Effect of cadmium oxide incorporation on the microstructural and optical properties of pulsed laser deposited nanostructured zinc oxide thin films

CdO doped (doping concentration 0, 1, 3 and 16 wt%) ZnO nanostructured thin films are grown on quartz substrate by pulsed laser deposition and the films are annealed at temperature 500 °C. The structural, morphological and optical properties of the annealed films are systematically studied using grazing incidence X-ray diffraction (GIXRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), atomic force microscopy (AFM), Micro-Raman spectra, UV–vis spectroscopy, photoluminescence spectra and open aperture z-scan. 1 wt% CdO doped ZnO films are annealed at different temperatures viz., 300, 400, 500, 600, 700 and 800 °C and the structural and optical properties of these films are also investigated. The XRD patterns suggest a hexagonal wurtzite structure for the films. The crystallite size, lattice constants, stress and lattice strain in the films are calculated. The presence of high-frequency E₂ mode and the longitudinal optical A₁ (LO) modes in the Raman spectra confirms the hexagonal wurtzite structure for the films. The presence of CdO in the doped films is confirmed from the EDX spectrum. SEM and AFM micrographs show that the films are uniform and the crystallites are in the nano-dimension. AFM picture suggests a porous network structure for 3% CdO doped film. The porosity and refractive indices of the films are calculated from the transmittance and reflectance spectra. Optical band gap energy is found to decrease in the CdO doped films as the CdO doping concentration increases. The PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. The 16CdZnO film shows an intense deep green PL emission. Non-linear optical measurements using the z-scan technique indicate that the saturable absorption (SA) behavior exhibited by undoped ZnO under green light excitation (532 nm) can be changed to reverse saturable absorption (RSA) with CdO doping. From numerical simulations the saturation intensity (I_s) and the effective two-photon absorption coefficient (β) are calculated for the undoped and CdO doped ZnO films.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Preparation and pseudo-capacitance of birnessite-type MnO2 nanostructures via microwave-assisted emulsion method

A microwave-assisted emulsion process has been developed to synthesize birnessite-type MnO₂ one-dimensional (1D) nanostructures. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). TEM images confirmed that the particles were composed of nanowires and nanobelts. As a consequence of the small size, such MnO₂ nanostructures exhibit a high specific capacitance of 277 F g⁻¹ at the current density of 0.2 mA cm⁻². Furthermore, the simple synthetic approach may provide a convenient route for the preparation of birnessite-type MnO₂ nanowires and other 1D nanostructured materials on a large scale.     

Optical and structural properties of zinc oxide films with different thicknesses prepared by successive ionic layer adsorption and reaction method

In this work, zinc oxide semiconducting films belonging to the II-VI group have been produced by successive ionic layer adsorption and reaction (SILAR) method on glass substrates with 10, 15, 20 and 25 cycles at room temperature. Following the deposition, the samples were dried in air at 400 °C for 1 h. The films were characterized by X-ray diffraction, field emission scanning electron microscopy and optical absorption measurement techniques. The X-ray diffractions of the films showed that they are hexagonal in structure. The crystallite size of ZnO films varied between 34 and 38 nm accordingly with the number of SILAR cycles. The material has exhibited direct band gap transition with the band gap values lying in the range between 3.13 and 3.18 eV. The red shift is observed in the absorption edge as the cycles increased. Transmission of the films decreased from 65 to 40% with increasing the number of cycles.     

Effect of preparation methods and optical band gap of ZnO nanomaterials on photodegradation studies

Improving of photo-oxidative efficiency of ZnO has become of importance to meet the requirements of environmental protection. In this research, ZnO nanomaterials prepared by three different methods (thermal decomposition, precipitation and sol-gel-combustion using metal nitrate and different fuels (urea, oxalic acid and citric acid)). Various molar ratios of citric acid to salt used as variable parameter (0.50, 0.75, 1.00, 1.25, and 1.50). These nanomaterials were characterized by studying their structural, morphological, surface and optical properties. The photocatalytic activity was evaluated by photocatalytic degradation of Remazol Red RB-133 (RR) under UV-light irradiation. The obtained results showed that the photocatalytic efficiency was affected by preparation method, type and ratio of fuel to salt. The optimum is a gel precursor containing zinc nitrate and citric acid prepared in the molar ratio of 1. The highly active nanomaterial was applied for photocatalytic degradation of mixtures of two dyes – (RR) and Methylene Blue (MB).     

Comparative study of structural and optical properties of ZnO nanostructures prepared by three different aqueous solution methods

In the present work, zinc oxide (ZnO) nanoparticles with different morphologies and sizes were successfully synthesized via three different aqueous solution routes named proteic sol–gel, PVA-assisted sol–gel and microwave-assisted hydrothermal method. Sol–gel samples were crystallized into hexagonal structure after calcination at 350 °C, presenting uniform growth and predominantly spherical particles. On the other hand, the sample produced via hydrothermal method assumed nanorod morphology, probably due to the adsorption of ammonium on the surface of ZnO nuclei, which affect the growth orientation of the crystals. All the samples exhibited a sharp UV emission peak, related to excitonic recombination, and a broad emission band in the visible region, attributed to internal transitions in color centers. Sol–gel samples calcined at the lowest temperatures presented an UV emission intensity that was 44 and 89 times higher than the visible emission, which can be related to the passivation of the defects by hydrogen ions. As-prepared hydrothermal sample presented a broad emission band centered at approximately 596 nm, which is possibly related to OH groups adsorbed on the particle surfaces. Nevertheless, the emission band of samples calcined above 800 °C was shifted to 540 nm, which is probably related to oxygen vacancy according to the results from chemical analysis.     

Effects of initial precursor and microwave irradiation on step-by-step synthesis of zinc oxide nano-architectures

ZnO nano-architectures were produced with the aid of a fast, simple and low cost microwave-assisted synthesis method. Solid semispherical ZnO nanoparticles on the order of 600 nm in diameter along with rice-like ZnO nanorods 95 nm thick were produced from butanol, triethanolamine (TEA), and zinc acetate dihydrate. Solid spherical ZnO nano-architectures with an average diameter of 250 nm were produced from the same starting materials in addition to NaOH. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to characterize the ZnO nano-architectures as well as the precursor. This method is cheap, fast and simple; capable of producing large quantities of each ZnO nanostructure. Investigation of the step-by-step formation mechanism for each ZnO nanostructure was conducted.     

Extraction of optical constants of zinc oxide thin films by ellipsometry with various models

Spectroscopic ellipsometry was used to extract the optical constants of zinc oxide (ZnO) thin films deposited on (100) silicon substrate by filtered cathodic vacuum arc technique. Three dispersion models, namely, Sellmeier dispersion model, Cauchy model and Forouhi–Bloomer model, were evaluated for determining the optical constants of ZnO thin films below the energy band gap. The study shows that the Cauchy model provides the best spectral fittings among these three models. Above the energy band gap, two ellipsometric models, namely, two-phase model and three-phase point-by-point fit, were used. This study reveals that the initial values used in the point-by-point fitting play a critical role. It also shows that the refractive index and the extinction coefficient calculated with the two-phase model can be used as the initial values for the point-by-point fitting. The spectral dependence of the refractive index and extinction coefficient obtained in this work is comparable with the data reported in the literature. In sum, a reliable methodology for determining the optical constants of ZnO thin films in the ultraviolet-visible-near infrared range (2501100 nm) has been developed.     

Role of precursors on morphology and optical properties of ZnS thin films prepared by chemical spray pyrolysis

This study investigates the effect of different growth parameters on the structural and optical properties of ZnS thin films, prepared using spray pyrolysis. The films were prepared using different Zn:S ratios (between 1:1 and 1:6) and in different growth solutions: (A), zinc chloride and thiourea and (B) dehydrated zinc acetate and thiourea, both in distilled water.By varying the Zn:S ratio in the films, the optical properties (absorption and photoluminescence) show that different species are created during film growth. This was deduced from the wide emission band appearing in the green region of the photoluminescence spectra, and from the change in band gap, which varies between 3.2 and 3.5 eV. Films formed from solution (A) with a Zn:S ratio of 1:3 or 1:4 show the best morphology and transmission. ZnS has a wider band gap than other conventional II-VI semiconductors utilized in various electronic and optical devices and can be expected to provide a useful window layer of solar cells which leads to an improvement in overall efficiency by decreasing absorption loss.     

Optical and electrical properties of zinc oxide/indium/zinc oxide multilayer structures

Zinc oxide/indium/zinc oxide multilayer structures have been obtained on glass substrates by magnetron sputtering. The effects of indium thickness on optical and electrical properties of the multilayer structures are investigated. Compared to a single zinc oxide layer, the carrier concentration increases from 8 × 10¹⁸ cm⁻³ to 1.8 × 10²⁰ cm⁻³ and Hall mobility decreases from 10 cm²/v s to 2 cm²/v s for the multilayer structure at 8 nm of indium thickness. With the increase of indium thickness, the transmittance decreases and optical band gap shifts to lower energy in multilayer structures. Results are understood based on Schottky theory, interface scattering mechanism and the absorption of indium layer.     

The effect of dopants on the morphology, microstructure and electrical properties of transparent zinc oxide films prepared by the sol-gel method

The influence of doping on the morphology, physical and electrical properties of zinc oxide produced by the sol-gel method was examined. Undoped zinc oxide was observed to form relatively porous films. Addition of an Al dopant influenced the sheet resistance, but did not result in a change in morphology, examined by atomic force microscopy when compared to undoped films. In the case of electrical measurements, undoped ZnO films were extremely resistive. A minimum dopant concentration of 2 at.%. Al was required to produce materials which were more conductive, as observed by sheet resistance measurements, which were shown to vary with annealing temperature. The versatile nature of sol-gel processing was demonstrated by selective ink-jet deposition of sol-gel droplets which were annealed to form oxide materials.     

Indium tin oxide films made from nanoparticles: models for the optical and electrical properties

Porous thin films comprising nanoparticles of In₂O₃:Sn (known as indium tin oxide, ITO) were made by spin coating followed by annealing. The nanoparticles were prepared by a wet chemical technique. The films had a luminous transmittance of ∼90% and an electrical resistivity of ∼10⁻² Ω cm. Spectral transmittance and reflectance were analyzed by first representing the ITO nanoparticles within the Drude theory, with a frequency-dependent scattering time characteristic for ionized impurity scattering, and then applying effective medium theory to account for the porosity. It was found that the individual nanoparticles had a resistivity of ∼2×10⁻⁴ Ω cm, i.e. their electrical properties were comparable to those in the best films made by physical or chemical vapour deposition. Temperature-dependent electrical resistivity data for the films could be reconciled with a model for fluctuation induced tunneling between micrometer-size clusters of internally connected ITO nanoparticles.     

Green synthesis of zinc oxide nanoparticles by aloe barbadensis miller leaf extract: Structure and optical properties

Biological methods for nanoparticle synthesis using microorganisms, enzymes, and plants or plant extracts have been suggested as possible ecofriendly alternatives to chemical and physical methods. In this paper, we report on the synthesis of nanostructured zinc oxide particles by both chemical and biological method. Highly stable and spherical zinc oxide nanoparticles are produced by using zinc nitrate and Aloe vera leaf extract. Greater than 95% conversion to nanoparticles has been achieved with aloe leaf broth concentration greater than 25%. Structural, morphological and optical properties of the synthesized nanoparticles have been characterized by using UV-Vis spectrophotometer, FTIR, Photoluminescence, SEM, TEM and XRD analysis. SEM and TEM analysis shows that the zinc oxide nanoparticles prepared were poly dispersed and the average size ranged from 25 to 40 nm. The particles obtained have been found to be predominantly spherical and the particle size could be controlled by varying the concentrations of leaf broth solution.     

Nanostructured zinc oxide films synthesized by successive chemical solution deposition for gas sensor applications

Nanostructured ZnO thin films have been deposited using a successive chemical solution deposition method. The structural, morphological, electrical and sensing properties of the films were studied for different concentrations of Al-dopant and were analyzed as a function of rapid photothermal processing temperatures. The films were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron and micro-Raman spectroscopy. Electrical and gas sensitivity measurements were conducted as well. The average grain size is 240 and 224 Å for undoped ZnO and Al-doped ZnO films, respectively. We demonstrate that rapid photothermal processing is an efficient method for improving the quality of nanostructured ZnO films. Nanostructured ZnO films doped with Al showed a higher sensitivity to carbon dioxide than undoped ZnO films. The correlations between material compositions, microstructures of the films and the properties of the gas sensors are discussed.     

Synthesis of sub-5 nm Co-doped SnO2 nanoparticles and their structural,microstructural, optical and photocatalytic properties

A swift chemical route to synthesize Co-doped SnO₂ nanopowders is described. Pure and highly stable Sn_1−xCo_xO_2−δ (0 ≤ x ≤ 0.15) crystalline nanoparticles were synthesized, with mean grain sizes <5 nm and the dopant element homogeneously distributed in the SnO₂ matrix. The UV–visible diffuse reflectance spectra of the Sn_1−xCo_xO_2−δ samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The samples' Urbach energies were calculated and correlated with their bandgap energies. The photocatalytic activity of the Sn_1−xCo_xO_2−δ samples was investigated for the 4-hydroxylbenzoic acid (4-HBA) degradation process. A complete photodegradation of a 10 ppm 4-HBA solution was achieved using 0.02% (w/w) of Sn_0.95Co_0.05O_2−δ nanoparticles in 60 min of irradiation.     

Effect of deposition distance and temperature on electrical, optical and structural properties of radio-frequency magnetron-sputtered gallium-doped zinc oxide

Films of gallium-doped zinc oxide (GZO) were deposited on glass substrates by radio-frequency magnetron sputtering using a ceramic target of Ga:ZnO (4 at.% Ga vs. Zn). Both the substrate temperature (T_s) and the target-substrate distance (d_ts) were varied and the effect on electrical, optical and structural properties of the resulting films were measured. The highest conductivity of 3200 S/cm was obtained at a deposition temperature of 250 °C, at a d_ts of 51 mm. This sample had the highest carrier concentration in this study, 9.6 × 10²⁰/cm³. Optical transmittance of all films was <90% in the visible range. The grain size of the film grown at d_ts = 51 mm was smaller than the grain size for films grown with a shorter d_ts; moreover, the films with d_ts = 51 mm exhibited the smoothest surface, with a root mean square surface roughness of 2.7 nm. Changes in T_s have a more pronounced effect on conductivity compared to changes in d_ts; however, variations in structure do not appear to be well-correlated with conductivity for samples in the 2000-3200 S/cm range. These results suggest that incorporation and activation of Ga is of key importance when attempting to obtain GZO films with conductivities greater than 2000 S/cm.     

Structural, electrical and optical properties of zirconium-doped zinc oxide films prepared by radio frequency magnetron sputtering

Transparent and conducting zirconium-doped zinc oxide films have been prepared by radio frequency magnetron sputtering at room temperature. The ZrO₂ content in the target is varied from 0 to 10 wt.%. The films are polycrystalline with a hexagonal structure and a preferred orientation along the c axis. As the ZrO₂ content increases, the crystallinity and conductivity of the film are initially improved and then both show deterioration. Zr atoms mainly substitute Zn atoms when the ZrO₂ content are 3 and 5 wt.%, but tend to cluster into grain boundaries at higher contents. The lowest resistivity achieved is 2.07 × 10^− 3 Ω cm with the ZrO₂ content of 5 wt.% with a Hall mobility of 16 cm² V^− 1 s^− 1 and a carrier concentration of 1.95 × 10²⁰ cm^− 3. All the films present a high transmittance of above 90% in the visible range. The optical band gap depends on the carrier concentration, and the value is larger at higher carrier concentration.     

Effect of vacuumization on the photoluminescence and photoresponse decay of the zinc oxide nanostructures grown by different methods

Influence of vacuumization on the photoluminescence (PL) spectra and photoresponse decay of ZnO nanostructures fabricated by different methods was investigated. The visible band of photoluminescence and ultraviolet (UV) photosensitivity of the samples grown from a vapor phase was associated with the intrinsic defects such as doubly charged zinc vacancies, and for the samples grown by hydrothermal method – with presence of the oxygen vacancies. The experimental results show that ZnO nanostructures grown from the vapor phase would be promising for producing of the low cost and effective UV detecting devices.     

Formation of zinc oxide film by boiling metallic zinc film in ultrapure water

A simple method for forming zinc oxide (ZnO) films has been discovered. Radio-frequency (rf) sputtered metallic zinc (Zn) film is boiled in ultrapure water at 368 K. The opaque Zn film changes into a transparent film. It is confirmed by transmission electron microscopy and X-ray diffraction that the transparent film is hexagonal ZnO. Optical and morphological properties of the ZnO film are discussed.     

Growth and characterization of electrosynthesised zinc oxide thin films

Zinc oxide (ZnO) films have been electrodeposited from an aqueous solution containing 0.1 M zinc nitrate as the electrolyte with pH around 5±0.1. The deposition was carried out by galvanostatic reduction with an applied cathodic current density in the range between 5 and 20 mA cm⁻². The influence of bath composition on the preparation of ZnO films is studied. The effects of zinc nitrate concentration and cathodic current density on the deposition rate of ZnO films were also studied. An optimum current density of 10 mA cm⁻² is identified for the growth of ZnO film with improved crystallinity and optical transmittance. The crystalline structure of the deposits studied by X-ray diffraction reveals the possibility of growing hexagonal ZnO films under suitable electrochemical conditions. The surface morphological studies by scanning electron micrographs revealed the presence of nodular appearance for films deposited at 800 °C bath temperatures.