PLD of Fe3O4 thin films: Influence of background gas on surface morphology and magnetic properties

Ablation of Fe₃O₄ targets has been performed using a pulsed UV laser (KrF, λ = 248 nm, 30 ns pulse duration) onto Si(100) substrates, in reactive atmospheres of O₂ and/or Ar, with different oxygen partial pressures. The as-deposited films were characterised by atomic force microscopy (AFM), X-ray diffraction (XRD), conversion electron Mössbauer spectroscopy (CEMS) and extraction magnetometry, in order to optimise the deposition conditions in the low temperature range. The results show that a background mixture of oxygen and argon improves the Fe:O ratio in the films as long as the oxygen partial pressure is maintained in the 10⁻² Pa range. Thin films of almost stoichiometric single phase polycrystalline magnetite, Fe_2.99O₄, have been obtained at 483 K and working pressure of 7.8 × 10⁻² Pa, with a high-field magnetization of ∼490 emu/cm³ and Verwey transition temperature of 112 K, close to the values reported in the literature for bulk magnetite.     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Microstructural, optical and spectroscopic studies of laser ablated nanostructured tantalum oxide thin films

Thin films of tantalum oxide (Ta₂O₅) have been prepared by pulsed laser deposition technique at different substrate temperatures (300-973 K) under vacuum and under oxygen background (pO₂ = 2 × 10⁻³ mbar) conditions. The films are annealed at a temperature of 1173 K. The as-deposited films are amorphous irrespective of the substrate temperature. XRD patterns show that on annealing, the films get crystallized in orthorhombic phase of tantalum pentoxide (β-Ta₂O₅). The annealed films deposited at substrate temperatures 300 K and 673 K have a preferred orientation along (0 0 1) plane, whereas the films deposited at substrate temperatures above 673 K show a preferred orientation along (2 0 0) crystal plane. The deposited films are characterized using techniques such as grazing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), micro-Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and UV-visible spectroscopy. FTIR and micro-Raman measurements confirm the presence of Ta-O, Ta-O-Ta and O-Ta-O bands in the films. Grain size calculations from X-ray diffraction and AFM show a decrease with increase in substrate temperature. The variation of transmittance and band gap with film growth parameters are also discussed.     

Structural investigations of TiO2:Tb thin films by X-ray diffraction and atomic force microscopy

In this work, structural investigations of TiO₂ thin films doped with Tb at the amount of 0.4, 2 and 2.6 at.% have been outlined. Thin films were deposited on Si and SiO₂ substrates by high energy reactive magnetron sputtering from mosaic Ti-Tb target. The influence of Tb dopant amount, post-annealing treatment and kind of applied substrate on microstructure has been discussed. Thin films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM). XRD analysis revealed the existence of crystalline TiO₂ in anatase and rutile forms, depending on Tb amount in examined samples. AFM images show that as-deposited samples with 0.4 at.% concentration of terbium (anatase structure) have bigger crystallites as compared to 2% and 2.6 at.% of Tb (rutile structure). The additional annealing at 1070 K results in a mixed anatase (77%) and rutile (23%) structure.     

Photocatalytic property of TiO2 thin films sputtered-deposited on unheated substrates

TiO₂ films deposited on unheated substrates of alumina silicate glass by rf. (13.56 MHz) magnetron sputtering in the mixture of O₂ and Ar gases have been studied with X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and optical spectroscopy. Structural and optical properties of TiO₂ films deposited at different O₂ concentrations and total pressures have been analyzed. Photocatalytic properties of TiO₂ films were characterized by following the degradation of methylene blue molecules under UV irradiation. It was found that the rate of methylene blue decomposition strongly depends on morphology and crystallinity of the deposited films, namely on the content of the anatase phase and on the size of the anatase grains. The best photocatalytic activity was found on TiO₂ films consisting of pure anatase phase with the size of grains of about 450 Å. With the help of those films a thin film reactor for water purification has been designed and tested.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

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.     

Ferromagnetism at 300 K in spin-coated films of Co doped anatase and rutile-TiO2

Thin films of Ti_1−xCo_xO₂ (x=0 and 0.03) have been prepared on sapphire substrates by spin-on technique starting from metalorganic precursors. When heat treated in air at 550 and 700 °C, respectively, these films present pure anatase and rutile structures as shown both by X-ray diffraction and Raman spectroscopy. Optical absorption indicate a high degree of transparency in the visible region. Such films show a very small magnetic moment at 300 K. However, when the anatase and the rutile films are annealed in a vacuum of 1×10⁻⁵ Torr at 500 and 600 °C, respectively, the magnetic moment, at 300 K, is strongly enhanced reaching 0.36μ_B/Co for the anatase sample and 0.68μ_B/Co for the rutile one. The ferromagnetic Curie temperature of these samples is above 350 K.     

Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.     

Au/TiO2/Ru(0 0 0 1) model catalysts and their interaction with CO

Au/TiO₂/Ru(0 0 0 1) model catalysts and their interaction with CO were investigated by scanning tunneling microscopy and different surface spectroscopies. Thin titanium oxide films were prepared by Ti deposition on Ru(0 0 0 1) in an O₂ atmosphere and subsequent annealing in O₂. By optimizing the conditions for deposition and post-treatment, smooth films were obtained either as fully oxidized TiO₂ or as partly reduced TiO_x, depending on the preparation conditions. CO adsorbed molecularly on both oxidized and reduced TiO₂, with slightly stronger bonding on the reduced films. Model catalyst surfaces were prepared by depositing submonolayer quantities of Au on the films and characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. From X-ray photoelectron spectroscopy, a weak interaction between the Au and the TiO₂ substrate was found. At 100 K CO adsorption occurred on both the TiO₂ film and on the Au nanoparticles. CO desorbed from the Au particles with activation energies between 53 and 65 kJ/mol, depending on the Au coverage. If the Au deposit was annealed to 770 K prior to CO exposure, the CO adsorption energy decreased significantly. STM measurements revealed that the Au particles grow upon annealing, but are not encapsulated by TiO_x suboxides. The higher CO adsorption energy observed for smaller Au coverages and before annealing is attributed to a significantly stronger interaction of CO with mono- and bilayer Au islands, while for higher particles, the adsorption energy becomes more bulk-like. The implications of these effects on the known particle size effects in CO oxidation over supported Au/TiO₂ catalysts are discussed.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

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.     

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO2 thin films by DC magnetron sputtering

Titanium dioxide (TiO₂) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO₂ films has been analyzed by X-ray photoelectron spectroscopy. The TiO₂ films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO₂ into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO₂/p-Si have been fabricated. The leakage current density of unbiased films was 1 × 10⁻⁶ A/cm² at a gate bias voltage of 1.5 V and it was decreased to 1.41 × 10⁻⁷ A/cm² with the increase of substrate bias voltage to −150 V owing to the increase in thickness of interfacial layer of SiO₂. Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at −150 V. The capacitance at 1 MHz for unbiased films was 2.42 × 10⁻¹⁰ F and it increased to 5.8 × 10⁻¹⁰ F in the films formed at substrate bias voltage of −150 V. Dielectric constant of TiO₂ films were calculated from capacitance–voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at −150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to −150 V.     

Structural and optoelectronic properties of antimony tin sulphide thin films deposited by thermal evaporation techniques

Thin films of SnSb₂S₄ have been prepared on glass substrate by using thermal evaporation techniques. The films were annealed in argon gas at low pressure in sealed glass ampoules at 85 °C, 150 °C, 275 °C and 325 °C. XRD of the films reveal that the low temperature annealed films are poly crystalline while the as deposited films and high annealed films are in amorphous states. There is no adequate variation in the photoconductivity response of the amorphous and crystalline phases. The transmittance of the films is low and having no transmittance below 740 nm. The band gap calculated by ellipsometry technique is in the range of 1.82–3.1 eV. The films have n-type conductivity but the film annealed at 325 °C show p-type conductivity.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

Optical properties of in situ doped and undoped titania nanocatalysts and doped titania sol-gel nanofilms

In this paper we present spectroscopic properties of doped and undoped titanium dioxide (TiO₂) as nanofilms prepared by the sol-gel process with rhodamine 6G doping and studied by photoacoustic absorption, excitation and emission spectroscopy. The absorption spectra of TiO₂ thin films doped with rhodamine 6G at very low concentration during their preparation show two absorption bands, one at 2.3 eV attributed to molecular dimmer formation, which is responsible for the fluorescence quenching of the sample and the other at 3.0 eV attributed to TiO₂ absorption, which subsequently yields a strong emission band at 600 nm. The electronic band structure and optical properties of the rutile phase of TiO₂ are calculated employing a fully relativistic, full-potential, linearized, augmented plane-wave (FPLAPW) method within the local density approximation (LDA). Comparison of this calculation with experimental data for TiO₂ films prepared for undoped sol-gels and by sputtering is performed.     

Structural properties of CuInSe2 films prepared by selenization of metallic precursors on MoNx film substrates

The aim of this work was to study the effect of MoN_x film substrates on the structural properties of CuInSe₂ films prepared by selenization of metallic Cu-In alloy precursors. MoN_x films were prepared by reactive dc-magnetron sputtering. All the CuInSe₂ films exhibit single phase chalcopyrite structure with (1 1 2) preferred orientation, which can be explained by the reduction of lattice mismatch between CuInSe₂ and MoN_x. The bulk composition of selenized CuInSe₂ films are near stoichiometric, but the surface composition analysis suggests Cu deficiency on surface area. Furthermore, ordered defect compound, CuIn₂Se_3.5 is found on the surface of CuInSe₂ films. The results will be helpful for fabricating Cd-free ZnO buffer layer CuInSe₂ and Cu(In_1−xGa_x)Se₂ based thin film solar cells.     

Structure, magnetic and optical properties of polycrystalline Co-doped TiO2 films

Co-doped TiO₂ films were fabricated under different conditions using reactive facing-target magnetron sputtering. Co doping improves the transformation of TiO₂ from anatase phase to rutile phase. The chemical valence of doped Co in the films is +2. All the films are ferromagnetic with a Curie temperature above 340 K. The average room-temperature moment per Co of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases from 0.74 μ_B at x=0.03 to 0.02 μ_B at x=0.312, and decreases from 0.54 to 0.04 μ_B as x increases from 0.026 to 0.169 for the Co-doped TiO₂ films fabricated at 0.27 Pa. The ferromagnetism originates from the oxygen vacancies created by Co²⁺ dopants at Ti⁴⁺ cations. The optical band gaps value (E_g) of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases linearly from 3.35 to 2.62 eV with the increasing x from 0 to 0.312. For the Co-doped TiO₂ films fabricated at 1.86 Pa, the E_g decreases linearly from 3.26 to 2.53 eV with increasing x from 0 to 0.350.     

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.