Structure of Pt3Co(1 1 0)c(2×4)-O surface studied by scanning tunneling microscopy

A Pt₃Co(1 1 0)c(2×4)-O surface has been investigated by scanning tunneling microscopy (STM), low-energy electron diffraction, and Auger electron spectroscopy. At a very initial oxidation stage exposed at 500°C, creation of missing and/or added row structures running to the [0 0 1] direction on clean Pt₃Co(1 1 0)2×1 surface was imaged from the steps. The surface is fully covered by a well-ordered c(2×4) structure at 2 L oxygen exposure. Atomic-resolution STM image shows the added row-type anti-phase Co-O zigzag chains along the [0 0 1] direction. Based on the images, the structure model for the c(2×4) surface was suggested as a first oxidized layer, which comes from the chemical reaction forming stoichiometric Co monoxide. Further oxygen exposure above 5 L, Co-O clusters imaged to large dots were formed on the surface with the size of about 5-7 Å.     

Ar assisted carbidization of TiO2 (1 1 0) supported Mo nanoparticles by decomposition of C2H4

Ar⁺ assisted carbidization of Mo nanoparticles supported on TiO₂ (1 1 0) is studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In order to activate the diffusion of carbon into the bulk of Mo nanoparticles we applied Ar ions (1 keV) during the exposure of C₂H₄. XPS exhibited that the decomposition of C₂H₄ at 850 K accompanied by ion bombardment results in an almost complete carbidization of nanocrystalline Mo while this treatment performed without ion bombardment results only in the carbidization of the particle surface. The modification of the crystallinity of the Mo-carbide particles was deduced from STM measurements.     

Influence of cobalt ion implantation on optical properties of titanium dioxide thin films

Nano-crystalline TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. In this study, the deposited TiO₂ coating with a grain size of 13 ± 2 nm was uniform without aggregation. Co ion implantation into the as-calcined TiO₂ thin films was conducted with fluences of 1 × 10¹⁵-1 × 10¹⁶ doses/cm² at 40 keV. In addition to the emission of TiO₂, the photoluminescence study showed the presence of another Co-related optical center at 405 nm in the Co-implanted TiO₂ thin films. Due to the strong capability of forming impurity compounds between the energetic cobalt ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

The optical properties of nanoporous structured titanium dioxide and the photovoltaic efficiency on DSSC

This study examined the characterization of nanoporous structured titanium dioxide and its application to dye-sensitized solar cells (DSSCs). TEM revealed nanopore sizes of 10.0 nm with a regular hexagonal form. When nanoporous structured TiO₂ was applied to DSSC, the energy conversion efficiency was enhanced considerably compared with that using nanometer sized TiO₂ prepared using a hydrothermal method. The energy conversion efficiency of the DSSC prepared from nanoporous structured TiO₂ was approximately 8.71% with the N719 dye under 100 mW cm⁻² simulated light. FT-IR spectroscopy showed that the dye molecules were attached perfectly to the surface and more dye molecules were absorbed on the nanoporous structured TiO₂ than on the nano-sized TiO₂ particles prepared using a conventional hydrothermal method. Electrostatic force microscopy (EFM) showed that the electrons were transferred rapidly to the surface of the nanoporous structured TiO₂ film.     

Lepidocrocite-like TiO2 and TiO2(110)–(1 × 2) supported on W(100)

Ultrathin films of TiO₂ were grown on a W(100)–O(2?×?1) substrate and characterised with a combination of scanning tunneling microscopy (STM) and low energy electron diffraction. In addition to islands of rutile TiO₂(110) with (1?×?1) termination that were reported previously, we also observed rutile TiO₂(110) islands with a (1?×?2) film termination. A lepidocrocite-like TiO₂ nanosheet was also observed on the W(100) surface. High resolution STM images show that the nanosheet grows in the principal orthogonal directions of the W(100) substrate and forms a commensurate (1?×?7) coincident cell.     

Fabrication of highly conductive Ta-doped SnO2 polycrystalline films on glass using seed-layer technique by pulse laser deposition

We discuss the fabrication of highly conductive Ta-doped SnO₂ (Sn_1 − xTa_xO₂; TTO) thin films on glass by pulse laser deposition. On the basis of the comparison of X-ray diffraction patterns and resistivity (ρ) values between epitaxial films and polycrystalline films deposited on bare glass, we proposed the use of seed-layers for improving the conductivity of the TTO polycrystalline films. We investigated the use of rutile TiO₂ and NbO₂ as seed-layers; these are isostructural materials of SnO_2, which are expected to promote epitaxial-like growth of the TTO films. The films prepared on the 10-nm-thick seed-layers exhibited preferential growth of the TTO (110) plane. The TTO film with x = 0.05 on rutile TiO₂ exhibited ρ  = 3.5 × 10^− 4 Ω cm, which is similar to those of the epitaxial films grown on Al₂O₃ (0001).     

Gas sensing mechanism of TiO2-based thin films

Two classes of thin film gas sensors have been studied: TiO₂ doped with Cr or Nb and TiO₂-SnO₂ mixed systems. Thin films have been prepared by the reactive sputtering from mosaic targets. It is demonstrated that titanium dioxide doped with Nb and Cr should be considered as a bulk sensor. Its performance is governed by the diffusion of point defects, i.e. very slow diffusion of Ti vacancies for TiO₂: 9.5 at% of Nb and fast diffusion of oxygen vacancies in the case of TiO₂: 2.5 at% Cr sensor. The corresponding response times are 55 min for TiO₂: 9.5 at% of Nb and 20 s for TiO₂: 2.5 at% Cr. In turn, sensors based on TiO₂-SnO₂, particularly those of the SnO₂-rich composition, belong to the group of surface sensors.     

Effect of TiO2-SiO2 sol-gel coating on the cpTi-porcelain bond strength

The effects of TiO₂-SiO₂ sol-gel coating with different firing temperatures (300 °C, 500 °C, and 750 °C) on the cpTi-porcelain bond strength were investigated in the present study. Prior to applying the low-fusing dental titanium porcelain, the phase, surface morphology, surface roughness and static water contact angle of the intermediate layer were evaluated. The cpTi-porcelain bond strength was measured using the three-point flexure test according to ISO 9693 standard. Statistical analyses were made using one-way ANOVA and Dunnett-t test. Significantly higher bond strength of TiO₂-SiO₂/750 °C (specimens coated with TiO₂-SiO₂ sol-gel coating and fired at 750 °C for 1 h) when compared to the control group was observed (p < 0.05). No rutile phase was found in all the tested specimens coated with TiO₂-SiO₂ sol-gel coating. The surface morphology of the intermediate layer was apparently different with different firing temperatures. It was found that the static water contact angle of TiO₂-SiO₂/750 °C significantly decreased (p < 0.05). However, no markedly different R_a of TiO₂-SiO₂/500 °C and TiO₂-SiO₂/750 °C in comparison to that of the control group was observed (p > 0.05). The results show that the TiO₂-SiO₂ sol-gel coating fired at 750 °C for 1 h can notably improve the cpTi-porcelain bond strength and may be suitable for clinical use.     

Growth of β-FeSi2 thin films on β-FeSi2 (110) substrates by molecular beam epitaxy

We have investigated the preparation of β-FeSi₂ substrate and growth condition of β-FeSi₂ thin film on β-FeSi₂ (110) substrate by molecular beam epitaxy. The surface of the substrate was prepared by a wet-etching using HF(50%):HNO₃(60%):H₂O = 1:1:5 solution at 25 °C. It is clear that the optimal etching period to obtain a flat surface was 3 min. The β-FeSi₂ thin film with streak RHEED pattern was obtained at Si/Fe flux ratio of 2.9. Average surface roughness (Ra) of the β-FeSi₂ film was about 0.5 nm in 5 × 5 μm² area.     

Epitaxial growth of p-sexiphenyl film on highly oriented pyrolytic graphite surface studied by scanning tunneling microscopy

The epitaxial growth of p-sexiphenyl (C₃₆H₂₆, 6P) on highly oriented pyrolytic graphite (HOPG) surface has been investigated by scanning tunneling microscopy (STM). 6P molecules prefer epitaxial growth with the long axis along the [110] direction (armchair direction) of the HOPG substrate, with the unit cell parameters b₁ = 0.67 ± 0.06 nm, b₂ = 5.97 ± 0.06 nm and angle of 88 ± 3° between them. The relation of the 6P overlayer lattice vectors with the HOPG substrate has also been deduced, i.e. the 5 × 1 supercell is in a point-on-point commensurate relation with respect to the HOPG substrate surface.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Optical properties of TiO2 thin films after Ag ion implantation

Metal plasma ion implantation has being successfully developed for improving the electronic and optical properties of semiconductor materials. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. The TiO₂ thin film was optimized to obtain a high-purity crystalline anatase phase by calcinations at 550 °C. The TiO₂ coating was uniform without aggregation, which provided good photo conversion efficiency. Ag ion implantation into the as-calcined TiO₂ thin films was conducted with 1 × 10¹⁵ ~ 1 × 10¹⁶ ions/cm² at 40 keV. The peak position and intensity of the photoluminescence and UV-Vis absorption spectra are quite sensitive to Ag doping. The optical characterization showed a shift in optical absorption wavelength towards infrared ray side, which was correlated with the structure variation of the Ag⁺ implanted TiO₂. Due to the strong capability of forming compounds between the energetic silver ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

One-pot synthesis of intestine-like SnO2/TiO2 hollow nanostructures

In the present study the intestine-like binary SnO₂/TiO₂ hollow nanostructures are one-pot synthesized in aqueous phase at room temperature via a colloid seeded deposition process in which the intestine-like hollow SnO₂ spheres and Ti(SO₄)₂ are used as colloid seeds and Ti-source, respectively. The novel core (SnO₂ hollow sphere)-shell (TiO₂) nanostructures possess a large surface area of 122 m²/g (calcined at 350 °C) and a high exposure of TiO₂ surface. The structural change of TiO₂ shell at different temperatures was investigated by means of X-ray diffraction and Raman spectroscopy. It was observed that the rutile TiO₂ could form even at room temperature due to the presence of SnO₂ core and the unique core-shell interaction.     

Low temperature facile synthesis of anatase TiO2 coated multiwalled carbon nanotube nanocomposites

Anatase TiO₂ coated multiwalled carbon nanotube (MWNT) nanocomposites were prepared by combining the sol-gel method with a self assembly technique at a low temperature. XRD, TEM, FTIR and XPS spectra were applied to characterize the crystal phase, microstructure, and other physicochemical properties of the sample. The results showed that MWNTs were covered with a 12-20 nm thickness layer of anatase TiO₂ or surrounded by a 30 -290 nm thickness coating of anatase TiO₂. The layer or coating is constructed of TiO₂ nanoparticles about 5.8 nm. Furthermore, as-prepared composite was rich in surface hydroxyl groups.     

Visible light absorption ability and photocatalytic oxidation activity of various interstitial N-doped TiO2 prepared from different nitrogen dopants

Nitrogen-doped TiO₂ was developed to enable photocatalytic reactions using the visible range of the solar spectrum. This work reports on the synthesis, characterisation and kinetic study of interstitial N-doped TiO₂ prepared by the sol–gel method using three different types of nitrogen dopants: diethanolamine, triethylamine and urea. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV–visible spectroscopy were used to analyse the titania. Different interstitial N-doped TiO₂ properties, such as absorption ability in the UV–visible light region, redshift in adsorption edge, good crystallisation and composition ratio of titania structures (anatase and rutile) could be obtained from different nitrogen dopants. Amongst investigated nitrogen precursors, diethanolamine provided the highest visible light absorption ability of interstitial N-doped TiO₂ with the smallest energy bandgap and the smallest anatase crystal size, resulting in the highest efficiency in 2-chlorophenol degradation. The photocatalytic activity of all N-doped TiO₂ can be arranged in the following order: TiO₂/diethanolamine > TiO₂/triethylamine > TiO₂/urea > un-doped TiO₂. The initial rate of 2-chlorophenol degradation using the interstitial N-doped TiO₂ with diethanolamine was 0.59 mg/L-min and the kinetic constant was 2.34 × 10⁻² min⁻¹ with a half-life of 98 min. In all cases, hydroquinone was detected as a major intermediate in the degradation of 2-chlorophenol.     

Transparent conducting Nb-doped anatase TiO2 (TNO) thin films sputtered from various oxide targets

Transparent conducting Nb-doped anatase TiO₂ (TNO) epitaxial films were sputtered from TiO₂-, Ti₂O₃-, and Ti-based targets at various oxygen partial pressures (Po₂). Using the TiO₂- and Ti₂O₃-based targets, highly conductive films showing a resistivity (ρ) of ~ 3 × 10^− 4 Ω cm could be formed without postdeposition treatment. In the case of the TNO films formed from the Ti-based target, reductive annealing had to be carried out at a temperature of 600 °C to achieve similar resistivity values. Thus, the use of oxide targets is preferable to obtain as-grown transparent conducting TNO films. In particular, the Ti₂O₃-based target is practically advantageous, because it offers a wide range of optimal Po₂ values at which ρ values of the order of 10^− 4 Ω cm are achievable.     

Refractory metal reactivity towards oxide surface: W/TiO2(1 1 0) case

Reactivity of deposited tungsten towards TiO₂(1 1 0) surface was studied using synchrotron radiation photoemission spectroscopy (both core levels, valence band and resonant photoemission) on Materials Science Beamline at ELETTRA. W depositions carried out at room temperature on TiO₂(1 1 0) surface give rise to an interfacial reaction which leads to a metastable situation due to kinetic limitations. Annealing induces chemical changes which are function of the initial coverage; for fractional coverage, annealing induces completion of oxidation of deposit whereas reduction to metallic tungsten occurs for highest coverage. These results demonstrate that interaction of W with TiO₂(1 1 0) surface is, as the one of molybdenum, driven by a balance between W-O interactions and W-W depending on tungsten atoms density on TiO₂ surface.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Thermal behaviour of the O2/TiO2 (110)-(1 × 2) surface

Synchrotron radiation ultra-violet photoemission at different photon energies (17.1, 19.3, and 21.5 eV) has been used to study the interaction of O₂ with the TiO₂ (110)-(1 × 2) surface reconstruction at temperatures between 77 and 320 K. At 77 K the results show a weak molecular chemisorption of the O₂ molecule on the surface. By analysing the thermal behaviour of the O₂/TiO₂ system in a temperature range from 77 to 320 K, it has been found that between 120 and 200 K the O₂ molecule is dissociated.     

Photocatalytic performance of TiO2 films produced with combination of oxygen-plasma and rapid thermal annealing

In this work, a combination of oxygen plasma and rapid thermal annealing was suggested in order to oxidize the surface of titanium into TiO₂. A plasma was formed by employing pure oxygen at 150 W, 300 W, and 400 W under a pressure of 7.5 to 8.5 Pa for 5 to 10 min. The TiO₂ was then subjected to rapid thermal annealing (RTA) at a temperature of 400 to 500 °C for 1 min. From the attained results, an RF power of 300 W for 5 min was observed to be sufficient to produce an optimal photocatalytic TiO₂ film. Optimal conditions were confirmed by additional experiments involving humic acid (HA) degradation of the TiO₂ films. When compared to a traditional TiO₂ film, a TiO₂ film prepared with an oxygen-plasma treatment and RTA system exhibited improved photocatalytic capability for HA photodegradation in an aqueous solution. Therefore, this process proposed in this work can be an excellent alternative to the traditional method for fabricating photocatalytic TiO₂ films.