Internal stress and the deformation phase transition in nanoscale barium-strontium titanate films

It has been established by varying the thickness of Ba_0.8Sr_0.2TiO₃ heteroepitaxial films grown via the layer-by-layer mechanism on (100) MgO substrates that there is a critical film thickness (～50 nm): the internal strain field in the films with a thickness below critical is much weaker than in the films with a thickness exceeding critical. Tensile and compressive stresses occur at thicknesses, respectively, below and above critical. The existence of critical thickness is confirmed by the X-ray diffraction data and Raman spectroscopy.     

Hydrothermal synthesis of BaTiO3 thin films on nanoporous TiO2 covered Ti substrates

It is well known that there is an upper limit (<0.25 μm) for the thickness of hydrothermal thin films grown on Ti substrate in the 100–200 °C temperature range, even the reaction time is extended to several weeks. In this paper, BaTiO₃ thin films have been firstly hydrothermally synthesized on titanium substrates covered with a nanoporous TiO₂ layer. By using TiO₂ covered substrates, the thickness of BaTiO₃ films can easily reach ∼1.0 μm at 110 °C after only 2 h hydrothermal treatment. It is found that the large quantity of pores with size at the tens of nanometer range in the oxide layer served as easy paths for the diffusion of Ba²⁺ and OH⁻ and enabled the film grow thicker. SEM and XRD results show that the films are crack-free and in polycrystalline phase.     

Apatite formation on TiO2 anatase microspheres

Titanium dioxide (TiO₂) coatings have been long considered as biocompatible interfaces to promote the physico-chemical bonding between the bone tissues and implant material (e.g., titanium and stainless steel). Monodispersed TiO₂ (anatase, the low temperature polymorph of TiO₂) microspheres, produced in the form of colloidal precipitates, were deposited on different substrates and apatite formation was induced on the resulted surface by immersing the coated substrates in simulated body fluid solution. Analytical and microstructural investigations, conducted by X-ray diffraction, energy depressive X-ray spectroscopy and scanning electron microscopy techniques, showed considerable higher rates of apatite formation, in vitro, on the anatase microspheres compared to the sol-gel-derived thin films of the same oxide. We concluded that the particular surface morphology of the packed TiO₂ microspheres, promotes a faster apatite formation in vitro.     

Preparation and characterization of ZnO-TiO2 films obtained by sol-gel method

The sol-gel route has been applied to obtain ZnO-TiO₂ thin films. For comparison, pure TiO₂ and ZnO films are also prepared from the corresponding solutions. The films are deposited by a spin-coated method on silicon and glass substrates. Their structural and vibrational properties have been studied as a function of the annealing temperatures (400-750 °C). Pure ZnO films crystallize in a wurtzite modification at a relatively low temperature of 400 °C, whereas the mixed oxide films show predominantly amorphous structure at this temperature. XRD analysis shows that by increasing the annealing temperatures, the sol-gel Zn/Ti oxide films reveal a certain degree of crystallization and their structures are found to be mixtures of wurtzite ZnO, Zn₂TiO₄, anatase TiO₂ and amorphous fraction. The XRD analysis presumes that Zn₂TiO₄ becomes a favored phase at the highest annealing temperature of 750 °C. The obtained thin films are uniform with no visual defects. The optical properties of ZnO-TiO₂ films have been compared with those of single component films (ZnO and TiO₂). The mixed oxide films present a high transparency with a slight decrease by increasing the annealing temperature.     

Photocatalytic TiO2 films prepared by chemical vapor deposition at atmosphere pressure

Nanometer semiconductor titanium dioxide thin films have excellent properties of photocatalysitic degeneration. The glass coated TiO₂ films is called self-cleaning glass. In this paper, chemical vapor deposition (CVD) method is employed to deposit TiO₂ films on glass. The effect of spacing between nozzle and glass and the effect of substrate temperature on deposition rate are studied. The crystalline structure at different deposition temperatures is analyzed by XRD and anatase was found. And the microstructure of the TiO₂ films is also determined by SEM. It shows that the size of crystal grain increases with the temperature.     

Structural,Morphological and Electrical Studies on Barium Strontium Titanate Thin Films Prepared by Sol‐Gel Technique

The crystal structure, surface morphology, compositional homogeneity and electrical properties of barium strontium titanate (BST) thin films are investigated. The films were deposited on bare silicon and platinum coated silicon substrates by spin coating process. The precursor solution with Ba/Sr ratio 70/30 was prepared by sol‐gel synthesis using metal alkoxides. The crystalline nature and morphology of the films are found to be strongly influenced by the heating cycle adopted to form the Ba_0.7Sr_0.3TiO₃ layer. The elemental composition analysis on the surface and in‐depth confirms the stoichiometry of the films. The dielectric constant at 100 kHz and dissipation factor at room temperature is found to be 120 and 0.0236 for the films with 400nm thickness annealed at 700°C for 2 hrs. The leakage current density of the film is found to be 4x10^‐8 A/cm² from I‐V measurements.     

Studies on a possible growth mechanism of silver nanoparticles loaded on TiO2 thin films by photoinduced deposition method

The TiO₂ thin films loaded with silver nanoparticles were prepared on soda-lime glass substrates by a photoinduced deposition method. The TiO₂ films immersed in AgNO₃ solution were vertically irradiated by UV light with center wavelength of 365 nm for 60 h. The as-produced films were characterized by X-ray diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The studies show that the film after UV excitation is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. A possible growth mechanism of silver nanoparticles on TiO₂ thin films under UV irradiation was proposed. The charge carriers of TiO₂ semiconductor are generated by photoexcitation. Owing to the conduction band position of TiO₂ which is above the standard potential of Ag⁺/Ag, the generated electrons could transfer from the conduction band to Ag⁺ adsorbed on the surface of the TiO₂ films. Therefore, the Ag⁺ was finally reduced into a Ag atom, which could preferentially localize in the grain boundaries of TiO₂ particles due to high surface free energy there. With the irradiation time extended, silver nanoparticles were shaped into certain morphologies on the surface of the TiO₂ films.     

Optical constants of DC magnetron sputtered titanium dioxide thin films measured by spectroscopic ellipsometry

Optical constants of DC magnetron sputtered TiO₂ thin film have been determined by Spectroscopic Ellipsometry in the photon energy range 1.2 to 5.5 eV at room temperature. The measured dielectric‐function spectra reveal distinct structures at energies of the E1, E1 + Δ1 and E2 critical points are due to interband transitions. The root mean square roughness of the magnetron sputtered TiO₂ thin films evaluated by ex‐situ atomic force microscopy is 5.8 nm. The Dielectric constant values were found to be substantially lower than those for the bulk TiO₂. The dielectric related Optical constants, such as the refractive index, extinction coefficient, absorption coefficient and normal incidence of reflectivity determined from the spectroscopic ellipsometry data are presented and analyzed. The optical constants of the films were also determined using the optical transmittance measurements and the results were discussed. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The microstructure and magnetic property of TiO2‐terminated SrTiO3 substrate selected growth cubic phase CaRuO3 film

CaRuO₃ thin films with various thicknesses were synthesized by pulsed laser deposition respectively on SrTiO₃ substrates with SrO‐ and TiO₂‐termination. The microstructure of these films was studied by transmission electron microscopy. The results demonstrate that the CaRuO₃ thin films grown on TiO₂‐terminated substrates show quite uniform morphology, whilst they do the facet morphology when the substrates are SrO‐terminated. In addition, there is a 5∼7 unit‐cell‐thickness cubic CaRuO₃ layer in the films grown on TiO₂‐terminated substrates. The measured ferromagnetic hysteresis loop is attributed to the cubic CaRuO₃ layer, which is supported by a first‐principles calculations. On the contrary, there is free of cubic CaRuO₃ layer in samples grown on SrO‐terminated substrates. The crystallographic domains, the orientation relationship between domains and substrates and crystal defects in these films were studied as well. The different growth mechanism of CaRuO₃ on SrO‐ and TiO₂‐terminated SrTiO₃ substrates may be correlated with the selective nucleation and growth.     

Synthesis of nanosized TiO2 powder by sol gel method at low temperature

ABSTRACT

Nanotechnology is all about making products from very small constituents, components or subsystems to gain greatly enhanced material properties and functionality. Nanocrystalline anatase TiO₂ was prepared by a facile sol–gel route at a temperature of 50°C under mild conditions. Titanium tetraisopropoxide (TTIP) was used as a titanium precursor, and 2-propanol was used as a solvent. XRD, TEM, SEM, FT-IR and BET were applied to characterize the crystal phase. The Crystalline size of TiO₂ powder has been obtained with diameter < 30 nm for anatase at 500°C using an acid.     

Photocatalytic properties of TiO2/ZnO thin film

ABSTRACT

TiO₂, ZnO and ZnO/TiO₂ thin films have been prepared by radio frequency magnetron sputtering method under different temperatures. Their photo catalytic activities have been investigated. The structural of the thin films were characterized by X-ray diffraction and Raman spectroscopy. The photo catalytic activities of TiO₂ and ZnO/TiO₂ samples were evaluated by the photo decomposition of methylene blue. We note that the structural proprieties of the thin films showed a perfect crystallization along the (002) for ZnO, Rutile (110) for TiO₂ and Anatase (101) for TiO₂. The experimental results show that the bilayer ZnO/TiO₂ were the most efficient photo catalysts compared to the layer of TiO₂. This increased catalytic effect can attributed to the interface between the ZnO layer and the TiO₂ one, which modify significantly the chemical potential of the bilayer.     

Electrical properties of TiO2 thin films

The electrical properties of n-type titanium dioxide thin films deposited by magnetron-sputtering method have been investigated by temperature-dependent conductivity. We observed that the temperature dependence of the electrical conductivity of titanium dioxide films exhibits a crossover from T^?1/4 to T^?1/2 dependence in the temperature range between 80 and 110 K. Characteristic parameters describing conductivity, such as the characteristic temperature (T₀), hopping distance (R_hop), average hopping energy (Δ_hop), Coulomb gap (Δ_C), localization length (ξ) and density of states (N(E_F)), were determined, and their values were discussed within the models describing conductivity in TiO₂ thin films.     

Surface enhanced Raman scattering in an amorphous matrix for Raman amplification

In order to improve the efficiency of Raman Amplifiers, the Surface Enhanced Raman Scattering (SERS) effect of an amorphous matrix of TiO₂ was studied. First, optimisation of the amorphous layer quality was performed by depositing thin films on glass substrates at different temperatures. Then, thin films of amorphous TiO₂ were deposited on silicon commercial gold SERS substrates (Klarite®) by a dip-coating process. The SERS effect was demonstrated by the great difference of Raman intensities of the amorphous TiO₂ matrix dip-coated on active and inactive parts of Klarite® substrate under 633 nm and 780 nm laser excitations in the tail of the Surface Plasmon Resonance band of gold nanoparticles.     

TiO2 thin films as sensing gas materials

TiO₂ thin films were prepared by DC reactive magnetron sputtering on heated Si, quartz and glass substrates using O₂ and water vapor as reactive gases. The percentage of anatase and rutile as well as the grain size strongly depend on the deposition conditions, as revealed by X-ray diffraction patterns. The films deposited on Si substrates are pure rutile, while a mixed anatase/rutile structure occurs in the films deposited on glass and quartz substrates. Smaller grain rutile and anatase films were prepared in a water vapor atmosphere, in contrast to the films grown in oxygen. The former choice considerably increases the sensing properties of titanium dioxide films. The gas sensitivity was investigated for some reducing gases (methane, acetone, ethanol and liquefied petroleum gas) and the optimum operating temperatures were found.     

Fabrication of two-dimensional lattices by using photosensitive sol-gel and four-beam laser interference

This work demonstrates a promising method to fabricate 2D lattices by using photosensitive sol-gel method combining with four-beam of a 350.7 nm Kr ion laser interference. Photosensitive TiO₂ gel films with chelate complexes as precursors are fabricated. The characteristics of UV and IR spectra of the films and their variations in the process of laser irradiation are investigated. The results show that the gel films had an absorption peak at about 358 nm due to the formation of chelate complex. This peak gradually decreases with irradiation in time, which indicates the photosensitive properties of the TiO₂ films. A flexible four-beam interference system is proposed. Given incident angles 20.5° and 44.5°, the lattices with pitch of 700 nm and 326 nm are fabricated, respectively. The diffraction phenomenon of the 700 nm lattices is investigated by inverse method. The results are fully consistent with the 2D crystal diffraction theory.     

Development of multifunctional photoactive self-cleaning glasses

Glasses for architecture must have many functions in addition to their transparency. For example, the glasses with the functions, of self-cleaning, light control, UV reduction, anti-bacterial, energy conversion, and so on, will be used in buildings in the near future. This paper reviews some results on multifunctional photoactive glasses based on multi-layer coatings containing TiO₂ film and other functional coatings developed by us recently. The self-cleaning of glasses can be realized by coating the photoinduced super-hydrophilic nanoporous thin films based on TiO₂ photocatalysts via sol–gel route. A new method to enhance the photocatalytic activity of TiO₂ thin films direct coated on soda-lime glass was developed by treating the films in acidic solutions. The films also have good photoinduced anti-bacterial properties. The doping of a small amount of silver into the TiO₂ porous film can enhance its anti-bacteria effect without UV light irradiation. The TiO₂ thin films by appropriate heat-treatment can operate as self-cleaning glass in the visible light region. The UV reduction self-cleaning glasses are prepared by magnetron sputtering two layers of TiO₂–CeO₂ and TiO₂ thin films on soda-lime glasses. The TiO₂–CeO₂ thin films can cut all of UV light through adjusting the ratio of TiO₂ and CeO₂. The TiO₂/TiN/TiO₂ type multi-layer coated on glass substrate can act as low-E self-cleaning glass. The potential water-repellent coating based on TiO₂ is discussed finally.     

Structural and optical properties of TiO2:SnO2 thin films prepared by sol gel method

ABSTRACT

TiO₂:SnO₂ thin films were deposited on glass substrates, by using sol gel spin coating method with different ratio (3%, 5% and 7%) at 3200 rpm, to study their effect on different properties of TiO₂: SnO₂ thin films. The structural and optical properties of films have studied for different ratio. These deposited films have been characterized by various methods such as X-Ray Diffraction (XRD), Ultra Visible spectroscopy. The (XRD) can be used to identify crystal structure of as deposited films. The Transmission spectra have shown the transparent and opaque parts in the visible and UV wavelengths.     

Nanocrystalline TiO2 films studied by optical, XRD and FTIR spectroscopy

We report the deposition of thin titanium dioxide films on Si(1 0 0) and silica glass at low temperatures between 200 and 350 °C by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) with 222 nm radiation. The composition and optical properties of the films deposited have been studied using a variety of standard characterisation methods. A strong absorption peak around 438 cm⁻¹, corresponding to Ti-O stretching vibration, was observed by Fourier transform infrared spectroscopy for different deposition temperatures. Nanostructured films on Si wafers were observed by atomic force microscopy while X-ray diffraction results showed that crystalline TiO₂ layers could be formed at deposition temperatures as low as 210 °C. The deposition kinetics and influence of the substrate temperature on the film are discussed. The activation energy for this photo-CVD process at temperatures between 200 and 350 °C was found to be 0.435 eV. This is much lower than the value (E_a=5.64 eV) obtained by conventional thermal CVD. The thicknesses of the films grown, from several nanometers to micrometers can be accurately controlled by changing the number of drops introduced by the injection liquid source. Under optimum deposition conditions, refractive index values as high as 2.5 and optical transmittance of between 85% and 90% in the visible region of the spectrum can be obtained.     

Atomic layer deposition of Al2O3, ZrO2, Ta2O5, and Nb2O5 based nanolayered dielectrics

Ta₂O₅, Ta-Nb-O, Zr-Al-Nb-O, and Zr-Al-O mixture films or solid solutions were grown on Si(1 0 0) substrates at 300 °C by atomic layer deposition. The equivalent oxide thickness of Ta₂O₅ based capacitors was between 1 and 3 nm. In Zr-Al-O films, the high permittivity of ZrO₂ was combined with high resistivity of Al₂O₃ layers. The permittivity, surface roughness and interface charge density increased with the Zr content and the equivalent oxide thickness was between 2.0 and 2.5 nm. In the Zr-Al-Nb-O films the equivalent oxide thickness remained at 1.8-2.0 nm.     

Structure and morphological stability of (Lu1–xEux)2O3 thin films

(Lu_1–xEu_x)₂O₃ smooth, crack‐free, transparent films were prepared by the Pechini sol–gel method and a spin‐coating technique. Thermogravimetric analysis, differential thermal analysis and FITR spectroscopy were used to study the chemical processes during annealing of the films. Film structure, morphology and optical properties were investigated. X‐ray diffraction (XRD) analysis reveals the cubic phase of (Lu_1–xEu_x)₂O₃ films annealed in the 600–1000 °C temperature range. Smooth and crack‐free films with thicknesses of 250–1000 nm were obtained in the 600–800 °C temperature range. The thickness upper limit (1000 nm) of morphological stability of films (Lu_1–xEu_x)₂O₃ on sapphire substrates has been studied.