The optical properties of Ti-doped TiO2 nanoceramic films deposited by simultaneous rf and dc magnetron sputtering

The Ti-doped TiO₂ (TiO₂:Ti) nanoceramic films were deposited by simultaneous rf magnetron sputtering of TiO₂ and dc magnetron sputtering of Ti. When dc power increased, TiO preferentially formed and the deposited films had lower O/Ti atomic ratio, especially at low substrate temperature. With the decrease of substrate temperature, the TiO₂:Ti film had relatively high optical energy gap, therefore the absorption edge showed the blue shift. The nonlinear refractive indices of TiO₂:Ti films prepared at different dc powers and substrate temperatures were measured by Moiré deflectometry, and were of the order of 10^?8 cm² W^?1. By decreasing dc power and increasing substrate temperature, TiO₂:Ti film exhibited lower surface roughness, higher linear refractive index and lower stress-optical coefficient.     

Absorption boost of TiO2 nanotubes by doping with N and sensitization with CdS quantum dots

A process of obtaining N-doped TiO₂ nanotubes sensitized by CdS nanoparticles is presented, including detailed characterizations performed along the synthesis. Transparent TiO₂ films consisting of nanotubes, 2.5 µm long and of ~60 nm inner diameter, were obtained after anodization of a titanium film deposited onto FTO glass substrate. N-doping was achieved by annealing of TiO₂ film in ammonia. X-ray Photoelectron Spectroscopy measurements showed that nitrogen was substitutionally incorporated in the TiO₂ matrix, with the N:Ti concentration ratio of 1:100. The doping changed the optical properties of the material in such a way that the absorption edge was shifted from 380 nm to 507 nm, as observed from diffuse reflectance spectra. The influence of the microwave (MW) irradiation on the synthesized CdS quantum dots and their optical properties was investigated. It was shown that the diameter of CdS nanoparticles was increased due to releasing of S^2- ions from dimethyl sulfoxide (DMSO) as a consequence of the MW treatment. The (N)TiO₂ films were then used as substrates for matrix assisted pulsed laser deposition of the CdS quantum dots with DMSO as a matrix. The laser parameters for the deposition were optimized in order to preserve the nanotubular structure open, the latter being an important feature of this type of photoanode. The structure obtained under optimized conditions has an additional absorption edge shift, reaching 603 nm.     

Colored films produced by electron beam deposition from nanometric TiO2 and Al2O3 pigment powders obtained by modified polymeric precursor method

Synthesis and the characterization of TiO₂:5%Co (green), TiO₃:5%Fe (brown-reddish), TiO₂:2%Cr (brown), Al₂O₃:5%Co (blue), Al₂O₃:5%Fe (brown-reddish) and Al₂O₃:2%Cr (light green) nanometric pigment powders using polymeric precursor (modified Pechini's method) is reported. Colored thick films were deposited on amorphous quartz substrates by electron beam physical vapor deposition (EB-PVD) using pellets of the pigment powders as target. The evaporation process was carried out in vacuum of 4 × 10⁻⁶ Torr and the amorphous quartz substrates were kept at 350 °C during deposition. The TiO₂-based pigment powders presented crystalline anatase phase and the Al₂O₃-based pigment powders showed corundum phase, investigated by X-ray diffraction (XRD). The average particle size of the pigment powders was about 20 nm, measured by scanning electron microscopy with field emission gun (SEM-FEG). Diffuse reflectance spectra and colorimetric coordinates L¹, a¹, b¹ using the CIE-L¹a¹b¹ method are shown for the pigment powders, in the 350–750 nm range. The colored thick films were characterized by transmittance (UV–Vis) and atomic force microscopy (AFM). The average film roughness was ∼5.5 nm and the average grain size obtained in the films was around 75 nm. Films with thickness from 400 nm to 690 nm were obtained, measured by talystep profiler. Transmission spectra envelop method has been used to obtain refractive index and thickness of the Al₂O₃ colored thick films.     

Fabrication of CaLa4(Zr0.05Ti0.95)4O15 thin films by RF magnetron sputtering

Crystalline CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films deposited on n-type Si substrates byRF magnetron sputtering at a fixed RF power of 100 W, an Ar/O₂ ratio of 100/0, an operating pressure of 3 mTorr, and different substrate temperatures were investigated. The surface structural and morphological characteristics analyzed by X-ray diffraction and atomic force microscopy were sensitive to the deposition conditions, such as the substrate temperature. The diffraction pattern showed that the deposited films had a polycrystalline microstructure. As the substrate temperature increased, the quality of the CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films improved, and the kinetic energies of the sputtered atoms increased, resulting in a structural improvement of the deposited CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films. A high dielectric constant of 16.7 (f=1 MHz), a dissipation factor of 0.19 (f=1 MHz), and a low leakage current density of 3.18×10⁻⁷ A/cm² at an electrical field of 50 kV/cm were obtained for the prepared films.     

Preparation and electrical properties of Bi2Zn2/3Nb4/3O7 thin films deposited at room temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited at room temperature on Pt/Ti/SiO₂/Si(1 0 0) and polymer-based copper clad laminate (CCL) substrates by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited in situ with no intentional heating under an oxygen pressure of 4 Pa and then post-annealed at 150 °C for 20 min. It was found that the films are still amorphous in nature, which was confirmed by the XRD analysis. It has been shown that the surface roughness of the substrates has a significant influence on the electrical properties of the dielectric films, especially on the leakage current. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates exhibit superior dielectric characteristics. The dielectric constant and loss tangent are 59.8 and 0.008 at 10 kHz, respectively. Leakage current density is 2.5 × 10^?7 A/cm² at an applied electric field of 400 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on CCL substrates exhibit the dielectric constant of 60 and loss tangent of 0.018, respectively. Leakage current density is less than 1 × 10^?6 A/cm² at 200 kV/cm.     

Lead zirconium titanate thin films prepared by thermal annealing of multilayer structures composed of PbO,ZrO2 and TiO2

Lead zirconium titanate [Pb(Zr_xTi_1?x)O₃ or PZT] thin films were prepared by the thermal annealing of multilayer films composed of binary oxide layers of PbO, ZrO₂ and TiO₂. The binary oxides were deposited by metal organic chemical vapor deposition. An interdiffusion reaction for perovskite PZT thin films was initiated at approximately 550 °C and nearly completed at 750 °C for 1 h under O₂ annealing atmosphere. The composition of Pb/Zr/Ti in perovskite PZT could be controlled by the thickness ratio of PbO/ZrO₂/TiO₂ where the contribution of each binary oxide at the same thickness was 1:0.55:0.94. The electrical properties of PZT (Zr/Ti = 40/60, 300 nm) prepared on a Pt-coated substrate included a dielectric constant ?_r of 475, a coercive field E_c of 320 kV/cm, and remnant polarization P_r of 11 μC/cm² at an applied voltage of 18 V.     

Preparation and ferroelectric properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 thin films deposited on Pt electrodes using LaNiO3 as buffer layer

(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1) and LaNiO₃/Pt/Ti/SiO₂/Si (1 1 1) substrates by a sol–gel process. The phase structure and ferroelectric properties were investigated. The X-ray diffraction pattern indicated that the (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin film deposited on Pt/Ti/SiO₂/Si (1 1 1) substrates is polycrystalline structure without any preferred orientation. But the thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates shows highly (1 0 0) orientation (f ≥ 81%). The leakage current density for the two thin films is about 6 × 10^?3 A/cm² at 250 kV/cm, and thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates possessed a much lower leakage current under high electric field. The hysteresis loops at an applied electric field of 300 kV/cm and 10 kHz were acquired for the thin films. The thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates showed improved ferroelectricity.     

Preparation of oriented SiO32− doped TiO2 film and degradation of methylene blue under visible light irradiation

SiO₃^2? doped TiO₂ films with oriented nanoneedle and nanorectangle block structure has been firstly synthesized by hydrothermal synthesis method. The prepared samples are characterized, X-ray diffraction (XRD) results demonstrate that the SiO₃^2? doped TiO₂ films are rutile and brookite phases. The scanning electron microscope (SEM) analysis reveals that the quantity of O₂ affects the morphology of the SiO₃^2? doped TiO₂ films (SiTiA films prepared with unmodified substrate). The SiO₃^2? doped TiO₂ films (SiTiB films prepared with modified substrate) display two layers, one is porous structure, the other is nanoneedle structure. UV–vis, IR, transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) microscopy all prove that SiO₃^2? have been doped in the TiO₂ crystal structure. They have remarkable red shift and higher photocatalytic activity of degradation of methylene blue than P-25 under visible light (λ > 420 nm) irradiation. Besides, photocatalytic activity of the film is stable during 4 times recycling.     

The effects of the post-annealing time on the growth mechanism of Bi2Sr2Ca1Cu2O8+∂ thin films produced on MgO (100) single crystal substrates by pulsed laser deposition (PLD)

Bi₂Sr₂Ca₁Cu₂O_8+∂ thin films were deposited on MgO (100) substrates by pulsed laser deposition (PLD). The effects of post-annealing time on the phase formation, the structural and superconducting properties of the films have been investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature dependent resistivity (R–T), atomic force microscopy (AFM), and DC magnetization measurements. The films deposited at 600 °C were post-annealed in an atmosphere of a gas mixture of Ar (93%) and O₂ (7%), at 860 °C for 10, 30, and 60 min. All films have demonstrated a mainly single phase of 2212 with a high crystallinity (FWHM≈0.159°) and c-axis oriented. The critical temperature, T_C, of the films annealed for 10, 30, and 60 min were obtained as 77, 78, and 78 K, respectively. The highest critical current density, J_C, was calculated as 3.34×10⁷ A/cm² for the film annealed at 860 °C for 30 min at 10 K.     

Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

Effects of plasma gas composition on bond strength of hydroxyapatite/titanium composite coatings prepared by rf-plasma spraying

The effects of plasma gas composition on the bond-strength of HA/Ti composite coatings were investigated. HA/Ti composite coatings were deposited on titanium substrates by a radio-frequency (rf) thermal plasma spraying method with input powers of 10–30 kW. The ratio of the HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the coating's composition from Ti-rich at the bottom to HA-rich at its upper layer. The bond (tensile) strength of the obtained HA/Ti composite coatings was 40–65 MPa when sprayed with plasma gas containing N₂ (i.e., Ar–N₂). On the other hand, HA/Ti composite coatings prepared with plasma gas containing O₂ (i.e., Ar–O₂) had significantly lower bond strength (under 30 MPa). XRD patterns of Ti coatings without HA showed that titanium nitride and titanium dioxide formed, respectively, on titanium deposits sprayed with Ar–N₂ and Ar–O₂ plasma. Scanning electron microscopic (SEM) observation showed an acicular texture on the Ti deposits prepared with Ar–N₂ plasma. SEM observations implied that, when sprayed with Ar–O₂ plasma, a thin TiO₂ layer formed at the interfaces between the Ti splats in the deposits.     

Thin-film nanocomposites of diamond-like carbon and titanium oxide; Osteoblast adhesion and surface properties

Thin films of a novel, nanocomposite material consisting of diamond-like carbon and polycrystalline/amorphous TiO_x (DLC-TiO_x, x ≤ 2) were prepared using pulsed direct-current plasma enhanced chemical vapour deposition (PECVD). Results from Raman spectroscopy indicate that the DLC and TiO_x deposit primarily as segregated phases. Amorphous TiO₂ is found to be present on the surface region of the film and there is evidence for the presence of crystalline TiO in the bulk of the film. The hydrophilicity of the DLC-TiO_x films increased with increasing titanium content. Culture studies with human osteoblasts revealed that the differences in three-day cell adhesion properties (count, morphology and area) between DLC and DLC-TiO_x films containing up to 13 at.% Ti were not statistically significant. However, the cell count was significantly greater for the films containing 3 at.% of Ti in comparison to those containing 13 at.% of Ti. A post-plasma treatment with Ar/O₂ was used to reduce the water contact angle, θ, by nearly 40° on the DLC-TiO_x films containing 3 at.% of Ti. A cell culture study found that the osteoblast count and morphology after three days on these more hydrophilic films did not differ significantly from those of the original DLC-TiO_x films. We compare these results with those for SiO_x-incorporated DLC films and evaluate the long-term osteoblast-like cell viability and proliferation on modified DLC surfaces with water contact angles ranging from 22° to 95°.     

Pulsed laser deposition BTS thin films: The role of substrate temperature

BaSn_0.15Ti_0.85O₃ (BTS) thin films were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrate by pulsed laser deposition and the effects of substrate temperature on their structure, dielectric properties and leakage current density were investigated. The results indicate that the substrate temperature has a significant effect on the structural and dielectric properties of the BTS thin films which exhibit a polycrystalline perovskite structure if the substrate temperature ranges within 550–750 °C. The dielectric constant and loss tangent of the BTS thin films deposited at 650 °C are 341 and 0.009 at 1 MHz, respectively, the tunability is 72.1% at a dc bias field of 400 kV/cm, while the largest figure of merit (FOM) is 81.1. The effect of the substrate temperature on the leakage current of the BTS thin films is discussed.     

Preparation and characterization of transparent indium- doped TiO2 films deposited by MOCVD

Titanium dioxide (TiO₂) films doped with different indium (In) concentrations have been prepared on SrTiO₃ (STO) substrates by high vacuum metalorganic chemical vapor deposition (MOCVD). X-ray diffraction (XRD) analyses revealed the TiO₂ films doped with low In concentrations to be [001] oriented anatase phase and the films with high In concentrations to present polycrystalline structures. The 1.8% In-doped TiO₂ film exhibited the best electrical conductivity properties with the lowest resistivity of 8.68×10⁻² Ω cm, a Hall mobility of 10.9 cm² V⁻¹ s⁻¹ and a carrier concentration of 6.5×10¹⁸ cm⁻³. The films showed excellent transparency with average transmittances of over 85% in the visible range.     

Electrophoretic deposition of surface-modified titanate nanosheets via layer-by-layer assembly and deposited film properties

The surface of H₂Ti₄O₉·xH₂O titanate nanosheets was modified using the sulfonated tetrafluoroethylene-based polymer Nafion^®, via layer-by-layer assembly. The surface modification allowed the titanate nanosheets to be highly dispersed in hydrophobic organic solvents. Thick films of surface-modified nanosheets were prepared on indium tin oxide (ITO)-coated glass substrates as a negative electrode by electrophoretic deposition. The thickness of the films increased with increasing deposition time and grew to more than 8 μm in 600 s under potentiostatic conditions at 7.5 V. The electrophoretically deposited thick films showed significant hydrophobicity with contact angle for water 95°, and enhanced adsorption and higher photocatalytic activity for hydrophobic dyes such as thionine than those of thick films prepared from unmodified titanate nanosheets.     

Synergy effect in the photocatalytic degradation of methylene blue on a suspended mixture of TiO2 and N-containing carbons

N-containing carbon materials were obtained from waste plum stones submitted to pyrolysis under Ar flow at 700 °C or to activation under steam at 800 °C and enriched with nitrogen by heating in a NH₃/air mixture at 270 °C or in NO at 300 °C. In situ mixtures of TiO₂ and carbons were prepared by the slurry method and methylene blue photodegradation was chosen as a model reaction to verify the influence of N-containing carbons on the photocatalytic activity of TiO₂ under artificial visible light irradiation. From the kinetics of methylene blue degradation an important synergy effect between both solids was detected with a remarkable increase up to a factor of 5.3 higher in the photocatalytic activity on TiO₂–C than that on TiO₂ alone. A mechanism for the photoassisting role of N-containing carbons upon the photoactivity of TiO₂ under visible light is discussed.     

Characterization of single crystalline a-TiO2 films on MgAl2O4(100) substrates by MOCVD

Anatase phase TiO₂ (a-TiO₂) films have been deposited on MgAl₂O₄(100) substrates at the substrate temperatures of 500–650 °C by the metal organic chemical vapor deposition (MOCVD) method using tetrakis-dimethylamino titanium (TDMAT) as the organometallic (OM) source. The structural analyses indicated that the TiO₂ film prepared at 600 °C had the best single crystalline quality with no twins. The out-of-plane and in-plane epitaxial relationships of the film were a-TiO₂(001)||MgAl₂O₄(100) and TiO₂[100]||MgAl₂O₄[100], respectively. A uniform and compact surface with stoichiometric composition was also obtained for the 600 °C-deposited sample. The average transmittance of all the TiO₂ films in the visible range exceeded 91% and the optical band gap of the films varied from 3.31 to 3.41 eV.     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Characterization of Cu(In,Ga)Se2 thin films prepared by RF magnetron sputtering using a single target without selenization

Cu(In_1?xGa_x)Se₂ (CIGS) thin films were prepared using a single quaternary target by RF magnetron sputtering. The effects of deposition parameters on the structural, compositional and electrical properties of the films were examined in order to develop the deposition process without post-deposition selenization. From X-ray diffraction analysis, as the substrate temperature and Ar pressure increased and RF power decreased, the crystallinity of the films improved. The scanning electron microscopy revealed that the grains became uniform and circular shape with columnar structure with increasing the substrate temperature and Ar pressure, and decreasing the RF power. The carrier concentration of CIGS films deposited at the substrate temperature of 500 °C was 2.1 × 10¹⁷ cm^?3 and the resistivity was 27 Ω cm. At the substrate temperature above 500 °C, In and Se contents in CIGS films decreased due to the evaporation and it led to the deterioration of crystallinity. It was confirmed that CIGS thin films deposited at optimal condition had similar atomic ratio to the target value even without post-deposition selenization process.     

Preparation of (0 2 0)-oriented BaTi2O5 thick films and their dielectric responses

Barium dititanate (BaTi₂O₅) thick films were prepared on a Pt-coated Si substrate by laser chemical vapor deposition, and ac electric responses of (0 2 0)-oriented BaTi₂O₅ films were investigated using several equivalent electric circuit models. BaTi₂O₅ films in a single phase were obtained at a Ti/Ba molar ratio (m_Ti/Ba) of 1.72–1.74 and deposition temperature (T_dep) of 908–1065 K as well as m_Ti/Ba = 1.95 and T_dep = 914–953 K. (0 2 0)-oriented BaTi₂O₅ films were obtained at m_Ti/Ba = 1.72–1.74 and T_dep = 989–1051 K. BaTi₂O₅ films had columnar grains, and the deposition rate reached 93 μm h^?1. The maximum relative permittivity of the (0 2 0)-oriented BaTi₂O₅ film prepared at T_dep = 989 K was 653 at 759 K. The model of an equivalent circuit involving a parallel combination of a resistor, a capacitor, and a constant phase element well fitted the frequency dependence of the interrelated ac electrical responses of the impedance, electric modulus, and admittance of (0 2 0)-oriented BaTi₂O₅ films.