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Laser ablation of metallic targets in gas atmospheres gives rise to the formation of nanoparticle (NP) powders when high laser irradiances (i.e., > 1 GW/cm² for aluminium targets) are used. The properties of the NPs so formed vary as a function of the laser irradiation parameters and the pressure and composition of the ambient gas. Here, we studied the composition and structure of NPs formed by laser ablation of Al targets with a nanosecond Nd:YAG laser emitting at 1064 nm. The laser irradiance was 2.5 GW/cm2. N2–O2 gas mixtures containing different amounts of nitrogen (100–80 vol% N2) were used as ambient gas at atmospheric pressure. The influence of the ambient gas composition on the morphology and the structure of the NPs was studied ex-situ by scanning and transmission electron microscopy, X-ray diffraction and micro-Raman spectroscopy. Their composition of light elements was determined by ion beam analysis. It was shown that together with metallic aluminium, different amounts of aluminium nitride and aluminium oxynitride were formed in the NPs as a function of the nitrogen concentration in the ambient gas. Below 95 vol% N2, the concentration of nitride phases decreases strongly. However, the formation of aluminium oxide (Al2O3) was not observed, whereas it was detected in NPs formed in air. A discussion of these results that takes into account the dynamics of the plasma plume is proposed.

In this study, the characterization of nanostructured Pt-doped CeO2 films with low platinum content and porous structure is reported, deposited on silicon substrate by direct liquid injection chemical vapor deposition. The platinum localization and concentration in the nanocomposite are determined by scanning transmission electron microscopy associated with energy dispersive X-ray spectroscopy. Films are made of approximate to 3 nm diameter CeO2 particles and platinum is homogeneously dispersed through the layers. X-ray photoelectron spectroscopy (XPS) also shows that platinum is mainly in an ionic Pt2+ state. After diffusion through the preformed porous structure of ceria films, the platinum precursor decomposes at the surface of each ceria particle forming the films, producing a homogeneous platinum-doped CeO2 nanocomposite. This result is supported by synchrotron radiation XPS experiment, where the measured relative Pt concentration demonstrates that platinum is decomposed only at the surface of ceria particles. Finally, when the saturation of Pt2+ sites at the surface of ceria particles is reached, metallic nanoclusters are formed from platinum excess.

The combination of photoelectron diffraction, density functional theory, and multiple scattering calculations is used for a quantitative analysis of the widely debated structure of ${\mathrm{TiO}}_{2}$ (011). The modeling of the diffraction patterns for different surface reconstructions allows one to discriminate the key structural constraints required or, on the contrary, prohibited in the reconstruction of this termination. In particular, photodiffraction rules out previously proposed reconstructions while it evidences the key feature of the ${\mathrm{TiO}}_{2}$ (011) termination: an oxygen splitting induced by missing rows.

An in-depth study of the first steps of electron beam assisted growth of Mo from molybdenum hexacarbonyl on Cu(1 1 1) has been carried out exploiting the complementarity of X-ray photoemission and X-ray absorption spectroscopies. Frank van der Merwe (2D) growth mode has been observed for the completion of the two first monolayers of adsorbed molecules through a simple physisorption process. Irradiation of the Mo(CO)6 deposit by 1 keV electron beam induces a modification of molybdenum coordination, the average number of C-neighbors decreasing from 6 to 3. Decomposed molecules remain on the surface after annealing at 520 K and organize themselves, the molybdenum atoms moving in Cu(1 1 1) surface fcc hollow sites. After annealing at 670 K, metallic molybdenum growth begins, if the total amount of adsorbed Mo atoms exceeds 1.2 monolayers.

International audience; KxWO3 nanorods, interesting as gas sensors, were elaborated on mica muscovite substrate and characterized by atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and mainly transmission electron microscopy. A combination of structural analyses allowed determining the morphology of these rods, and selected area electron diffraction experiments pointed out the simultaneous presence of the exotic hexagonal and stable monoclinic phases. Moreover, the presence of potassium inside the nanorods, coming from the mica substrate, was revealed. By combining all the observations, a growth model is proposed, consisting of the stacking of two different crystallographic structures. An interfacial hexagonal KxWO3 tungsten bronze grows in epitaxy on the mica substrate, followed by the growth of monoclinic trioxide tungsten. The stability of these nanometric objects was studied by annealing up to 870 K, indicating that the transformation of the presumed metastable hexagonal phase never occurred.

International audience; Molybdenum carbonyl Mo(CO)(6) was adsorbed on the Cu(111) surface at 160 K in the monolayer coverage range and studied by scanning tunneling microscopy. A well-ordered monolayer of hexacarbonyl molecules was observed experimentally for the first time. The monolayer has a hexagonal structure compatible with a (root 7 x root 7)R19 superlattice on the copper (111) plane. The arrangement and orientation of the molecules on the surface were determined by density functional theory calculations, including van der Waals interactions. The comparison of adsorption and cohesive energies reveals that the molecule-substrate interaction is stronger than the intermolecular one, which explains the observed two-dimensional growth.

International audience; Tunneling induced decomposition of Mo(CO)(6) from the gas phase was studied on TiO2(110) surface by scanning tunneling microscopy (STM) and spectroscopy (STS). The efficiency of the procedure was followed by measuring the dot volume as a proportional indicator of the amount of the decomposed precursor. It was found that below 1 x 10(-5) Pa background pressure of Mo(CO)(6), there is no measurable effect and above 1 x 10(-4) Pa, the nanodot size is too large compared to the curvature of the tip (20-40 nm). A threshold bias of +3.1(+/- 0.1) V on the sample was measured for the decomposition of Mo(CO)(6) in gas ambient. In the absence of the precursor, dot formation was observed only above +3.7(+/- 0.2) V, in good agreement with the results reported in our earlier work about nanolithography on clean TiO2(110) substrate (E. Krivan, A. Berko: J. Vac. Sci. & Tech. B 15(1) (1997)25). By applying voltages in the range of 3.1-3.5 V, a systematic enlargement of the created nanodots was found in the range of 2-20 s of duration and 0.01-1.0 nA of tunneling current. The I-V curves detected on the top of the nanodots have shown that the created features are of insulator character. This observation indicates that the decomposition of Mo(CO)(6) is also accompanied by oxidation of the deposited Mo species. (C) 2011 Elsevier Ltd. All rights reserved.

Import JabRef; International audience; Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

International audience; WOx and MoOx nano phases were prepared on TiO2(1 1 0) surfaces by a CVD procedure consisting of adsorption and decomposition of W(CO)(6) or Mo(CO)(6) precursors followed by annealing under UHV. Metal amount involved in each elaborated sample is in the fractional range from 0.1 to 0.35 equivalent monolayer (eqML) of W or Mo. Evolution of sample stoichiometry as a function of subsequent treatment is followed by valence band and core level photoemission as well as work function measurement. In each case, exposure of samples to molecular oxygen at room temperature induces an increase of sample work function in a range of several tenth of eV. Such a work function change is related to oxidation of sample involving both titanium and tungsten (or molybdenum) ions. Such an oxidation is reversible through an annealing under UHV at 470 K for molybdenum oxide and 670 K for tungsten oxide. Several cycles of exposure/annealing are possible without changes in work function or stoichiometry. (C) 2011 Elsevier B.V. All rights reserved.

The evolution of the nanoscale structure and the chemical bonds formed in Ti–C–N–O films grown by reactive sputtering were studied as a function of the composition of the reactive atmosphere by increasing the partial pressure of an O2+N2 gas mixture from 0 up to 0.4 Pa, while that of acetylene (carbon source) was constant. The amorphisation of the films observed by transmission electron microscopy was confirmed by micro- Raman spectroscopy, but it was not the only effect associated to the increase of the O2+N2 partial pressure. The chemical environment of titanium and carbon, analysed by X-ray photoemission spectroscopy, also changes due to the higher affinity of Ti towards oxygen and nitrogen than to carbon. This gives rise to the appearance of amorphous carbon coexisting with poorly crystallized titanium oxynitride. The evolution of the films colour is explained on the basis of these structural changes., Fundação para a Ciência e a Tecnologia (FCT) - PTDC/CTM/69362/2006, SFRH/BPD/27114/2006, CRUP (Acção Integrada Luso-francesa N° F-2307) and the GRICES/CNRS collaboration (Proc. 4.1.1 França)

International audience; This study is concerned with the elaboration of barium silicate thin films by metal organic chemical vapor deposition (MOCVD) and in situ characterization by X-ray photoemission spectroscopy (XPS) with an apparatus connected to the deposition reactor. The difficulty to find an efficient metal organic precursor for barium is described. After characterizations of the selected reactant, Ba(TMHD)2tetraglyme, the development of an original specific vapor delivering source which allows reactant sublimation in the CVD reactor was performed. In the most optimized cases, including use of oxygen introduction during the deposition, barium silicate films were obtained. Moreover, non-negligible amounts of carbon and presence of barium oxide on the top of the layers were observed.

International audience; Synchrotron based photoemission spectroscopy was used to study the adsorption of tungsten hexacarbonyl on SiO2 surfaces modified by potassium. Results were compared with the ones obtained when no potassium was present. Experiments using W4f and Si2p intensities variations show that, at 140 K, the tungsten hexacarbonyl growth proceeds via a simultaneous multilayer mode for the two kinds of surfaces but with differences in compositions of growing layers. Indeed, it is evidenced that, even at cryogenic temperatures, the presence of potassium induces decomposition of a significant part of tungsten hexacarbonyl molecules through a strong interaction between tungsten and potassium atoms in opposition to potassium-free surface cases where W(CO)6 molecules are simply physisorbed. Additional irradiation of adsorbed molecules with photons coming from 0-order synchrotron radiation, subsequent going back to room temperature and additional thermal treatments up to about 700 K were then used to induce further decomposition of the adsorbed precursor. It allows as well to get rid of carbon and, finally, to stabilize different W-based species on the surface. The state of tungsten remaining on the surface is then strongly influenced by presence of potassium. When potassium is present, highly oxidized tungsten species are observed, whereas reduced species are mainly detected for potassium-free surfaces. Moreover, as diffusion of potassium is revealed during formation of tungsten phase, one should guess that potassium plays a crucial role in tungsten oxidation mechanism.

Laser treatment of a titanium surface at certain conditions initiates the formation of titanium oxide layers as well as micro (nano) scale powder ejected from the surface of the substrate. The resultant morphology of the surface as well as the size and the structure of the particles are all strongly dependent on the treatment parameters (laser fluence, pulse frequency, overlap parameter, etc.). In this study, titanium substrates were treated with an industrial pulsed Nd:YAG laser in air, with varying parameters. Surface layers and ejected materials were compared using scanning and transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The rutile phase of TiO(2) dominates in the surface layers, while the ejected powder is mainly formed of anatase nanoparticles. (C) 2008 Elsevier B. V. All rights reserved.

International audience; Incorporation of oxygen into TiN lattice results in formation of titanium oxynitrides, TiOxNy that have become particularly interesting for photocatalytic applications. Elaboration as well as characterization of TiN and in situ oxygen-doped thin films is the subject of this paper. Thin films, 250–320nm in thickness, have been deposited by dc-pulsed magnetron reactive sputtering from Ti target under controllable gas flows of Ar, N2 and O2. Optical monitoring of Ti plasma emission line at = 500nm has been implemented in order to stabilize the sputtering rate. Scanning electron microscopy (SEM), X-ray diffraction in grazing incidence (GIXRD), micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), optical spectrophotometry and four-point probe electrical resistivity measurements have been performed in order to follow evolution of film physical parameters as a function of the oxygen flow rate O2 at which the films were deposited. The relationship between O2 expressed in standard cubic centimetres per minute, sccm and the nitrogen/oxygen content in thin films has been established by means of the analysis of the XPS spectra. GIXRD studies indicate that incorporation of oxygen results in a progressive loss of preferential orientation in 111 direction, a change in the grain size from 16nm for TiN to about 3 nmfor films deposited at O2 = 1.32 sccm and a decrease in the lattice constant. A systematic shift of all X-ray diffraction (XRD) lines towards higher diffraction angles is consistent with substitution of oxygen for nitrogen. Micro-Raman investigations indicate amorphisation of thin films upon oxidation. Binding energies determined fromfitting of the XPS results concerning the N1s and Ti2p lines give evidence of the presence of TiOxNy compound. Red-shift of the plasma reflectance edge upon TiN oxidation is correlated with a decreased carrier concentration. Metal–semiconductor transition can be expected on the basis of the electrical conductivity decrease and development of the fundamental absorption across the forbidden band of TiO2 upon increase in the oxygen flow rate. Additional absorption feature in the visible range, being a consequence of coexistence of free-electron and interband absorption within almost the same spectral range ( = 400–600 nm) seems to be very promising for photocatalytic applications of titanium oxynitride thin films.

International audience; Titanium oxynitride layerswere formed by surface laser treatment of Ti plates in air using a Nd:YAG laser source of short pulse duration about 5 ns. The cumulated laser fluence was varied in the 100–1200 J cm2 range and its influence on the composition and the structure of the formed layers was studied by different characterization techniques providing physico-chemical and structural information. It was shown that the laser treatment induces the insertion of light elements as O, N and C in the formed layer with the amount increasing with the laser fluence. The in-depth composition of the layers and the co-existence of different phases were also studied. The way in which the laser parameters such as fluence affect the insertion of nitrogen and oxygen was discussed in connection with the effects of the plasma plume formed above the target.

International audience; We report a first principles study on the structure and energetics of thin films of molybdenum on a (1 1 0) surface of rutile TiO2. Mo films with 1 × 1 epitaxy in the coverage range between 0.5 and 2 monolayer are investigated. The most stable structures are those which maximize the number of Mo–Mo bonds. This leads to two-dimensional structures with zigzag Mo–Mo coordination for 1 monolayer coverage and three-dimensional structures with approximately body-centered cubic coordination for higher coverage. For a coverage up to 1.5 monolayers, the interface Mo atoms preferentially occupy the so-called upper hollow adsorption site with three Mo–O bonds

International audience; A study on the field-induced tip–surface oxygen transfer at room temperature and its influence on the tunneling conditions for stable STM imaging of the TiO2(110) (1 1) surface is reported. A simple model of field-induced transfer is applied to tungsten and platinum–iridium tips. The oxygen transition rates from the sample to the tip or from the tip to the sample depend on the oxygen desorption barriers formed at tunneling distance. For stable imaging the applied bias voltage has to balance the oxygen transfer probabilities in both directions. In the case of Pt/Ir tips, the tunneling conditions for images with clear evidence of bridging oxygen point defects have been established.

International audience; Room temperature depositions of barium on a thermal silicon oxide layer were performed in ultra high vacuum (UHV). In-situ X-ray photoelectron spectroscopy (XPS) analyses were carried out as well after exposure to air as after subsequent annealings. These analyses were ex-situ completed by secondary ion mass spectrometry (SIMS) profiles and transmission electron microscopy (TEM) cross-sectional images. The results showed that after air exposure, the barium went carbonated. Annealing at sufficient temperature permitted to decompose the carbonate to benefit of a barium silicate. The silicate layer was formed by interdiffusion of barium with the initial SiO2 layer.

International audience; TiO2 thin films were deposited on soda–lime glass substrates by reactive direct current magnetron sputtering in a mixture of pure argon and oxygen. The influence of both the deposition time, td, and the post-annealing treatments on the films morphology, composition and structure was analyzed by scanning electron microscopy, ellipsometry, X-ray photoelectrons spectroscopy, X-ray diffraction (XRD) and Raman spectroscopy. Amorphous TiO2 was obtained for the shortest deposition time, td=15 min. Increasing td up to 30 min, poorly crystallized anatase and rutile phases were formed together with amorphous TiO2, as was revealed by complementary XRD patterns and Raman spectra. For longer td, the growth of the anatase phase dominates that of the rutile phase. The post-annealing treatment of the films in air at 450 °C. induced the complete crystallization of the films leading to mainly anatase films for all the deposition times. All these results show the feasibility to fabricate stoichiometric TiO2 thin films with amorphous to crystalline structures by means of soft fabrication conditions: low substrate temperature and moderate annealing treatment.

International audience; Tungsten oxide nanorods are grown at atmospheric pressure and low temperature (360 1C), by sublimation of WO3 and condensation on mica substrates. The nanorods are characterized by atomic force microscopy, high-resolution electron microscopy, energy-dispersive X-ray spectroscopy and high energy electron diffraction. The experimental results evidence the formation of a hexagonal tungsten bronze at the nanorod–substrate interface. The epitaxial relationships of the nanorods on mica are determined and the role of epitaxial orientation of the interfacial bronze in the nanorod growth and morphology are discussed.

Synchrotron-based photoemission spectroscopies were used to study the adsorption of tungsten hexacarbonyl on (1 1 0) TiO 2 surfaces: experiments using W4f and Ti2p intensities variations show that, at 140 K, the hexacarbonyl growth proceeds via a layer-by-layer mode. Moreover, it was evidenced using both core levels and valence band experiments that, after back to room temperature, W(CO) 6 desorbs without significant decomposition. However, low energy (500 eV) ion (Ar + ) irradiation can allow partial decomposition of tungsten hexacarbonyl molecules leading to sub-carbonyl tungsten molecules. The bonding of sub-carbonyl species to the TiO 2 surface was then stronger than the one of hexacarbonyl: these chemisorbed species do not desorb when going back to room temperature allowing a higher amount of metal to remain on the surface. Subsequent annealing gets rid of remaining carbonyl groups. This phenomenon leaves tungsten atoms at the TiO 2 surface. The annealing organizes these W atoms in the 400–600 K temperature range leading to WO x phases, which are almost free of carbon. The oxidation degree of these phases is strongly related to tungsten amount remaining at the surface.

International audience; In situ Angle Resolved X-ray Photoemission Spectroscopy (ARXPS) characterizations of TiO2 thin films grown on silicon by Metal Organic Chemical Vapour Deposition were performed in order to get information on interfacial reactions at the first stages of the growth, one of the aims being to understand the influence of deposition conditions. Thickness measurements were also carried out from ARXPS analyses. As the real structure of the films was shown to be a double layer system such as TiO2/SiO2/Si, an ARXPS model of thickness and surface coverage determination was applied to each layer independently. However, the application of this model to very thin films underestimates the surface coverage of the interfacial layer. A “Double Layer” model taking into account the attenuation of the silicon oxide and substrate signals by the external layer was also developed.

Molybdenum was deposited in two steps (3 eq. ML and 1 eq. ML) on the light blue rutile TiO2 10) (1 x 1) surface at room temperature, each Mo deposition cycle being followed by an annealing up to 950-1000 K. This procedure was found to lead to formation of separated clusters having a size in very wide range (1-20 nm). Scanning tunneling microscopy showed a dependence of the cluster morphology as a function of the size. The scanning tunneling spectra of Mo clusters was studied as a function of cluster dimensions and discussed in comparison with photoelectron spectroscopy results previously obtained for homogeneous Mo films. The dI/d V curves do not display the valence band structure of deposited material, which could be explained by the Schottky barrier formation. (C) 2007 Elsevier B.V. All rights reserved.

International audience; The adsorption and decomposition of molybdenum hexacarbonyl on (110) TiO2 surfaces were studied using both core levels and valence band photoemission spectroscopies. It was found that after an adsorption at 140 K, when going back to room temperature, only a small part of molybdenum compounds, previously present at low temperature, remained on the TiO2 surface. This indicates that the desorption temperature on such a surface is lower than the decomposition one. The use of photon irradiation to decompose the hexacarbonyl molecule was also studied. It was shown that during such a decomposition molecular fragments were chemisorbed on the surface allowing a higher amount of metal to remain on the surface. It was also shown that it was possible to get rid of adsorbed subcarbonyl groups and to organize the metal atoms by thermal treatments at temperatures as low as 400 K, i.e. much lower than the one needed to obtain the same structures using physical vapour deposition (PVD). Moreover, due to lower used temperatures, this chemical way of deposition allows a better control of the interface than during PVD growth.

International audience; 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.

We report photoelectron diffraction (PED) experiments of weakly sub-stoichiometric TiO 2 (100) rutile surfaces. Apart from standard core-level PED from the Ti-2p3/2 line, we have studied valence band PED from the defect induced Ti-3d states in the insulating band gap. For maximum yield, the latter were resonantly excited at the Ti-2p absorption edge. The PED patterns have been analyzed within the forward scattering approximation as well as by comparison with simulated PED patterns obtained in multiple scattering calculations. The analysis shows that the defect induced Ti-3d charge is mainly located on the second layer Ti atoms. © 2007 Elsevier B.V. All rights reserved.

International audience; This study is concerned with the chemical characterization of metallic gallium droplets, obtained on silicon (1 0 0) substrates with a single growth step, by the LP-MOCVD technique with TMGa like precursor. These structures are characterized by SIMS, XPS and TEM. The analyses results lead to a structure proposition for the droplets. The core is composed of metastable metallic gallium with a non-negligible carbon quantity probably coming from incomplete precursor decomposition. The outer part, composed of gallium oxide maintains the structure stability. Covering of the substrate by a thin gallium layer of gallium compounds is observed.

International audience; Angle-resolved X-ray photoelectron spectroscopy (ARXPS) experiments were performed to study in situ the reaction at the film–substrate interface during metal organic chemical vapor deposition (MOCVD) growth of TiO2 thin films deposited on the silicon substrate. The in-depth distribution of chemical species was determined using several ARXPS thickness calculation models considering either single or bilayer systems. By the comparison of two single-layermodels, the presence of a second layer composed of silicon oxidewas evidenced. High-resolution transmission electron microscopy (HRTEM) observations confirmed the stratification of the film in two layers, as well as the perfect wetting of the surface by TiO2, irrespective of the model used. The contribution of the ARXPS bilayer model was demonstrated by the agreement of the values of film thickness obtained by both techniques. Nevertheless, the correlation between each layer's thickness was only possible by taking into account chemical species mixing. Indeed, the presence of oxidised silicon in the upper TiO2 layer, in addition to that of the SiOx interlayer, has to be considered to interpret ARXPS results in a correct way.

International audience; Homogeneous collections of Pd−Ni core−shell nanoparticles have been prepared by decomposition of metal−organic compounds and studied by several electron microscopy techniques: transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM), energy-filtered microscopy (EFTEM), and by X-ray photoelectron spectroscopy (XPS). The physical and chemical properties of the Pd shell are supposed to depend on its electronic properties, which are influenced by the presence of the Ni core and by the deformation in the Pd lattice. Here, the interfacial structure of Pd/Ni and the lattice deformations in the core and the shell are studied in detail. The catalytic properties of the pure metal and the bimetallic particles, toward CO oxidation, have been investigated.

The electronic structure of titanium dioxide surfaces having undergone different preparations leading to different stoichiometries and crystallinities has been studied using resonant photoemission spectroscopy. Valence band photoemission spectra through the Ti 3p–3d/4s absorption edge between 45 and 55 eV were measured and allowed a characterization of defects present at the surface as well as of the quality of the surface organization. Indeed, from the comparison of the resonance results obtained for each kind of surface with the LEED patterns on the one hand and the corresponding Ti 2p core level lines on the other hand, it was evidenced that the high binding energy part of the valence band seems rather related to the ordering of the surface than to the amount of defects.

International audience; The ability to determine the nature and the occurrence of defects is a central need of ceramic surface chemistry. In titanium oxides, the Ti-LMV Auger decays line shape is very sensitive to the titanium degree of oxidation, and has long been empirically used as a qualitative probe of the stoichiometry. In the present work, resonant Auger and resonant valence-band measurements at the Ti-L2,3 edges in TiO2, TiO2–x and metallic titanium provide a clear evidence that the evolutions of the Ti-LMV Auger line shape are due to drastic changes in the valence-band profile and in the probability of L2L3V Coster-Kronig decay processes when a fraction of titanium ions is reduced. Both are shown to be consequences of the filling of Ti-3d states near the Fermi level on defects sites. These conclusions are confirmed by Auger-photoelectron coincidence experiments.

TiO2/TiNxOy δ-doping structures were grown on the top of (1 1 0)TiO2 rutile substrates by low pressure metal-organic vapor phase epitaxy (LP-MOVPE) technique at 750 °C. The samples were analyzed by high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS) and X-ray diffraction techniques (rocking curves and φ-scans). The presence of satellites in the (1 1 0)TiO2 rocking curve revealed the epitaxial growth of 10 period δ-doping structures. The thickness of the TiO2 layers, 84 nm, was deduced from the satellites period. HRTEM observations showed around 1.5 nm thick δ-doping layers, where the presence of nitrogen was detected by EELS. The analysis of the Bragg surface diffraction peaks observed in the φ-scans points to an almost negligible strain in this sample which was confirmed by substrate curvature radius measurements.

Molybdenum was deposited on blue (i.e. non-stoichiometric) TiO2(1 1 0) surface using a very low deposition rate (less than 0.05 eqML min−1). The resulting deposit was investigated by means of X-ray photoelectron diffraction (XPD), LEED and XPS. Just after deposition, the film is mainly constituted of metallic molybdenum, contains oxygen homogeneously dispersed through the whole deposit and the broad features detected in XPD scans are interpreted as a coarse epitaxy between TiO2(1 1 0) surface and the (0 0 1) face of bcc molybdenum. The orientation relationship is: Mo(1 0 0)[0 0 1]//TiO2(1 1 0)[0 0 1]. After annealing the deposit at 673 K, XPD scans become sharper and epitaxy is achieved even if no LEED pattern is observed. Moreover, the annealing induces a noticeable decrease of the oxygen content inside the film.

International audience; We report the percolation behaviour of the conductivity of titanium oxynitride films grown by low-pressure metal-organic chemical vapour deposition, composed of TiNxOy mixed with TiO2. The usual DC parameters (t, s and Φc), obtained from the effective media theory equations, are compared to the universal values (s = sun while t < tun because of the film anisotropy). This is the first example of an electrical continuum percolation applied to columnar films with chemically similar conducting and insulating units (non-heterogeneous percolation) whose mixing is based upon the growth temperature during the film growth.