Cation site environment in ultrathin TiOx films grown on Pt(1 1 1) probed by X-ray absorption spectroscopy at the Ti 2p edge

We present the results of a XAS experiment carried out at the Ti 2p edge on well-ordered TiO_x ultrathin films grown on the Pt(1 1 1) surface. XAS at the Ti 2p edge has been extensively applied to the study of Ti bulk compounds, particularly to the study of titania. According to the literature, the corresponding Ti 2p edge spectral shape is related to the stoichiometry and crystal field symmetry at the Ti sites. In the present study we aim at extending the potential of the XAS technique by discussing Ti 2p spectra obtained on several, dimensionally confined, TiO_x phases in the form of ultrathin films. One of the main features of these films is their high degree of structural order. Furthermore, the results of previous studies provide valuable information about the chemistry and structure of the films, so that we are able to analyse the current XAS data in detail and to compare them with the appropriate Ti 2p XAS data of bulk oxides. We find that in the case of ultrathin film with a fully oxidised Ti⁴⁺ stoichiometry, the Ti 2p XAS data display features that are very similar to the ones observed in related bulk systems. The XAS data of the reduced TiO_x films (with x < 2) show a rather different and specific shape. By comparing the experimental spectra with an atomic type of model calculation we show that the Ti 2p XAS profiles can be attributed mainly to stoichiometry-symmetry effects.     

Ion irradiation induced nano pattern formation on TiO2 single crystal

Nanodots have been fabricated on rutile TiO₂(1 1 0) single crystals using Ar ion beam. Ion beam sputtering creates oxygen vacancies, leading to a 45 nm thick Ti rich layer, on the surface. Post-sputtering, rutile TiO₂ also exhibits a decrease in the inter planar separation along [1 1 0] direction. Additionally, blueshift in the E_g Raman mode, representing the vibrations of oxygen atoms along c-axis, is also observed. Both these results suggest the development of a compressive stress along c-axis upon sputtering. Enhancement in intensity of A_1g Raman mode also indicates modification in TiO vibrational influence.     

Computational study of the adsorption of dimethyl methylphosphonate (DMMP) on the (0 1 0) surface of anatase TiO2 with and without faceting

The adsorption of dimethyl methylphosphonate (DMMP) on the (0 1 0) surface of anatase TiO₂, which is isostructural with the (1 0 0), has been studied using density functional theory and two-dimensionally-periodic slab models. The experimentally-observed faceting of this surface has, for the first time, been included in the modeling. The relaxations of bare surfaces both with and without faceting are similar, leading to an atomic-scale roughening due to inward (outward) displacement of fivefold-coordinated Ti_5c (sixfold-coordinated T_6c) atoms together with outward displacement of threefold-coordinated O_3c atoms. Molecular adsorption occurs by formation of a Ti_5c?OP dative bond with one or more CH?O_2c bonds between CH₃ groups and unsaturated, twofold-coordinated (O_2c) sites. The energies for molecular adsorption, obtained using the B3LYP functional, are virtually identical (about ?21.0 kcal/mol) for the two surfaces and are also close to those found elsewhere for the rutile (1 1 0) and anatase (1 0 1) surfaces. A possible first step in the dissociative adsorption of DMMP has also been modeled and is found to be thermodynamically favored over molecular adsorption to a degree which depends on faceting.     

Effect of the crystalline constitution of TiO2 substrates on the growth of ultrathin Mo layer

Metallic molybdenum was deposited by magnetron sputtering on amorphous and (110) rutile TiO₂ substrates. An interfacial reaction between the deposited Mo and the TiO₂ substrates generating Ti^3 +, Ti^2 + oxidation states is evidenced by X-ray photoelectron spectroscopy. Our XPS data suggest, as compared to the (110) rutile substrate, a higher reactivity of the amorphous TiO₂ leading to a stronger Mo oxidation. In both cases, this reaction, leads to the formation of MoO_x nanostructures at the interfaces. The growth mechanism of the Mo deposit as a function of the crystalline constitution of the TiO₂ substrate was analyzed by processing the XPS data using the Quases ® software. The data reveal a layer-by-layer growth of the Mo deposit on the (110) rutile substrate and a Stranski–Krastanov growth on the amorphous one. We explain these different growth modes based on the TiO₂ surface reactivity and electronic structure using the Cabrera–Mott theory. This explanation is supported by Time-of-Flight Secondary Ion Mass spectrometry profiling.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Lithium insertion into nanometer-sized rutile-type TixSn1 − xO2 solid solutions

The electrochemical properties of rutile-type Ti_xSn_1?xO₂ solid solutions (x = 0–1.0) as an anode for a lithium–ion battery were investigated using nanosized crystals prepared by an aqueous solution process. The reduction of the crystal size to nanoscale allowed a smooth lithium insertion into the rutile framework at room temperature. The lithium-insertion behavior of TiO₂, SnO₂, and the solid solutions was evaluated without any structural change of the rutile-type crystal structure in the potential range of 1.2–3.5 V (versus Li/Li⁺). The interstitial spaces for lithium ions were found to be derived from the crystal structure of the rutile framework and independent of the metal species.     

Methylene bromide chemistry and photochemistry on rutile TiO2(110)

The chemistry and photochemistry of methylene bromide (CD₂Br₂) on the rutile TiO₂(110) surface was probed using temperature programmed desorption (TPD). CD₂Br₂ desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η¹-CD₂Br₂ species and a bridging η²-CD₂Br₂ species, respectively. The latter two TPD states presumably involve binding of CD₂Br₂ molecules to the surface through Br coordination at five-coordinate Ti⁴⁺ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti⁴⁺ site density (5.2 × 10¹⁴ cm^? 2). No thermal decomposition of CD₂Br₂ was observed on either the clean surface or with preadsorbed O₂. UV irradiation of CD₂Br₂ on TiO₂(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD₂Br₂ photodesorption from TiO₂(110) occurred with a low cross section (~ 2 × 10^? 21 cm²) similar to that expected from direct optical excitation of CD₂Br₂. This observation suggests that charge carriers generated in TiO₂(110) were no more effective in activating adsorbed CD₂Br₂ molecules than would be expected through direct molecular excitation. These findings suggest that photocatalytic destruction of halocarbons such as CD₂Br₂ on TiO₂ may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO₂ by bandgap excitation.     

TPD and ITPD study of materials used as chemoresistive gas sensors

Temperature-programmed desorption (TPD) and a differential form of it, called intermittent temperature-programmed desorption (ITPD), turned out to be powerful characterising techniques for chemoresistive materials applied to gas sensing. We investigated samples of SnO₂, TiO₂ and solid solutions of them (Ti_xSn_1 ? xO₂). TPD and ITPD experiments were carried out in vacuum, with samples previously treated in pure O₂ (100 Torr, 500 °C, 30 min). Amounts of desorbed O₂ corresponded for all Ti-containing samples to less than 10% of a compact monolayer of ions O^2?. Corresponding values of the apparent activation energy of desorption (E_app) were calculated directly from the Arrhenius plots for each partial TPD and ranged from about 100 to 330 kJ mol^? 1 (1.16 to 3.82 eV).     

Effects of composition and frozen-in conditions on bulk and grain boundary conductivities of Yb2Ti2O7-based materials

The present work provides a comprehensive interpretation of factors which affect cation and/or anion disordering in Yb₂Ti₂O₇-based materials, and their effects on transport properties. It also provides guidelines for further improvements of transport properties. Powder processing and thermal history may play major roles, especially when anti-site cation exchange is likely to occur at typical sintering temperatures, as confirmed by structural refinement. One found that the cooling rate may also determine changes in frozen-in conditions. Excessive sintering temperatures affect both the bulk and grain boundary properties of samples with composition Yb₂Ti₂O₇; this was ascribed to the formation of a Ti-rich amorphous phase, and corresponding excess of Yb in the bulk phase. Anti-site occupancy of B-site positions was found to affect ionic conductivity, as demonstrated for conditions that cause cation heterogeneities in Yb₂Ti₂O₇, and also by analysing conductivity data for compositions with excess of Yb. The conductivity data obtained for Yb_2 + xTi_2 ? xO_7 ? d become less dependent on sample preparation, possibly because deliberate composition changes play a prevailing role, compared to intrinsic cationic and anionic disorders. Samples with slight excess of Ti retain prevailing ionic conductivity, which differs significantly from the effects of a typical donor additive on ionic and electronic conductivities.     

First principles and classical modeling of the oxidized titanium (0001) surface

The formation of a native oxide layer on the Ti(0001) surface is studied by means of FPMD simulations. In agreement with experimental findings, at low temperature we observe quick saturation of the surface reactivity, whereas incorporation of further O₂ molecules in the oxide network takes place after thermal annealing at ～ 800 K. At an O coverage of 2 ML the oxide layer presents an amorphous structure, an approximate TiO stoichiometry, and a broad distribution of Ti oxidation states from + 1 to + 4. We find consistency between the computed Bader atomic charges on Ti atoms and the correspondent charges computed classically by simple electrostatic minimization methods. On this basis we develop an analytic potential to simulate Ti/TiO_x interfaces, including only Coulomb interaction and short-range atomic repulsion terms. Two different parameter sets are proposed and their transferability among TiO₂ allomorphs and thin-layer oxide structures is tested both in static relaxations and in room-temperature MD simulations. These show only negligible changes in the topology of the oxide network after annealing and relaxation of the reference quantum model at the classical level. Moreover, we show that superficial oxide layers can be successfully generated purely classically by truncation of a large-scale Ti/amorphous–TiO₂ system. This may enable large-scale applications of our potential to tribology and biomolecular adsorption phenomena.     

Segregation at the surfaces of CuxPd1 − x alloys in the presence of adsorbed S

The influence of adsorbed S on surface segregation in Cu_xPd_1 ? x alloys (S/Cu_xPd_1 ? x) was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu_xPd_1 ? x CSAF was observed at all bulk compositions, x, but the extent of Cu segregation to the S/Cu_xPd_1 ? x surface was lower than the Cu segregation to the surface of a clean Cu_xPd_1 ? x CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH_seg(x) and ΔS_seg(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu_xPd_1 ? x is exothermic (ΔH_seg < 0) for all bulk Cu compositions, it is endothermic (ΔH_seg > 0) for S/Cu_xPd_1 ? x. Segregation to the S/Cu_xPd_1 ? x surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu_xPd_1 ? x appear to be related to formation of energetically favored PdS bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.     

The improvement of pyroelectric properties of PZT thick films on Si substrate by TiOx barrier layer

The effects of TiO_x diffusion barrier layer thickness on the microstructure and pyroelectric characteristics of PZT thick films were studied in this paper. The TiO_x layer was prepared by thermal oxidation of Ti thin film in air and the PZT thick films were fabricated by electrophoresis deposition method (EPD). To demonstrate the barrier effect of TiO_x layer, the electrode/substrate interface and Si content in PZT thick films were characterized by scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS), respectively. The TiO_x barrier thickness shows significant influence on the bottom electrode and the pyroelectric performance of the PZT thick films. The average pyroelectric coefficient of PZT films deposited on 400 nm TiO_x layer was about 8.94 × 10⁻⁹ C/(cm² K), which was improved by 70% than those without diffusion barrier layer. The results showed in this study indicate that TiO_x barrier layer has great potential in fabrication of PZT pyroelectric device.     

Phase stability and structure of alkali doped-beta-gallia rutile intergrowths

The incorporation of alkali cations into the tunneled structure of Ga₄TiO₈ was investigated and compared to predictions based on atomistic computer simulations. Samples were prepared as A_xGa_4−xTi_1−xO₈, A=Li, Na, and K, x ≤ 0.7, and as Na_xGa_4+xTi_2−xO₁₀ (x = 0.7, 0.85, and 1.0) using solid-state reactions at 1050–1350 °C. The sodium-containing tunneled structure, Na_xGa_4−xTi_1−xO₈, formed via solid-state reaction, but the potassium and lithium analogs did not. Instead, these systems formed mixed-phase assemblages, which are discussed in reference to compatibility triangles in the Li₂O–Ga₂O₃–TiO₂ and K₂O–Ga₂O₃–TiO₂ systems. Experimental results were compared to the results of energy minimization calculations using the General Utility Lattice Program (GULP). For the lithium-containing system, the computer simulations correctly predicted the formation of a mixed-phase assemblage containing LiGa₅O₈, Ga₂O₃, and TiO₂. For the sodium- and potassium-containing system, the computer simulations suggested that mixtures of the single-cation oxide components should be the stable phase assemblages, in contradiction with experimentally observed results. Energy minimization calculations conducted on structurally different Na_xGa_4+xTi_2−xO₁₀ and Na_xGa_4+xTi_3−xO₁₂ phases indicated that those based on the n = 6 and n = 7 β-gallia rutile intergrowth structures have lower lattice energies than the experimentally observed sodium titanogallate structures reported previously in literature.     

Unusual oxygen re-equilibration kinetics of TiO2−δ

Oxygen re-equilibration kinetics, along with the equilibrium conductivity, have been measured on undoped, single-crystal TiO_2−δ, by a four-probe d.c. conductivity relaxation technique, against oxygen partial pressure in the range of − 16 < log(P_O2/atm) ≤ 0 at different temperatures in the range of 1173 ≤ T/K ≤ 1373. The isothermal conductivity varies as σ ∝ P_O2^m with m ≈ − 1/4, − 1/5 and − 1/6 in turn with increasing P_O2 up to 1 atm, suggesting a sequential variation of the majority ionic disorder types from Ti_i to Ti_i to V_O, respectively. Contrary to the conventional knowledge that due to the local (defect) equilibrium postulate there should be one and only one chemical diffusivity or single relaxation time for a binary oxide, the oxygen re-equilibration kinetics has turned out to be twofold with two different relaxation times depending on oxygen activities. This is interpreted as being due to the independent relaxation of each sublattice of TiO₂ in an oxygen activity gradient applied, indicating a failure of local equilibrium during oxygen re-equilibration. From the two different relaxation times the chemical diffusion coefficients of component Ti and O are separately evaluated and subsequently, their self-diffusion coefficients. The latter are found to be in a good agreement with the literature data.     

Electrical properties of yttrium doped strontium titanate with A-site deficiency as potential anode materials for solid oxide fuel cells

Yttrium doped strontium titanate with A-site deficiency ((Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ) was synthesized by conventional solid state reaction. The deficiency limit of A-site in (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ is below 6 mol% in Ar/H₂ (5%) at 1500 °C. The sinterability of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples decreases slightly with increasing A-site deficiency level (x). The ionic conductivity of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples increases while the electronic conductivity decreases with increasing A-site deficient amount. The defect chemistry analysis indicates that the introduction of A-site deficiency results in not only the increase of oxygen vacancy concentration but also the decrease of Ti³⁺-ion concentration. The latter plays the main role in the electrical conduction. (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ shows good thermal-cyclic performance in electrical conductivity and has an excellent chemical compatibility with YSZ electrolyte below 1500 °C.     

Investigations on structural,elastic, thermodynamic and electronic properties of TiN,Ti2N and Ti3N2 under high pressure by first-principles

The lattice parameters, cell volume, elastic constants, bulk modulus, shear modulus, Young's modulus and Poisson's ratio are calculated at zero pressure, and their values are in excellent agreement with the available data, for TiN, Ti₂N and Ti₃N₂. By using the elastic stability criteria, it is shown that the three structures are all stable. The brittle/ductile behaviors are assessed in the pressures from 0 GPa to 50 GPa. Our calculations present that the performances for TiN, Ti₂N and Ti₃N₂ become from brittle to ductile with pressure rise. The Debye temperature rises as pressure increase. With increasing N content, the enhancement of covalent interactions and decline of metallicity lead to the increase of the micro-hardness. Their constant volume heat capacities increase rapidly in the lower temperature, at a given pressure. At higher temperature, the heat capacities are close to the Dulong–Petit limit, and the heat capacities of TiN and Ti₂N are larger than that of c-BN. The thermal expansion coefficients of titanium nitrides are slightly larger than that of c-BN. The band structure and the total Density of States (DOS) are calculated at 0 GPa and 50 GPa. The results show that TiN and Ti₂N present metallic character. Ti₃N₂ present semiconducting character. The band structures have some discrepancies between 0 GPa and 50 GPa. The extent of energy dispersion increases slightly at 50 GPa, which means that the itinerant character of electrons becomes stronger at 50 GPa. The main bonding peaks of TiN, Ti₂N and Ti₃N₂ locate in the range from −10 to 10 eV, which originate from the contribution of valance electron numbers of Ti s, Ti p, Ti d, N s and N p orbits. We can also find that the pressure makes that the total DOS decrease at the Fermi level for Ti₂N. The bonding behavior of N–Ti compounds is a combination of covalent and ionic nature. As N content increases, valence band broadens, valence electron concentration increases, and covalent interactions become stronger. This is reflected in shortening of Ti–N bonds.     

An XAS study of the defect structure of Ti-doped α-Cr2O3

The bulk defect structure in Cr_2−xTi_xO₃ (x = 0.05, 0.20 and 0.30) has been studied by X-ray absorption spectroscopy measurements at the Cr and Ti K-edges. The results show that the Ti is predominantly present in the IV oxidation state and resides on the normal Cr host lattice site. The dopant is charge compensated by Cr³⁺ vacancies and there is evidence for the formation of defect clusters; however, the detailed structure of these clusters could not be deduced.     

Synthesis and visible light photocatalysis water splitting property of chromium-doped Bi4Ti3O12

Photocatalysts Bi₄Ti_3 ? xCr_xO₁₂(x = 0.00, 0.06, 0.15, 0.30, 0.40, and 0.50) with perovskite structure were synthesized by sol–gel method and their electronic structures and photocatalytic activities were investigated. The Bi₄Ti_2.6Cr_0.4O₁₂ photocatalyst exhibited the highest performance of H₂ evolution in methanol aqueous solution (58.1 μmol h^? 1 g^? 1) under visible light irradiation (λ > 400 nm) without a co-catalyst, whereas no H₂ evolution is observed for Bi₄Ti₃O₁₂ under the same conditions. The UV–vis spectra indicated that the Bi₄Ti_2.6Cr_0.4O₁₂ had strong photoabsorption in the visible light region. The results of density functional theory (DFT) calculation illuminate that the conduction bands of Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 6p orbitals, and the valence bands are composed of O 2p + Bi 6s hybrid orbitals, while the conduction bands of chromium-doped Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 2p + Cr 3d orbitals, and the O 2p + Cr 3d hybrid obitals are the main contribution to the valence band.     

LiMn2−xTixO4 spinel-type compounds (x ≤ 1): Structural,electrical and magnetic properties

LiMn_2−xTi_xO₄ compounds with 0 ≤ x ≤ 1 were prepared by solid state reaction and Pechini technique. Powder X-ray diffraction showed that all samples crystallize with the spinel crystal structure (S.G. Fd3¯m). The cubic unit-cell parameter increases with the Ti content. The influence of the Ti content and cationic distribution on the magnetic properties of the compounds was studied by measuring the temperature and magnetic field dependences of the magnetization: substitution by non-magnetic d⁰ Ti⁴⁺ ions appeared to weaken the magnetic interactions between the manganese ions. The electrical properties of LiMnTiO₄ were studied by AC impedance spectroscopy and DC polarisation measurements, which revealed the electronic character of the conduction process.