Structural properties of single and multilayer ITO and TiO2 films deposited by reactive pulsed laser ablation deposition technique

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. The films were deposited on SiO₂ substrates heated at 200 and 400 °C. ITO and TiO₂ films with uniform thicknesses of about 400 and 800 nm, respectively, over large areas were prepared. X-ray diffraction (XRD) analysis revealed that the ITO films are formed of highly orientated nanocrystals with an average particle size of 10-15 nm. Atomic force microscopy (AFM) observations indicate rough ITO films surfaces with average roughness of 26-30 nm. Pores were also observed. TiO₂ films deposited on the prepared ITO films result less crystalline. Annealing at 300 and 500 °C for three consecutive hours promoted formation of TiO₂ anatase phase, with crystal size of ∼6-7 nm. From the scanning transmission electron microscope (STEM) images, it can be seen that the TiO₂ films deposited onto the prepared ITO films present a relatively high pore sizes with an average pore diameter of ∼40 nm and excellent uniformity. In addition, STEM cross-sectional analysis of our films showed a columnar structure but no evidence of voids in the structure. Therefore, films exhibited large surface area, well suited for dye-sensitized solar cells (DSSC) applications.     

Uniform thin films of TiO2 nanoparticles deposited by matrix-assisted pulsed laser evaporation

We report morphological and optical properties of a colloidal TiO₂ nanoparticle film, deposited on a quartz substrate by using the Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. Atomic Force Microscopy demonstrated that a good uniformity of the deposition can be obtained. The presence of agglomerates with dimensions of about 1 μm in size was noticed. Form UV-vis transmission spectra, recorded in the 200-800 nm range, the optical constants and the energy gap were determined besides the film thickness. The optical constants resulted in agreement with the values reported in literature for TiO₂ nanoparticle thin films.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Enhanced optical properties of Al-doped TiO2 thin films in oxygen or nitrogen atmosphere

Al-doped TiO₂ (TiO₂:Al) films were deposited by simultaneous RF magnetron sputtering of TiO₂ and DC magnetron sputtering of Al. The advantage of this method is that the Al content could be independently controlled. By depositing in a mixed Ar-O₂ or a mixed Ar-N₂ atmosphere, the TiO₂:Al film became more stoichiometric and the nanocrystallinity was enhanced. The nonlinear refractive index of TiO₂:Al film deposited in a pure Ar, a mixed Ar-O₂ or a mixed Ar-N₂ atmosphere was measured by Moiré deflectometry, and was of the order of 10⁻⁸ cm² W⁻¹. For the TiO₂:Al film deposited in a pure Ar atmosphere, the porosity was higher corresponding to the lower transmission. However, the porosity of TiO₂:Al film decreased as the oxygen or nitrogen pressure increased. Especially, as the ratio of O₂ to Ar pressure increased to 0.22, TiO₂:Al film exhibited lower porosity, higher visible transmission, higher linear refractive index, lower stress and lower stress-optical coefficient.     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

Investigation on properties of TiO2 thin films deposited at different oxygen pressures

TiO₂ thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on optical, mechanical and structural properties of TiO₂ thin films were studied. The results showed that with the increase of oxygen partial pressure, the optical transmittance gradually increased, the transmittance edge gradually shifted to short wavelength, and the corresponding refractive index decreased. The residual stresses of all samples were tensile, and the value increased as oxygen partial pressure increasing, which corresponded to the evolutions of the packing densities. The structures of TiO₂ thin films all were amorphous because deposition particles did not possess enough energy to crystallize.     

Characterization of TiO2/Au/TiO2 films deposited by magnetron sputtering on polycarbonate substrates

Transparent and conducting TiO₂/Au/TiO₂ (TAuT) films were deposited by reactive magnetron sputtering on polycarbonate substrates to investigate the effect of the Au interlayer on the optical, electrical, and structural properties of the films. In TAuT films, the Au interlayer thickness was kept at 5 nm. Although total thickness was maintained at 100 nm, the stack structure was varied as 50/5/45, 70/5/25, and 90/5/5 nm.In XRD pattern, the intermediate Au films were crystallized, while all TAuT films did not show any diffraction peaks for TiO₂ films with regardless of stack structure. The optical and electrical properties were dependent on the stack structure of the films. The lowest sheet resistance of 23 Ω/□ and highest optical transmittance of 76% at 550 nm were obtained from TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films. The work function was dependent on the film stack. The highest work function (4.8 eV) was observed with the TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm film stack. The TAuT film stack of TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films is an optimized stack that may be an alternative candidate for transparent electrodes in flat panel displays.     

Room temperature ferromagnetism in vacuum-annealed TiO2 thin films

Thin films of pure TiO₂ have been prepared using both spin-coating and sputter-deposition techniques on sapphire and quartz substrates. The structural characteristics of the films have been investigated in detail using Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM). When annealed in vacuum, all films demonstrate room temperature ferromagnetism, while the air-annealed samples show much smaller, often negligible, magnetic moments. The magnetization of the vacuum-annealed sputtered samples depends on film thickness, with the volume magnetization decreasing monotonically with increasing thickness. Furthermore, the magnetization per unit area also decreases slightly with increasing film thickness. These results suggest that ferromagnetism in the vacuum-annealed TiO₂ films is mediated by surface defects or interfacial effects, but does not arise from stoichiometric crystalline TiO₂.     

Crystallisation of TiO2 thin films induced by excimer laser irradiation

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass substrate and subsequently irradiated by UV radiation using a KrF excimer laser. In this work, we have study the influence of the laser fluence (F) ranging between 0.05 and 0.40 mJ/cm² on the constitution and microstructure of the deposited films. Irradiated thin films are characterized by profilometry, scanning electron microscopy and X-ray diffraction. As deposited films are amorphous, while irradiated films present an anatase structure. The crystallinity of the films strongly varies as a function of F with maximum for F = 0.125 J/cm². In addition to the modification of their constitution, the irradiated areas present a strongly modified microstructure with appearance of nanoscale features. The physico-chemical mechanisms of these structural modifications are discussed based on the theory of nucleation.     

Annealing temperature effect on the properties of mercury-doped TiO2 films prepared by sol-gel dip-coating technique

This work presents the annealing temperature effect on the properties of mercury (Hg)-doped titanium dioxide (TiO₂). Thin films and polycrystalline powders have been prepared by sol-gel process. The structure, surface morphology and optical properties, as a function of the annealing temperature, have been studied by atomic force microscopy (AFM), Raman, reflectance and ellipsometric spectroscopies. In order to determine the transformation points, we have analyzed the xerogel-obtained powder by differential scanning calorimetry (DSC). Raman spectroscopy shows the crystalline anatase and rutile phases for the films annealed at 400 °C and 1000 °C respectively. The AFM surface morphology results indicate that the particle size increases from 14 to 57 nm by increasing the annealing temperature. The complex index and the optical band gap (E_g) of the films were determined by the spectroscopic ellipsometry analysis. We have found that the optical band gap decreases by increasing the annealing temperature.     

Optical and hydrophilic properties of Cr doped TiO2-SiO2 nanostructure thin film

Cr doped TiO₂-SiO₂ nanostructure thin film on glass substrates was prepared by a sol-gel dip coating process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structural and chemical properties of the films. A UV-vis spectrophotometer was used to measure the transmittance spectra of the thin film. The hydrophilicity of the thin film during irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicated that Cr doping has a significant effect on the transmittance and super-hydrophilicity of TiO₂-SiO₂ thin film.     

Influence of annealing process on conductive properties of Nb-doped TiO2 polycrystalline films prepared by sol-gel method

Nb-doped TiO₂ (TNO) thin films were prepared by sol-gel dip-coating method with Nb content in a wide range of 0-20 at.%. The prepared films were preheated at 400 °C and then undertaken by two different post-annealing processes: (a) three times vacuum annealing and (b) multi-round annealing. The designed multi-round annealing was shown to be an effective way to improve the conductive properties of the films, compared to the traditional vacuum annealing process. The minimum resistivity reached approximately 0.5 Ω cm with Nb doping concentration around 12 at.%, and the carrier density increased with Nb-doping concentration until the critical point of 12 at.%, which might be the optimal doping content for our TNO films prepared by sol-gel method.     

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.     

Microstructures and magnetic properties of CoPt-TiO2 nanocomposite films prepared by annealing CoPt/TiO2 multilayers

CoPt-TiO₂ nanocomposite films were synthesized by rapid thermal annealing of CoPt/TiO₂ multilayers. The effects of annealing temperature, annealing time, Ag addition and TiO₂ volume fraction on the microstructures and magnetic properties of the CoPt-TiO₂ nanocomposite films were studied. Results showed that the ordering degree of CoPt and coercivity of CoPt-TiO₂ nanocomposites increased with annealing temperature. Increasing annealing time and Ag addition were able to increase the ordering degree and coercivity of CoPt. However, complete L1₀-ordering of CoPt at 550 °C annealing was not realized by increasing annealing time up to 30 min and Ag addition up to 30 vol.%. Increasing TiO₂ volume fraction at 700 °C annealing did not lead to the change of ordering of CoPt. However, the grain structure of the films changed slightly when TiO₂ volume fraction was larger than 56%. The coercivity of the film decreased slightly with the addition of TiO₂.     

Structural, optical and electrochemical properties of TiO2 thin films grown by APCVD method

Atmospheric pressure chemical vapor deposition (APCVD) of TiO₂ thin films has been achieved onto glass and onto ITO-coated glass substrates, from the reaction of TiCl₄ with ethyl acetate (EtOAc). The effect of the synthesis temperature on the optical, structural and electrochemical properties was studied through spectral transmittance, X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS) measurements. It was established that the TiO₂ films deposited onto glass substrate, at temperatures greater than 400 °C grown with rutile type tetragonal structure, whereas the TiO₂ films deposited onto ITO-coated glass substrate grown with anatase type structure. EIS was applied as suitable method to determine the charge transfer resistance in the electrolyte/TiO₂ interface, typically found in dye-sensitized solar cells.     

Substrate effects on the oxygen gas sensing properties of SnO2/TiO2 thin films

In this study, SnO₂/TiO₂ thin films are fabricated on SiO₂/Si and Corning glass 1737 substrates using a R.F. magnetron sputtering process. The gas sensing properties of these films under an oxygen atmosphere with and without UV irradiation are carefully examined. The surface structure, morphology, optical transmission characteristics, and chemical compositions of the films are analyzed by atomic force microscopy, scanning electron microscopy and PL spectrometry. It is found that the oxygen sensitivity of the films deposited on Corning glass 1737 substrates is significantly lower than that of the films grown on SiO₂/Si substrates. Therefore, the results suggest that SiO₂/Si is an appropriate substrate material for oxygen gas sensors fabricated using thin SnO₂/TiO₂ films.     

Morphology and natural wettability properties of sol-gel derived TiO2-SiO2 composite thin films

Previous studies suggest that granular interfaces induce a natural and persistent super-hydrophilicity in TiO₂-SiO₂ composite thin films deposited by sol-gel route. This effect enables to consider self-cleaning applications that do not require a permanent UV exposure, whereas such a permanent exposure is necessary for pure TiO₂ films. In this study, TiO₂-SiO₂ composite thin films have been deposited from a TiO₂ anatase crystalline suspension and different SiO₂ polymeric sols. Wettability studies show that a suitable control of the TiO₂-SiO₂ mixed sol formulations noticeably enhances persistence of the natural super-hydrophilicity in composite films. It is shown that, beside granular interface effects, modifications in the composite film morphologies can noticeably influence wettability properties.     

The structure and photocatalytic activity of TiO2 thin films deposited by dc magnetron sputtering

This paper seeks to determine the optimal settings for the deposition parameters, for TiO₂ thin film, prepared on non-alkali glass substrates, by direct current (dc) sputtering, using a ceramic TiO₂ target in an argon gas environment. An orthogonal array, the signal-to-noise ratio and analysis of variance are used to analyze the effect of the deposition parameters. Using the Taguchi method for design of a robust experiment, the interactions between factors are also investigated. The main deposition parameters, such as dc power (W), sputtering pressure (Pa), substrate temperature (°C) and deposition time (min), were optimized, with reference to the structure and photocatalytic characteristics of TiO₂. The results of this study show that substrate temperature and deposition time have the most significant effect on photocatalytic performance. For the optimal combination of deposition parameters, the (1 1 0) and (2 0 0) peaks of the rutile structure and the (2 0 0) peak of the anatase structure were observed, at 2θ ∼ 27.4°, 39.2° and 48°, respectively. The experimental results illustrate that the Taguchi method allowed a suitable solution to the problem, with the minimum number of trials, compared to a full factorial design. The adhesion of the coatings was also measured and evaluated, via a scratch test. Superior wear behavior was observed, for the TiO₂ film, because of the increased strength of the interface of micro-blasted tools.     

Structural, morphological and optical properties of CuAlS2 films deposited by spray pyrolysis method

The structural, morphological and optical properties of CuAlS₂ films deposited by spray pyrolysis method have been investigated. CuAlS₂ in the form of films is prepared at different deposition conditions by a simple and economical spray pyrolysis method. The structural, surface morphology and optical properties of the films were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM) and absorbance spectra, respectively. The films were polycrystalline, crystallized in a tetragonal structure, and are preferentially orientated along the (1 1 2) direction. Grain size values, dislocation density, and d% error of CuAlS₂ films were calculated. The optical band gap of the CuAlS₂ film was found to be 3.45 eV. The optical constants such as refractive index, extinction coefficient and dielectric constants of the CuAlS₂ film were determined. The refractive index dispersion curve of the film obeys the single oscillator model. Optical dispersion parameters E_o and E_d developed by Wemple-DiDomenico were calculated and found to be 3.562 and 12.590 eV.     

Effect of spin polarization on the optical properties of Co-doped TiO2 thin films

A non-linear variation of bandgap energy with Co doping is observed in sputter deposited Co-doped TiO₂ thin films. This peculiar behavior is explained on the basis of mechanical stress in the films together with spin polarization due to s,p-d exchange interaction between the localized Co 3d electrons and delocalized electrons. Quantitative analyses of mechanical stress and grain boundary barrier potential due to spin polarization are performed from the below bandgap absorption tail. Furthermore, anomalous variations in both the refractive indices and extinction coefficients with Co doping are noted and are explained on the basis of ab-initio calculations based on density functional theory.