Structural, optical and electrical characterization of spray-deposited TiO2 thin films

Titanium oxide (TiO₂) thin films were deposited onto glass substrates by means of spray pyrolysis method using methanolic titanyl acetyl acetonate as precursor solution. The thin films were deposited at three different temperatures namely 350, 400 and 450 °C. As-deposited thin films were amorphous having 100–300 nm thickness. The thin films were subsequently annealed at 500 °C in air for 2 h. Structural, optical and electrical properties of TiO₂ thin films have been studied. Polycrystalline thin films with rutile crystal structure, as evidenced from X-ray diffraction pattern, were obtained with major reflexion along (1 1 0). Surface morphology and growth stages based on atomic force microscopy measurements are discussed. Electrical properties have been studied by means of electrical resistivity and thermoelectric power measurements. Optical study shows that TiO₂ possesses direct optical transition with band gap of 3.4 eV.     

Templated synthesis of ordered porous TiO2 films and their application in dye-sensitized solar cell

Ordered porous TiO₂ thin films were fabricated on conductive glass by using colloid crystal template of polystyrene (PS) spheres. Microstructural characterization by scanning electron microscopy techniques was carried out to explore the porous structural changes due to the PS templates which could be controlled by adjusting the drawing rate. Photovoltaic performance was measured and this revealed the effect of microstructural changes. The results showed that monolayer porous TiO₂ films and multilayer porous TiO₂ films could be successfully prepared. And multilayer porous TiO₂ films provided large surface area for dye absorption to increase the efficiency of dye-sensitized solar cells (DSSCs) which were assembled by porous TiO₂ films.     

Influence of Nb dopant on the structural and optical properties of nanocrystalline TiO2 thin films

In this study, preparation of Nb-doped (0-20 mol% Nb) TiO₂ dip-coated thin films on glazed porcelain substrates via sol-gel process has been investigated. The effects of Nb on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Surface topography and surface chemical state of thin films was examined by atomic force microscope and X-ray photoelectron spectroscopy. XRD and Raman study showed that the Nb doping inhibited the grain growth. The photo-catalytic activity of the film was tested on degradation of methylene blue. Best photo-catalytic activity of Nb-doped TiO₂ thin films were measured in the TiO₂-1 mol% Nb sample. The average optical transmittance of about 47% in the visible range and the band gap of films became wider with increasing Nb doping concentration. The Nb⁵⁺ dopant presented substitutional Ti⁴⁺ into TiO₂ lattice.     

Spray deposition and property analysis of anatase phase titania (TiO2) nanostructures

Anatase phase titanium dioxide thin films have been deposited at various substrate temperatures by chemical spray pyrolysis of an aerosol of titanyl acetylacetonate. Deposited TiO₂ films were nanocrystalline and preferentially oriented along [101] direction, uniform and adherent to the glass substrate. Best films processed at 450 °C were characterized to analyze its phase composition, texture, roughness, optical and electrical properties. X-ray photoelectron spectroscopy revealed that the surface of the film has only the Ti⁴⁺ cations to form perfect TiO₂ stoichiometry with less amount of hydration. Atomic force microscopy image demonstrated the existence of homogeneous and rough surface, suitable for electrocatalytic applications. The film has an optical transmittance more than 90% and the refractive index of 2.07 was recorded at the wavelength 633 nm. Due to nano-sized grains, obtained optical band gap (3.65 eV) of the TiO₂ thin film was larger than that of the bulk TiO₂ (3.2 eV). Calculated porosity of the films 0.44, revealed the porous nature of the films. Hall measurements indicated that these materials are p-type and yield a carrier density of the order 8.8 × 10²⁰ cm⁻³ and a carrier mobility of 0.48 × 10⁻⁶ cm²/Vs. The dc electrical conductivity was therefore very low (8.91 × 10⁻⁶ S/cm) because of lower value of mean free path of the charge carriers (4.36 × 10⁻¹¹ cm). It gives an impression that the process of spray pyrolysis provides an easy way to tailor make thin films possessing superior properties.     

Directional enhancement of refractive index and tunable wettability of polymeric coatings due to preferential dispersion of colloidal TiO2 nanorods towards their surface

We demonstrate the fabrication of nanocomposite coatings, of organic-capped colloidal TiO₂ nanorods dispersed into a poly(methyl methacrylate) matrix, with rising value of refractive index from the bottom to the top layers, and UV-induced surface wettability alteration, in a reversible manner. This behaviour is attributable to preferential dispersion of the TiO₂ nanoparticles towards the superficial layers of the coatings. Above a critical TiO₂ loading, the nanorods at the surface form aggregates deteriorating the optical and the surface properties of the nanocomposites. The optimal conditions for nanocomposite films preparation in terms of optimized nanorods dispersion, optical clarity, and surface smoothness are determined.     

Broad band optical characterization of sol-gel TiO2 thin film microstructure evolution with temperature

Titanium dioxide (TiO₂) thin films have been produced by spin coating a titanium isopropoxide sol on silicon wafer substrates. The structural evolution of the thin films in terms of decomposition, crystallization and densification has been monitored as a function of annealing temperature from 100 to 700 °C using optical characterization and other techniques. The effect of annealing temperature on the refractive index and extinction coefficient of these TiO₂ thin films was studied in the range of 0.62 to 4.96 eV photon energy (250-2000 nm wavelength) using spectroscopic ellipsometry. Thermal gravimetric analysis and atomic force microscopy support the ellipsometry data and provide information about structural transformations in the titania thin films with respect to different annealing temperatures. These data help construct a coherent picture of the decomposition of the sol-gel precursors and the creation of dense layers of TiO₂. It was observed that the refractive index increased from 2.02 to 2.45 at 2.48 eV (500 nm) in sol-gel spin coated titania films for annealing temperatures from 100 °C to 700 °C.     

SiO2 and Al2O3/SiO2 coatings for increasing emissivity of Cu(In, Ga)Se2 thin-film solar cells for space applications

In this study, optical coatings were investigated as substitutes for the coverglass on flexible thin-film space solar cells. The inherent low emissivity of copper-indium-gallium-diselenide (CIGS) thin-film solar cells was increased using optical coatings for thermal balance in space. Evaporated silicon dioxide (SiO₂) and an additional aluminum oxide (Al₂O₃) coating on the CIGS solar cell increased the emissivity from 0.18 to 0.77. Higher emissivity was realized with the Al₂O₃/SiO₂ double-layer coating than with the SiO₂ single-layer coating. The straightforward double-layer coating gives the CIGS solar cells appropriate radiative properties for keeping the cell within a permissible temperature range in space.     

Densification of amorphous sol-gel TiO2 films: An X-ray reflectometry study

Sol-gel TiO₂ thin films were dip coated on soda lime glass substrate using tetraisopropoxide as titania precursor. Four withdrawal speeds were tested and the resulting dried thin films have been annealed at 400 °C, 450 °C and 500 °C for 1 h. Glancing Incidence X-ray Diffraction has revealed the amorphous nature of the thin films whatever is the annealing temperature. In order to study the thin films densification, X-ray Reflectometry curves have been fitted by a three layers Parrat model and by the Distorded Wave Born Approximation (DWBA) box model which provides more details on the Electron Density Profile. The presence of high density layers localized at the film surface and at the substrate-film interface has been evidenced for the annealed films. The DWBA fitting method allows us to point out a density gradient, probably arising from the initial packing density and to the constraint due to the substrate, along the film thickness.     

Enhancement of the Photoelectric Performance of Dye-sensitized Solar Cells by Sol-gel Modified TiO2 Films

Modified TiO2 films have been prepared by combining commercial titania powders (Degussa P25) with sol-gel made by titanium chloride (Ti-sol). The result shows that clusters are formed by nanoparticles and large pores can be seen on the surface of the TiO2 films. The short circuit photocurrent density and photoelectric conversion efficiency of the solar cells are obviously enhanced compared with those without modification. The relationship between the photoelectric conversion efficiency and the amount of Ti-sol was investigated. With the addition of 30 wt% Ti-sol, the photoelectric conversion efficiency as high as 9.75% is achieved, increasing by 28.3% compared with the solar cells without modification.     

Anodic TiO2 from stirred Na2SO4/NaF electrolytes: Effect of applied voltage and stirring

TiO₂ was anodically formed on titanium from electrolyte containing 1M Na₂SO₄ and 0.5 wt.% NaF. Oxidation was carried out for 1 h at potentiostatic 20, 30 and 40 V from unstirred as well as stirred baths. At 20 V amorphous and nanotubular oxide is produced irrespective of the stirring conditions. Stirring increased the tubular length compared to the unstirred condition at 20 V. Oxidations at 30 and 40 V produced flat, crystalline anatase under both the bath conditions. A nanotubular network may be formed in the first 5 min and then anodic oxidation may occur laterally, perpendicular to the long-axis of the nanotubes.     

Thermal properties of TiO2 films grown by atomic layer deposition

We study the thermal properties of amorphous TiO₂ thin films of various thicknesses t, grown by atomic layer deposition. The thermo-optic coefficient dn/dT and the temperature coefficient dρ/dT of film density ρ are determined from ellipsometric data in wavelength range 380 < λ < 1800 nm with the Cauchy model and the Lorentz-Lorenz relation. It is found that dn/dT exhibits negative values for films with t < 150 nm and positive values for thicker films, while no significant changes in the two coefficients take place if t < 200 nm. A qualitative physical explanation based on porosity of the thin films is suggested. Films with t = 60 nm are illustrated in detail at λ = 640 nm: the room-temperature values of the coefficients are found to be dn/dT = − 3.1 × 10^− 5 °C^− 1 and dρ/dT = − 4.8 × 10^− 5g cm^− 3° C^− 1.     

Optical studies of ZSM-5 crystals infiltrated with TiO2

ZSM-5 crystals, of which granule size is about 120 µm along c axis, are employed as a good host material for TiO₂ loading. Optical microscopy photographs, X-ray powder diffraction spectra and surface area calculated from nitrogen adsorption data at − 196 °C have been carried out and show that the titanium dioxide clusters are infiltrating into the pores of ZSM-5. TiO₂/ZSM-5 host-guest material, regardless of whether being prepared by microwave and water bath heating, shows similar features except for the TiO₂ contents. The materials have a photoluminescence emission peak at 2.85 eV, which is ascribed to the band edge emission. A red shift was observed on the photoluminescence emission spectra when NH₃ adsorbed into the pores of TiO₂/ZSM-5 material.     

Optical and structural properties of nanocrystalline anatase (TiO2) thin films prepared by non-aqueous sol-gel dip-coating

Anatase (TiO₂) thin films were grown by non-aqueous sol-gel dip-coating using titanium (IV) n-butoxide as precursor and 1-butanol as solvent. High withdrawal speed of 4.7 mm/s in dip-coating resulted in defect free films of 100 nm average film thickness after subsequent heat treatments. According to scanning electron microscope and X-ray diffraction measurements, the films consisted of nanocrystalline anatase with 30 nm mean crystallite size. Refractive index n(λ) and extinction coefficient k(λ) were determined over the wavelength range from 200 to 1650 nm. The optical band gap of the film material was approximately 3.2 eV. The results showed very similar optical characteristics to those that are accomplished with chemically more reactive aqueous sol-gel processes. Furthermore, it was found that in addition to porosity, coordination number of Ti atoms to nearest oxygen neighbors is likely to have a significant role in explaining differences of optical properties between bulk anatase and thin film materials of the present work.     

Microstructure and optical properties of photoactive TiO2:N thin films

In this work, we have chosen oxidation of TiN thin films as a feasible method for preparation of nitrogen-doped titanium dioxide thin films, TiO₂:N, for photocatalytic applications. DC reactive magnetron sputtering with the plasma emission control was used for deposition of stoichiometric TiN thin films. The microstructure and chemical composition of films before and after oxidation were investigated by means of RBS, X-ray diffraction (XRD) in grazing incidence diffraction (GID) configuration, AFM and XPS techniques. The electrical conductivity was measured by the van der Pauw method as a function of the oxidation temperature. The optical transmittance and reflectance spectra of the films were measured over the visible and UV ranges of the light spectrum. GID diffraction patterns of as-sputtered TiN thin films and those after oxidation indicate that TiO₂ rutile is formed at around 300 °C. Nitrogen is still present as indicated by XPS studies even when XRD detects the rutile only. Optical absorption of thin films oxidized at 450 °C is shifted towards the visible range of the light spectrum.     

Radiation-induced luminescence from TiO2 by 10 keV O, N and Ar ion irradiation

Radiation-induced luminescence (RIL) produced by 10 keV O⁺, N⁺ and Ar⁺ irradiation at room temperature has been used to study energy transfer in titanium dioxide (TiO₂) targets. RIL spectra in the UV-visible region show numerous atomic lines and three bands. Two visible bands by crystalline defects and an UV band at 3.9 eV originating from radiation transitions between the Ti³⁺ 3d and O²⁻ 2 s states in the TiO₂ crystal are observed. The experimental results suggest that the excitations were not mainly produced by transitions from the ground state to excited states but by cascade radiations from higher excited states.     

VO2 thin films deposited on silicon substrates from V2O5 target: Limits in optical switching properties and modeling

Thermochromic VO₂ thin films presenting a phase change at T_c = 68 °C and having variable thickness were deposited on silicon substrates (Si-001) by radio-frequency sputtering. These thin films were obtained from optimized reduction of low cost V₂O₅ targets. Depending on deposition conditions, a non-thermochromic metastable VO₂ phase might also be obtained. The thermochromic thin films were characterized by X-ray diffraction, atomic force microscopy, ellipsometry techniques, Fourier transform infrared spectrometry and optical emissivity analyses. In the wavelength range 0.3 to 25 μm, the optical transmittance of the thermochromic films exhibited a large variation between 25 and 100 °C due to the phase transition at T_c: the contrast in transmittance (difference between the transmittance values to 25 °C and 100 °C) first increased with film thickness, then reached a maximum value. A model taking into account the optical properties of both types of VO₂ film fully justified such a maximum value. The n and k optical indexes were calculated from transmittance and reflectance spectra. A significant contrast in emissivity due to the phase transition was also observed between 25 and 100 °C.     

TiO2 coated SnO2 nanosheet films for dye-sensitized solar cells

TiO₂-coated SnO₂ nanosheet (TiO₂-SnO₂ NS) films about 300 nm in thickness were fabricated on fluorine-doped tin oxide glass by a two-step process with facile solution-grown approach and subsequent hydrolysis of TiCl₄ aqueous solution. The as-prepared TiO₂-SnO₂ NSs were characterized by scanning electron microscopy and X-ray diffraction. The performances of the dye-sensitized solar cells (DSCs) with TiO₂-SnO₂ NSs were analyzed by current-voltage measurements and electrochemical impedance spectroscopy. Experimental results show that the introduction of TiO₂-SnO₂ NSs can provide an efficient electron transition channel along the SnO₂ nanosheets, increase the short current density, and finally improve the conversion efficiency for the DSCs from 4.52 to 5.71%.     

Characterization of thin TiO2 films prepared by plasma enhanced chemical vapour deposition for optical and photocatalytic applications

Thin titanium oxide films were deposited using a radio frequency (RF) plasma enhanced chemical vapour deposition method. Their optical properties and thickness were determined by means of ultraviolet-visible absorption spectrophotometry. Films of the optical parameters very close to those of titanium dioxide have been obtained at the high RF power input. Their optical quality is high enough to allow for their use in a construction of stack interference optical filters. At the same time, these materials exhibit strong photocatalytic effects. The results of structural analysis, carried out by Raman Shift Spectroscopy, show that the coatings posses amorphous structure. However, Raman spectra of the same films subjected to thermal annealing at 450 °C disclose an appearance of a crystalline form, namely that of anatase. Surface morphology of the films has also been characterized by Atomic Force Microscopy revealing granular, broccoli-like topography of the films.     

Engineering of luminescence from Gd2O3:Eu nanophosphors by pulsed laser deposition

Nanostructured Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The dependence of structural, morphological and optical properties of these films on photoluminescence was systematically studied by varying the annealing temperature, Eu³⁺ incorporation concentration and laser fluence. The intensity of the XRD peak from (2 2 2) crystal plane was found to increase with annealing temperature in the range 973–1173 K. Films annealed at 1173 K show a preferential growth along (2 2 2) crystal plane of the cubic Gd₂O₃ and enhanced photoluminescence at 612 nm. XRD and Micro-Raman spectra and lattice strain investigations suggest that Eu³⁺ incorporation introduce a strong lattice distortion in Gd₂O₃ matrix. Morphological investigations using atomic force microscopy indicate a strong influence of the annealing process on the surface roughness and particle size. This kind of transparent thin film phosphors may promise for applications in flat-panel displays and X-ray imaging systems.     

The effect of Li intercalation on different sized TiO2 nanoparticles and the performance of dye-sensitized solar cells

The effect of Li⁺ insertion into different sized TiO₂ nanoparticles and their influences on the photoconversion efficiency of dye-sensitized solar cells (DSSC) were investigated. TiO₂ nanoparticles with different particle sizes (22 nm, 14 nm and 6 nm) doped with Li⁺ were employed to form thin film electrodes and their properties were characterized by X-ray diffraction (XRD) and electrochemical impedance spectroscopy analysis. XRD evidenced the presence of anatase as the main phase. From the XRD analysis, it was observed that the Li⁺ ions could be inserted into both the surface and bulk of the TiO₂ nanoparticles. In the larger particle size, the Li⁺ ions are inserted into the bulk anatase where as Li⁺ ions bounded on the TiO₂ surface for the smaller crystallite size. The photovoltaic properties were measured by a current-voltage meter under AM1.5 simulated light radiation. It exhibited that the overall photoconversion efficiency of DSSC was decreased in the larger particles while it was enhanced in the smaller nanoparticles when Li⁺ was doped into the TiO₂ nanoparticles. A nearly 40% decrease in the efficiency (η) of DSSC was observed upon intercalation of Li⁺ ions into 22 nm sized TiO₂ nanoparticles (P25). The 14 nm sized TiO₂ nanoparticles (P90) showed slightly less efficiency (η) upon Li⁺ doping than that of the undoped sample. However, the smallest sized TiO₂ nanoparticles (6 nm) showed higher efficiency than that of the undoped one. This phenomenon is explained based on electron trapping and charge recombination due to lithium doping.