Optical, structural and adsorption properties of zinc peroxide/hydrogel nanohybrid films

Hybrid nanofilms from zinc-peroxide/poly(acrylamide) (ZnO₂/PAAm) and zinc-peroxide/poly(N-isopropyl-acrylamide) (ZnO₂/PNIPAAm) were prepared using the photopolymerization procedure. The thin layers were prepared by the combination of the Layer-by-Layer (LbL) self-assembly method and photopolymerization using UV light in every step of the procedure. The hybrid multilayer films consisting of layers of zinc peroxide nanoparticles and hydrogel alternating in a sandwich-like fashion with thicknesses of 65-246 nm. The chemical structures of the hybrid films were investigated by FTIR spectroscopy, their morphology was studied by atomic force microscopy (AFM). The build up of the films was studied by measuring the optical reflection spectrum, and we have calculated the refractive index and layer thickness of the hybrid layers using simulating software. The adsorption properties of the ZnO₂/hydrogel nanohybrid composite networks were investigated by measuring water and ethanol vapour adsorption by a quartz crystal microbalance (QCM). It was established that on partially hydrophobic ZnO₂/PNIPAAm hybrids the adsorbed amounts were lower, against the hydrophilic ZnO₂/PAAm film the vapour amount was higher. These results correspond to those of the bulk gel swelling results.     

The influence of titanium on the properties of zinc oxide films deposited by radio frequency magnetron sputtering

TiO₂-doped zinc oxide thin films were deposited on glass substrates by radio frequency (RF) magnetron sputtering with TiO₂-doped ZnO targets in an argon atmosphere. The structural properties of TiO₂-doped ZnO films doped with different TiO₂ contents were investigated. The experimental results show that polycrystalline TiO₂-doped ZnO films had the (0 0 2) preferred orientation. The deposition parameters such as the working pressure and substrate temperature of TiO₂-doped ZnO films were also investigated. The crystalline structure of the TiO₂-doped ZnO films gradually improved as the working pressure was lowered and the substrate temperature was raised. The lowest electrical resistivity for the TiO₂-doped ZnO films was obtained when the Ti addition was 1.34 wt%; its value was 2.50 × 10⁻³ Ω cm, smaller than that found in previous studies. The transmittance of the TiO₂-doped ZnO films in the visible wavelength range was more than 80%. The optical energy gap was related to the carrier concentration, and was in the range of 3.30-3.48 eV.     

FTIR and spectroscopic ellipsometry investigations of the electron beam evaporated silicon oxynitride thin films

FTIR and variable angle spectroscopic ellipsometer in conjunction with computer simulation were employed to investigate the electron beam evaporated SiO_xN_y thin films. FTIR showed a large absorption band located between 600 and 1250 cm⁻¹, which indicates that Si-O and Si-N bands are overlap in SiO_xN_y films. A three layers model was used to fit the calculated data to the experimental ellipsometric spectra. The main layer was described by Cauchy model while the interface layer and the surface layer were described using Tauc-Lorenz oscillator and Bruggeman effective medium approximation, respectively. The thickness, the refractive index and the extinction coefficient were accurately determined. The refractive index at 630 nm was found to increase from 1.74 to 1.85 with increasing the film thickness from 191.6 to 502.2 nm. The absorption coefficient was calculated from the obtained extinction coefficient values and it has been used to calculate the Tauc and Urbach energies.     

Characterization and properties of ZnO1−xSx alloy films fabricated by radio-frequency magnetron sputtering

A series of ZnO_1−xS_x alloy films (0 ≤ x ≤ 1) were grown on quartz substrates by radio-frequency (rf) magnetron sputtering of ZnS ceramic target, using oxygen and argon as working gas. X-ray diffraction measurement shows that the ZnO_1−xS_x films have wurtzite structure with (0 0 2) preferential orientation in O-rich side (0 ≤ x ≤ 0.23) and zinc blende structure with (1 1 1) preferential orientation in S-rich side (0.77 ≤ x ≤ 1). However, when the S content is in the range of 0.23 < x < 0.77, the ZnO_1−xS_x film consists of two phases of wurtzite and zinc blende or amorphous ZnO_1−xS_x phase. The band gap energy of the films shows non-linear dependence on the S content, with an optical bowing parameter of about 2.9 eV. The photoluminescence (PL) measurement reveals that the PL spectrum of the wurtzite ZnO_1−xS_x is dominated by visible band and its PL intensity and intensity ratio of UV to visible band decrease greatly compared with undoped ZnO. All as-grown ZnO_1−xS_x films behave insulating, but show n-type conductivity for w-ZnO_1−xS_x and maintain insulating properties for β-ZnO_1−xS_x after annealed. Mechanisms of effects of S on optical and electrical properties of the ZnO_1−xS_x alloy are discussed in the present work.     

Room temperature transparent conducting oxides based on zinc oxide thin films

Doped zinc oxide thin films are grown on glass substrate at room temperature under oxygen atmosphere, using pulsed laser deposition (PLD). O₂ pressure below 1 Pa leads to conductive films. A careful characterization of the film stoichiometry and microstructure using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) concludes on a decrease in crystallinity with Al and Ga additions (≤3%). The progressive loss of the (0 0 2) orientation is associated with a variation of the c parameter value as a function of the film thickness and substrate nature. ZnO:Al and ZnO:Ga thin films show a high optical transmittance (>80%) with an increase in band gap from 3.27 eV (pure ZnO) to 3.88 eV and 3.61 eV for Al and Ga doping, respectively. Optical carrier concentration, optical mobility and optical resistivity are deduced from simulation of the optical data.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

Dependences of the surface and the optical properties on the O2/O2 + Ar flow-rate ratios for ZnO thin films grown on ZnO buffer layers

ZnO active layers on ZnO buffer layers were grown at various O₂/O₂ + Ar flow-rate ratios by using radio-frequency magnetron sputtering. Atomic force microscopy images showed that the surface roughnesses of the ZnO active layers grown on ZnO buffer layers decreased with decreasing O₂ atmosphere, indicative of an improvement in the ZnO surfaces. The type of the ZnO active layer was n-type, and the resistivity of the layer increased with increasing O₂ atmosphere. Photoluminescence spectra from the ZnO active layers grown on the ZnO buffer layers showed dominant peaks corresponding to local levels in the ZnO energy gap resulting from oxygen vacancies or interstitial zinc vacancies, and the peak positions changed significantly with the O₂/O₂ + Ar flow rate. These results can help improve understanding of the dependences of the surface and the optical properties on the O₂/O₂ + Ar ratio for ZnO thin films grown on ZnO buffer layers.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Sol-gel preparation and characterization of nanoporous ZnO/SiO2 coatings with broadband antireflection properties

Nanoporous ZnO/SiO₂ bilayer coatings were prepared on the surface of glass substrates via sol-gel dip-coating process. The structural, morphological and optical properties of the coatings were characterized. The refractive indices of ZnO layer and SiO₂ layer are 1.34 and 1.21 at 550 nm, respectively. The transmittance and reflectance spectra of the coatings were investigated and the broadband antireflection performance of the bilayer structure was determined over the solar spectrum. The solar transmittances in the range of 300-1200 nm and 1200-2500 nm are increased by 6.5% and 6.2%, respectively. The improvement of transmittance is attributed to the destructive interference of light reflected from interfaces between the different refractive-index layers with an optimized thickness. Such antireflection coatings of ZnO/SiO₂ provide a promising route for solar energy applications.     

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.     

Structural-optical study of high-dielectric-constant oxide films

High-k polycrystalline Pr₂O₃ and amorphous LaAlO₃ oxide thin films deposited on Si(0 0 1) are studied. The microstructure is investigated using X-ray diffraction and scanning electron microscopy. Optical properties are determined in the 0.75-6.5 eV photon energy range using spectroscopic ellipsometry. The polycrystalline Pr₂O₃ films have an optical gap of 3.86 eV and a dielectric constant of 16-26, which increases with film thickness. Similarly, very thin amorphous LaAlO₃ films have the optical gap of 5.8 eV, and a dielectric constant below 14 which also increases with film thickness. The lower dielectric constant compared to crystalline material is an intrinsic characteristic of amorphous films.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

Effect of annealing temperature on the optical constants of zinc oxide films

In this paper, the effect of annealing temperature on optical constants was studied. The ZnO films were deposited on microscopic glass substrates using the sol-gel method for various annealing temperatures. The deposited zinc oxide (ZnO) films were characterized by an X-ray diffractometer (XRD), a spectrophotometer and scanning electron microscopy (SEM). The transmittance spectra recorded through the spectrophotometer exhibits 90% transmittance. The XRD spectra showed polycrystalline nature of ZnO film. Optical constants were determined through transmittance spectra using an envelope method. It was found that there was a significant effect of annealing temperature on the refractive index and extinction coefficient of deposited ZnO films. In this experiment, the optimum refractive index value of 1.97 was obtained at 350 °C annealing temperature at visible (vis) wavelength. The optical energy gap was found to be of ∼3.2 eV for all the samples. The top view of SEM showed the ZnO grain growth on the glass substrates.     

Optical characterization and microstructure of BaTiO3 thin films obtained by RF-magnetron sputtering

BaTiO₃ thin films were deposited on Pt/Ti/SiO₂/Si by rf planar-magnetron sputtering. The films thickness increases with the decrease of both deposition pressure and sample-discharge centre distance. The films annealed at 900 °C, for 8 h, present direct band gap energy ranged between 3.57 and 3.59 eV. The dependence of the structure and microstructure (texture, degree of crystallinity), as well as of the optical characteristics on the deposition parameters, was analysed. Using spectroscopic ellipsometry (SE) measurements coupled with the Bruggeman Effective Medium Approximation (B-EMA), the layer structure and the surface roughness, were determined. The root mean square roughness values of the surface layer, estimated by atomic force microscopy (AFM) analyses, are ranged between 10 and 20 nm and were in good agreement with SE data.The obtained films have tetragonal unit cell and show densely packed, non-columnar morphology and hexagon-like crystallite shape.     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

Effects of depositing temperatures on structure and optical properties of TiO2 film deposited by ion beam assisted electron beam evaporation

TiO₂, which is high in refractive index and dielectric constant, plays an important role in the fields of optics and electronics. In this work, TiO₂ films were prepared on glass substrates by the technique of ion beam assisted electron beam evaporation. The films were deposited at 50, 150 and 300 °C, respectively. Then the as-deposited TiO₂ films were annealed at 450 °C for 1 h in vacuum atmosphere. Structures and optical properties of TiO₂ films were characterized by XRD, SEM, ellipsometry and spectrophotometer. As a result, the structure and the refractive index of films were improved by both the annealing and the increasing of the deposition temperature. The UV-vis transmittance spectra also confirmed that the deposition temperature has a significant effect on the transparency of the thin films. The highest transparency over the visible wavelength region of spectra was obtained at the deposition temperature of 300 °C. The allowed direct band gap at the deposition temperature ranging from 50 to 300 °C was estimated to be in the range from 3.81 to 3.92 eV.     

Microstructural, optical and photocatalytic properties of CdS doped TiO2 thin films

CdS doped TiO₂ thin films (with CdS content=0, 3, 6, 9 and 12 at%) were grown on glass substrates. The X-ray diffraction analysis revealed that the films are polycrystalline of monoclinic TiO₂ structure. The microstructure parameters of the films such as crystallite size (D_ν) and microstrain (e) are calculated. Both the crystallites size and the microstrain are decreased with increasing CdS content. The optical constants have been determined in terms of Murmann's exact equations. The refractive index and extinction coefficient are increased with increasing CdS content. The optical band gap is calculated in the strong absorption region. The possible optical transition in these films is found to be an allowed direct transition. The values of E_g^opt are found to decrease as the CdS content increased. The films with 3 at% CdS content have better decomposition efficiency than undoped TiO₂. The films with 6 at% and 9 at% CdS content have decomposition efficiency comparable to that of undoped TiO₂, although they have lower band gap. The CdS doped TiO₂ could have a better impact on the decomposing of organic wastes.     

Morphology transition of ZnO films with DMZn flow rate in MOCVD process

We used a metal-organic chemical vapor deposition (MOCVD) method to grow ZnO films on MgAl₂O₄ (1 1 1) substrate, and succeeded in preparing films with microstructures from well-aligned ZnO nanorods to continuous and dense films by adjusting the ratio of the input rates of oxygen and zinc sources (VI/II). At the growth temperature of 350 °C, the ZnO nanorods were formed under a low flow rate of a zinc precursor. On the other hand, continuous and dense ZnO films were formed under a high flow rate of the zinc precursor. There is a transition zone at medium zinc precursor flow rate, where nanorods transform to dense films. We proved that the height of ZnO nanorods and the thickness of ZnO dense films both increase with zinc flow rate, and are consistent with the mass-transport mechanism for ZnO growth. The XRD spectra of the sample in the transition zone show both (0 0 2) and (1 0 1) peaks, where (1 0 1) peaks are formed only in the transition zone. We consider that there are (0 0 2) and (1 0 1) ZnO grains in the early growth stage of dense ZnO films.     

Development of rf plasma sputtered Al2O3-TiO2 multilayer broad band antireflecting coatings and its correlation with plasma parameters

TiO₂/Al₂O₃/TiO₂/Al₂O₃ multilayer structures were obtained at different oxygen:argon gas ratios of 20:80, 30:70, 50:50 and 60:40 sccm and constant rf power of 200 W using reactive magnetron sputtering. Grain size and elemental distribution in the films were studied from AFM image and XPS spectra respectively. The deposited grain size increased with increasing oxygen:argon gas ratio. The optical band gap, refractive index, extinction coefficient were calculated from UV-vis transmittance and reflectance spectra. It was observed that the value of refractive index, extinction coefficient and band gap increased with increasing oxygen. These variations are due to the defects levels generated by the heterostructure and explained by the PL spectrum. The antireflecting (AR) efficiency of the films was estimated from the reflectance spectra of the films. Broad band antireflecting coating for the visible range was achieved by varying oxygen content in the film. The plasma chemistry controlled the antireflecting property by the interface interdiffusion of atoms during layer transition in multilayer deposition. The in situ investigation of the plasma chemistry was performed using optical emission spectroscopy. The plasma parameters were estimated and correlated with the characteristics of the films.