmission Spectroscopy techniques, and the Van der Pauw method, respectively. The results indicated that the structural and optical properties of the zinc oxide films were improved by increasing the laser energy density of the ablating laser. The surface roughness of the zinc oxide film increased with the decrease of laser energy density and both the optical bang gap and the electrical resistivity of the film were significantly affected by the laser energy density.