Effect of the Mo atom flow on the molybdenum growth on TiO2 (110) surface

Abstract Molybdenum has been deposited at room temperature on stoichiometric TiO 2 (1 1 0) surfaces with two deposition rates: 0.1 equivalent monolayer (eqML) and 1.5 eqML min −1 . X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy studies clearly reveal an effect of the deposition rate upon the growth mode and the interfacial reaction. Indeed, whereas a strong interfacial reaction between Mo and TiO 2 involves a Stranski–Krastanov growth mode with the formation of amorphous molybdenum oxide monolayers for the lowest deposition rate, no reaction can be observed for the highest deposition rate. Moreover in this latter case, the growth mode seems to be a 3D …

Molybdenum deposition on TiO2 (110) surfaces with different stoichiometries

Abstract The deposition of ultra thin molybdenum films has been carried out on three different TiO 2 surfaces: a stoichiometric and flat one obtained after annealing, a non stoichiometric and rough surface made by Ar + bombardment and a stoichiometric and rough surface obtained by oxygen bombardment. Whatever the substrate preparation, in situ AES and XPS studies and ex situ AFM and RHEED characterizations have revealed a Stranski–Krastanov growth mode: the completion of three monolayers followed by island growth is observed in any case. The three monolayers are composed of amorphous molybdenum oxide with a molybdenum oxidation state between III and IV. The oxidation of the molybdenum layer…

Structure and Deformations of Pd−Ni Core−Shell Nanoparticles

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 t…

Development of dark Ti(C,O,N) coatings prepared by reactive sputtering

Accepted manuscript

Structural and electrical properties of magnetron sputtered Ti(ON) thin films:The case of TiN doped in situ with oxygen.

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…

Experimental and theoretical evidence for substitutional molybdenum atoms in theTiO2(110)subsurface

Molybdenum was deposited at room temperature on the ${\mathrm{TiO}}_{2}(110)$ surface in the 0--1.3 equivalent monolayer (eqML) range and was then annealed at $400\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$ in order to reach a kind of equilibrium state. A threshold was found in the behavior of the deposit: below 0.2 eqML, substitutional molybdenum occurs in titanium sites located under the bridging oxygen atoms of the ${\mathrm{TiO}}_{2}(110)$ surface. In this position, molybdenum atoms are in a structural and chemical ${\mathrm{MoO}}_{2}$-like environment. Density-functional theory calculations show that this molybdenum site is actually the most stable one in …

Nitrogen plasma pressure influence on the composition of TiNxOy sputtered films

Thin films of TiNxOy were deposited by d.c. magnetron sputtering on glass substrates using an (Ar+,N2) plasma and Ti target. The N2 partial pressure was changed from 2.3 × 10−4 mbar to 4.6 × 10−3 mbar in order to obtain films with increasing nitrogen contents. X-ray photoelectron spectroscopy was used to determine the as-deposited composition. The presence of oxygen, which is probably due to contamination from the residual atmosphere in the vacuum chamber, is always detected, both in the surface layers and in the bulk of the films, confirming the formation of TiNxOy. When the nitrogen partial pressure was increased, a maximum for the nitrogen content in the films was reached, corresponding …

Electronic exchanges between adsorbed Ni atoms and TiO2(110) surface evidenced by resonant photoemission

Abstract Nickel was deposited on stoichiometric TiO2(1 1 0) surface in the 0.02–2.1 equivalent monolayer (eqML) range and analyzed by means of photoemission and resonant photoemission. In the case of very low coverage (lower than 0.1 eqML), deposited nickel reacts with the surface through an electronic transfer from nickel atoms towards titanium ions. This exchange caused the filling of unoccupied Ti3d states leading to the increase of a peak in the TiO2 band gap. These states can be better characterized through resonant photoemission experiments at the Ti 3p → 3d absorption edge: for very low coverage, these states in the TiO2 band gap have resonant behavior of Ti3d electrons rather than N…

Defects at the TiO2(100) surface probed by resonant photoelectron diffraction.

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.

Structure and chemical bonds in reactively sputtered black Ti–C–N–O thin films

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 nitro…

Chemical characterization of gallium droplets grown by LP-MOCVD.

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.

Anisotropic and non-heterogeneous continuum percolation in titanium oxynitride thin columnar films

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.

Reversible oxidation of WOx and MoOx nano phases

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 i…

MoO (x≤2) ultrathin film growth from reactions between metallic molybdenum and TiO2 surfaces

Abstract Exposures to oxygen at room temperature and annealings under vacuum were carried out on deposits obtained from molybdenum interacting with (1 1 0) TiO 2 surfaces in order to obtain molybdenum oxide ultra thin films. Exposures to oxygen at room temperature show that the interfacial molybdenum oxide layers resulting from the TiO 2 /Mo interactions are inactive towards oxygen whereas the metallic molybdenum clusters, which grew on top of the interfacial layers, oxidise into MoO 3 . Besides, during annealings under vacuum, substrate oxygen anions can diffuse into the deposit. Thus, between 400 and 500°C, molybdenum oxide layers are progressively oxidised into MoO 2 . Moreover, from the…

CVD elaboration and in situ characterization of barium silicate thin films.

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,…

Structural characterization of original 3D gallium structures grown by LP‐MOCVD

This study is concerned with the growth and characterization of metallic gallium 3D structures, obtained with a single growth step, by the LP-MOCVD technique on various substrates. Commercial organo-metallic is used as gallium precursor and nitrogen as carrier gas. The growth temperature and the reactor pressure are ranking between 500 and 700 °C, and between 150 and 700 torr, respectively. Depending on the elaboration conditions, different 3D structures are obtained such as droplets, cauliflowers, aggregates or thin stems, with micrometer sizes. The morphology, substrate surface density and thermal stability are studied by optical and scanning electron microscopy. At last, X-ray microanaly…

Surface preparation influence on the initial stages of MOCVD growth of TiO2 thin films

In situ chemical surface analyses using X-ray photoelectron spectroscopy (XPS), completed by ex situ atomic force microscopy (AFM) analyses, were performed in order to compare the initial stages of MOCVD growth of TiO 2 thin films on two different surface types. The first type was a silicon native oxide free hydrogen terminated surface and the second one was a silicon dioxide surface corresponding to a thin layer of 3.5 nm thick in situ thermally grown on silicon substrate. Si(100) was used as substrate, and the growths of TiO 2 thin films were achieved with titanium tetraisopropoxide (TTIP) as precursor under a temperature of 675 °C, a pressure of 0.3 Pa and a deposition time of 1 h. Whate…

Pd–Pt alloys: correlation between electronic structure and hydrogenation properties

Abstract Palladium and its alloys have been extensively studied because of their faculty to store reversibly hydrogen isotopes. Here, the substitution of palladium with platinum is investigated. Thermodynamical studies have shown an anomalous behaviour regarding to the classical models. This original behaviour is explained by the study of the electronic structure of the binary solid solutions. The drastic decrease of the hydrogen solubility in the Pd–Pt alloys is accounted for by the filling up of the palladium conduction band by the valence electrons of platinum. The anomalous decrease of the stability of the hydride is explained by the large broadening of the valence band due to the subst…

MOVPE growth of Ga 3D structures for fabrication of GaN materials

Abstract This paper presents the growth and characterization of metallic gallium three-dimensional (3D) structures and preliminary results of their transformation into GaN-like structures. The structures were grown by metal-organic vapour phase epitaxy (MOVPE), using trimethyl gallium as gallium precursor on silicon (1 0 0). The growth temperature was between 550°C and 750°C. Interesting and new metallic structures were obtained with our growth parameters: balloon (montgolfier-like structure) and cauliflower-like. These metallic structures can grow up perpendicular to the substrate surface and have diameters between 0.1 and 5 μm, depending on the growth conditions. Moreover, selective metal…

Defect States at theTiO2(110)Surface Probed by Resonant Photoelectron Diffraction

The charge distribution of the defect states at the reduced ${\mathrm{TiO}}_{2}(110)$ surface is studied via a new method, the resonant photoelectron diffraction. The diffraction pattern from the defect state, excited at the $\mathrm{Ti}\mathrm{\text{\ensuremath{-}}}2p\mathrm{\text{\ensuremath{-}}}3d$ resonance, is analyzed in the forward scattering approach and on the basis of multiple scattering calculations. The defect charge is found to be shared by several surface and subsurface Ti sites with the dominant contribution on a specific subsurface site in agreement with density functional theory calculations.

Field-induced tip–sample oxygen transfer in scanning tunneling microscopy on TiO2(110) (1 1).

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…

A static SIMS study of superficial reactions (O2, (CN)2) on silver

Abstract The exposure of silver surfaces to oxygen under about 10 −6 mbar at room temperature was studied mainly by secondary ion mass spectrometry (SIMS) used in a static mode. No reactivity of oxygen appeared under these exposure conditions in accordance with previous works. No modifications in the AES spectra, but an unexpected and huge increase in the intensities of secondary ions such as CN − , CNO − , Ag(CN) − 2 , Ag 2 CN + were observed. Different experiments were performed in order to specify the origin of this unexpected reaction in presence of pure oxygen. Moreover, exposures to pure (CN) 2 and to a mixture of cyanogen and oxygen were performed in order to compare the reactivity o…

Molybdenum thin-film growth on rutile titanium dioxide ()

Molybdenum films were deposited at room temperature on rutile TiO2(1 1 0) surfaces having different stoichiometries, surface roughnesses and crystallinities. The film structures and compositions and the substrate–film interfaces were investigated by X-ray diffraction, high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. Different substrate pretreatments resulted in markedly different film and interface structures. Under the growth conditions studied, no amorphous molybdenum oxide interlayers were formed upon deposition in contrast to previous studies. Preferred (1 1 0) textured Mo films grew on both air-annealed and oxygen-bombarded substrates. While sh…

Watching adsorption and electron beam induced decomposition on the model system Mo(CO)(6)/Cu(111) by X-ray absorption and photoemission spectroscopies

Abstract 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 …

Structural and in depth characterization of newly designed conducting/insulating TiN O /TiO2 multilayers obtained by one step LP-MOCVD growth

Abstract TiNxOy/TiO2 multilayers have been grown by LP-MOCVD using titanium isopropoxide (TIP) precursor during the whole growth, but with an ammonia flow interrupted for the TiO2 layers. The one step growth process used to grow these structures allowed to stack the conducting and insulating layers without any growth breakdown. SIMS and TEM analyses showed the presence of an alternated insulating/conducting layers structure. Moreover, electrical measurements allowed to measure the dielectric part of insulating TiO2 stacked in these structures, whose permittivity was found to be about 80 for a MOS structure. Thus, such multilayers may lead to very promising applications in the microelectroni…

A photoemission study of molybdenum hexacarbonyl adsorption and decomposition on TiO2(110) surface.

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 …

Effect of the surface stoichiometry on the interaction of Mo with TiO2 (110)

Abstract Molydenum has been deposited at room temperature on (110) TiO2 surfaces with different stoichiometries, roughnesses and crystallinities. Whatever the substrate preparation is, in-situ Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) studies as well as ex-situ atomic force microscopy (AFM) and reflexion high-energy electron diffraction (RHEED) studies reveal a Stranski–Krastanov growth mode: the completion of three monolayers followed by islands growth is observed in every case. The three monolayers are always composed of amorphous molybdenum oxide with an oxidation state of molybdenum less than IV. The oxidation of the molybdenum layers generates Ti3+ an…

Tunneling induced decomposition of Mo(CO)(6) onto TiO2(110) surface

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 …

Comparative study of air and vacuum annealing atmosphere towards Pt/Ti–W/SiO2 stability

Abstract The thermal stability of Pt/Ti–W/SiO2 system was studied after annealing under air or vacuum in the present work. A Ti–W adhesive film (30 at. % Ti) was deposited on a SiO2 substrate followed by a thicker Pt layer. Depositions were performed using DC magnetron sputtering. The whole as-deposited films are metallic with a columnar growth of platinum deposit which totally wets the substrate. Whatever the atmosphere is, annealing at 500 °C for 12 h does not change the platinum state but modifies the morphology of platinum particles, the lateral average size of which increasing from less than 10 nm up to ca. 75 nm. Besides, a noticeable diffusion of metallic tungsten through Pt film is …

Redox reactions in the Pt/TiO2–WO3/SiO2 planar system

Abstract The thermal behavior of the titanium–tungsten adhesive layer (30–70 at.%) deposited on a SiO2 substrate followed by a thicker Pt layer was investigated. The resulting Pt/TiW/SiO2 planar system was annealed under air or vacuum. Morphological and chemical characterizations at different stages of the annealing, as a function of several parameters such as treatment atmosphere, annealing temperature and thickness of the Pt film were performed through surface science analyses. When annealing under air, even at mild temperature (773 K), the whole interlayer oxidizes while a low amount of tungsten diffuses through platinum film. This phenomenon is related to tungsten oxidation which acts a…

Evidence of hexagonal WO3 structure stabilization on mica substrate

International audience; WO3 nanorods are grown by a simple vapor deposition method on a mica substrate and characterized by Selected Area Electron Diffraction and Energy Dispersive X-rays Spectroscopy. Experimental results show the clear evidence of an unexpected WO3 hexagonal structure as well as an epitaxial growth on the mica substrate. Besides, potassium is evidenced inside the nanorods. It is thus deduced that a metastable WO3 hexagonal phase is stabilized by epitaxy through a tungsten bronze interlayer having same hexagonal structure.

Intrinsic Nature of the Excess Electron Distribution at theTiO2(110)Surface

The gap state that appears upon reduction of TiO2 plays a key role in many of titania's interesting properties but its origin and spatial localization have remained unclear. In the present work, the TiO2(110) surface is reduced in a chemically controlled way by sodium adsorption. By means of resonant photoelectron diffraction, excess electrons are shown to be distributed mainly on subsurface Ti sites strikingly similar to the defective TiO2(110) surface, while any significant contribution from interstitial Ti ions is discarded. In agreement with first principles calculations, these findings demonstrate that the distribution of the band gap charge is an intrinsic property of TiO2(110), indep…

Iron deposition on TiO2(110): effect of the surface stoichiometry and roughness

Abstract Characterizations of ultra-thin iron films deposited on TiO 2 (110) surfaces with different stoichiometries, roughnesses and crystallinities have been carried out by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). For a high initial roughness of the substrate, a 2D growth mode is observed up to three monolayers. But, if the initial roughness is low, clusters grow on the TiO 2 surface. Whatever the initial surface stoichiometry, electronic exchanges occur between titanium and iron leading to a reduction of titanium and an oxidation of iron. This interaction between iron and titanium dioxide surface takes place only at the interface between the metal and…

Structural characterization of TiNxOy/TiO2 single crystalline and nanometric multilayers grown by LP-MOCVD on (110)TiO2

TiO2/TiNxOy superlattices were grown by Low Pressure-Metal-Organic Vapor Phase Epitaxy (LP-MOVPE) technique at deposition temperatures ranking from 650 to 750°C. The growth was performed on top of TiO2(110) rutile substrates. Intense peaks observed in the X-rays rocking curves and θ-2θ diffraction patterns show the presence of crystalline epilayers. The TiNxOy layers were grown in a (200) cubic structure on the (110) quadratic TiO2 epilayer structure. Transmission electron microscopy confirmed the XRD results and showed the formation of periodic and well structured epilayers.

First stages of the growth of TiO2 thin films on silicon ; growth of tungsten based nanostructures on TiO2 and K modified TiO.

Conductimetry and impedance spectroscopy study of low pressure metal organic chemical vapor deposition TiN O films as a function of the growth temperature: a percolation approach

Abstract Titanium oxinitride thin films have been grown by low pressure metal organic chemical vapor deposition (LP-MOCVD) using titanium isopropoxide, Ti(OCH(CH 3 ) 2 ) 4 (TIP) and NH 3 precursors in a growth temperature range from 450 to 750°C on sapphire substrates. The electrical behaviour of these films was studied between 400 and 173 K, revealing three different behaviours, ranking from a hopping conductivity (450–500°C) to a conducting one (700–750°C), with a dual behaviour for the intermediate growth temperatures. Moreover, at room temperature, both conductimetry and impedance spectroscopy highlighted a percolation behaviour, interpreted in terms of continuum percolation. The effect…

MOCVD growth of porous cerium oxide thin films on silicon substrate

Abstract Porous cerium oxide thin films were grown by pulsed direct liquid injection metal organic chemical vapor deposition (DLI-MOCVD) on silicon substrate, using cerium tetrakis (1-methoxy-2-methyl-2-propanolate) dissolved in cyclohexane as precursor as well as oxygen as oxidant agent. The chemical and morphological characteristics of the films were investigated by XPS, SEM and TEM. The influence of the growth conditions on the morphological features of the thin films and the cerium chemical states are reported and discussed. The decrease of the oxygen and/or alkoxide flow rate induces the decrease of both the film thickness and the porosity of the layer. Moreover, the growth of silicate…

Investigation on sol–gel synthesized Ag-doped TiO2 cermet thin films

Abstract Undoped TiO 2 and Ag–TiO 2 (up to 23 at.% Ag) cermet thin films and polycrystalline powders have been prepared by sol–gel process. Their structure, composition, surface morphology and optical properties have been investigated by X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and ultraviolet–visible spectroscopy (UV–VIS spectroscopy). It has been observed that while Ag does not form a solid solution with TiO 2 , it promotes the anatase to rutile phase transformation. The transformation temperature decreases from 827 °C for undoped TiO 2 to about 650 °C fo…

Reactive direct current magnetron sputtered TiO2 thin films with amorphous to crystalline structures.

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…

Study of surface layers and ejected powder formed by oxidation of titanium substrates with a pulsed Nd:YAG laser beam.

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) dominate…

Growth and characterization of AP-MOCVD iron doped titanium dioxide thin films

Abstract Atmospheric pressure metal organic chemical vapor deposition (AP-MOCVD) was used to prepare iron doped titanium dioxide thin films. Thin films, between 40 and 150 nm thick, were deposited on Si, SiO 2 and Al 2 O 3 substrates using titanium tetra isopropoxide and ferrocene as metal organic precursors. TiO 2 iron doping was achieved in the range of 1–4 at.%. The film morphology and thickness, polycrystalline texture and doping content were studied using respectively scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of growth temperature, deposition time, substrate type and dopant partial pressure were studied. Electr…

Influence of laser–target interaction regime on composition and properties of surface layers grown by laser treatment of Ti plates

Surface laser treatment of commercially pure titanium plates was performed in air using two different Nd : YAG sources delivering pulses of 5 and 35 ns. The laser fluence conditions were set to obtain with each source either yellow or blue surface layers. Nuclear reaction analysis (NRA) was used to quantify the amount of light elements in the formed layers. Titanium oxinitrides, containing different amounts of oxygen and nitrogen, were mainly found, except in the case of long pulses and high laser fluence, which led to the growth of titanium dioxide. The structure of the layers was studied by x-ray diffraction and Raman spectroscopy. In addition, reflectance spectra showed the transition fr…

Structural characterization of TiO2/TiN O (δ-doping) heterostructures on (1 1 0)TiO2 substrates

Abstract 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 analy…

Temperature and substrate influence on the structure of TiN O thin films grown by low pressure metal organic chemical vapour deposition

Abstract This paper presents the growth and characterization of titanium oxinitride (TiN x O y ) films grown by low pressure metal organic chemical vapour deposition (LP-MOCVD). The film nitrogen content, obtained by Rutherford backscattering spectroscopy (RBS), increases as the growth temperature increases (from 23 at.% at 450°C to 46 at.% at 750°C). Below 550°C, the films do not show any X-ray diffraction pattern. Above 550°C, the deposited films present the (111) and (200) TiN textures. Films deposited on (100) Si exhibit a 2 θ shift to higher Bragg angles, depending on the N/O ratio. These shifts are explained by using a substitutional oxygen model. Moreover, the atomic structure of suc…

Monolayer Formation of Molybdenum Carbonyl on Cu(111) Revealed by Scanning Tunneling Microscopy and Density Functional Theory

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, whi…

Sodium Adsorption on the TiO2110 Surface an XAFS Structural Study

The adsorption site of sodium atoms deposited onto a clean TiO2(110) surface has been determined by EXAFS. The best result is obtained for an 'in-between' site where the sodium is bound to two bridging oxygen atoms at 2.25 A and one in-plane one at 2.40 A in full agreement with DFT calculations. At higher coverage the site becomes a hollow site where Na is equidistant to the three oxygen atoms at 2.30 A.

An epitaxial hexagonal tungsten bronze as precursor for WO3 nanorods on mica.

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.

Interpretation of absorption edges by resonant electronic spectroscopy: experiment and theory

Abstract Resonant electronic spectroscopy consists in measuring a non-radiative decay process (Auger or autoionization process) excited with photon energies around an absorption edge. The resonant spectra carry information both on the nature of the electronic transitions near the absorption edge by scanning the very first empty orbitals above the Fermi level (through the absorption process), and, on the other hand, on the atomic electronic configuration through the lineshape of the observed decay process. In this paper, after a quick review of the pioneering works in this field, we show that resonant measurements and their theoretical modeling can be used to precisely interpret complex abso…

Scanning tunneling microscopy and spectroscopy of Mo clusters grown on TiO2(110).

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 deposi…

Dynamics of molybdenum nano structure formation on the TiO2(110) surface: A kinetic Monte Carlo approach

Abstract The rutile TiO 2 (1 1 0) surface is a highly anisotropic surface exhibiting “channels” delimited by oxygen rows. In previous experimental and theoretical DFT works we could identify the molybdenum adsorption sites. They are located inside the channels. Moreover, experimental studies have shown that during subsequent annealing after deposition, special molybdenum nano structures can be formed, especially two monolayer high pyramidal chains of atoms. In order to better understand the dynamics of nano structure formation, we present a kinetic Monte Carlo study on diffusion and adsorption of molybdenum atoms on a TiO 2 (1 1 0) surface. A quasi one-dimensional lattice gas model has been…

Trivalent cation substitution of pulverulent cobalt—iron molybdates Co1 − xFexMoO4

Abstract Different mixed cobalt—iron molybdates Co1 − xFexMoO4 (0 ≤ x ≤ 1) have been prepared by means of a ceramic process. The oxidation of pulverulent samples leads to ferric molybdate Fe2(MoO4)3, spinelle Co3O4 and cobalt molybdate CoMoO4. After a strong grinding which reduces the grain size (about 0.1 μm) and induces crystallographic defects in the grains, the cobalt—iron molybdates can be partially oxidized into cation-deficient phases. This oxidation corresponds to an isostructural substitution of part of the Fe2+ and Co2+ ions by Fe3+ and Co3+ ions and the creation of cation vacancies. The concomitant presence of trivalent cations and associated cation vacancies in the lattice stabi…

SEM and XPS studies of titanium dioxide thin films grown by MOCVD

Abstract The metal organic chemical vapour deposition (MOCVD) method was used to prepare titanium dioxide thin films. Thin films of TiO2, about 100 nm thick, were deposited on (100)Si and (1102)Al2O3 sapphire substrates using titanium isopropoxide (Ti(OC3H7)4) as metal organic precursor. The morphology of the films and the presence of impurities on the thin films surfaces were studied using respectively, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The influence of the growth parameters such as the deposition temperature, the carrier gas (nitrogen) flow rate and the presence of an additional oxygen flow on the characteristics of the titanium dioxide films h…

Thermal stability under air of tungsten–titanium diffusion barrier layer between silica and platinum

Abstract The present work investigated the thermal stability of tungsten–titanium diffusion barrier layers intercalated between SiO 2 substrate and platinum thin film. The resulting structures were annealed under air in the temperature range 400–600 °C for annealing times up to 100 h. Chemical and structural characterizations at different stages of the treatment evidenced several phenomena occurring during annealing under air, especially the complete oxidation of the adhesive layer, the diffusion of tungsten oxide through platinum film at particle boundaries as well as the sublimation process of tungsten oxide. The results of film surface chemistry and microstructure were correlated with di…

Mo(CO)6 dissociation on Cu(111) stimulated by a Scanning Tunneling Microscope

Abstract The surface of Cu(111) was exposed to molybdenum hexacarbonyl Mo(CO)6 with monolayer coverage at temperature 160 K and studied by a Scanning Tunneling Microscope. The monolayer structure has a hexagonal arrangement and forms a (√7 × √7) R19 superlattice on the copper (111) plane. Upon repeated scanning the monolayer is transformed into a (1 × 2) superstructure with 3-fold oriented domains. The domains of (1 × 2) superstructure can change orientation under scanning according to 3-fold surface symmetry. From analysis of the domain mobility, it follows that CO groups of carbonyl fragments are organized in the (1 × 2) superstructure conditioning the domain reorientation. The observed s…

Intra-atomic versus interatomic process in resonant Auger spectra at the TiL23edges in rutile

The two components of the Ti ${L}_{23}{M}_{23}V$ Auger transition recorded on a stoichiometric rutile crystal are identified as ${L}_{2}{M}_{23}V$ and ${L}_{3}{M}_{23}V$ contributions. This assignment is evidenced by concordant data relative to resonances of the LMV decay at the Ti ${L}_{23}$ thresholds and to Auger emission recorded in coincidence with the ${2}_{1/2}$ and ${2}_{3/2}$ photoemission at a photon energy far above the Ti ${L}_{23}$ edges. The ${L}_{3}{M}_{23}V$ transition is shown to follow either the direct photoexcitation of a ${2}_{3/2}$ electron or the fast Coster-Kronig decay of a ${2}_{1/2}$ photohole. Although specific LMV contributions related to valence orbitals are id…

Study by static SIMS, XPS and UPS of the adsorption of cyanogen on (100) Ni surfaces

Abstract The interaction of cyanogen with (100) Ni surfaces at room temperature was studied using secondary ion mass spectrometry in a static mode, and photoemission spectroscopies (XPS and UPS). It has been shown that cyanogen is adsorbed on this nickel surface in a dissociative mode: atomic carbon and nitrogen are present on the surface as well as CN fragments. These adsorbed species have been characterized by XPS and UPS. Increasing the temperature in the 400 K range increases the rate of the dissociation reaction of CN into atomic carbon and nitrogen. Moreover carbon is found to dissolved into the bulk for temperatures as low as 475 K. No evidence has been found of a polymerized form of…

Interfacial reaction during MOCVD growth revealed by in situ ARXPS.

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 …

Molybdenum thin film growth on a TiO2 (1 1 0) substrate.

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

Stoichiometry-related Auger lineshapes in titanium oxides: Influence of valence-band profile and of Coster-Kronig processes

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.…

Angle resolved X-ray photoemission spectroscopy double layer model for in situ characterization of metal organic chemical vapour deposition nanometric films.

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 underestima…

Nanostructured Pt–TiO2 composite thin films obtained by direct liquid injection metal organic chemical vapor deposition: Control of chemical state by X-ray photoelectron spectroscopy

Abstract Nanostructured Pt–TiO 2 composite thin films were synthesized by direct liquid injection metal organic chemical vapor deposition process, using trimethyl(methylcyclopentadienyl)platinum and titanium isopropoxide as precursors. Surface and cross-sectional morphologies obtained by scanning electron microscopy and transmission electron microscopy evidenced the uniform distribution of platinum nanoparticles in the TiO 2 matrix. At higher Pt content, the X-ray diffraction analysis showed that the face-centered cubic phase of platinum appeared together with an anatase TiO 2 structure. In addition, as far as the platinum chemical state is concerned, the co-deposition of TiO 2 and Pt allow…

Elaboration and characterization of barium silicate thin films.

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.

Spectroscopies d'électrons et rayonnement synchrotron.

The defined adsorption site of sodium on the TiO2(110)–(1×1) surface

The adsorption site of sodium on the TiO2(1 1 0)–(1 × 1) surface was studied by extended X-ray absorption fine structure. For coverage ranging between 0.25 and 0.5 ML, we find that sodium is on an ‘in-between' site where it is bound to two bridging oxygen atoms at 2.25 Å and one in-plane oxygen atom at 2.40 Å, in full agreement with DFT calculations. At higher coverage the site becomes an hollow site where the sodium atom is equidistant to the three oxygen atoms at 2.30 Å, while metallic sodium clusters are also formed at the surface.

Le dioxyde de titane, réactivité de couches minces et de surfaces monocristallines.

Hard X-ray resonant electronic spectroscopy in transition metal oxides

K-edge X-ray absorption and 2p-XPS spectra of 3d-element oxides present spectral features which cannot be explained within a simple one-electron model. These features reveal the fine electronic structure of transition metal (TM) oxides valence states resulting from hybridized TM-3d and O-2p states, and the correlations between these valence electrons. In this paper, we show how resonant electronic spectroscopy (resonant Auger or resonant photoelectron spectroscopy) around the TM K-edge can be used to interpret the structures of the threshold and, with the help of theoretical calculation, to determine the electronic configuration of the excited ion. Quadrupolar transitions towards localized …

Superficial defects induced by argon and oxygen bombardments on (110) TiO2 surfaces

Abstract Compositional and chemical changes of titanium dioxide monocrystalline surfaces induced by bombardment with 4 keV argon and oxygen ions have been studied by AES, XPS and AFM. Argon ion bombardment induced strong changes in the composition and chemical state of the surface: loss of oxygen due to preferential sputtering occurred, and, related to this, Ti4+ species were reduced to Ti3+ and Ti2+. During oxygen bombardment, competition between preferential sputtering of oxygen ions of the oxide surface and oxygen implantation was observed. This phenomenon was found to be strongly dependent upon the incidence angle of the oxygen ions. Moreover, an oxygen bombardment with normal incidence…

Epitaxial growth of molybdenum on TiO2(110)

Abstract 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 ach…

Surface composition analysis during the oxidation of ferrites: A necessity

The cationic composition of a titanium ferrite (Fe 2.5 Ti 0.5 O 4 ) has been followed by XPS during its oxidation in cation deficient phases (without crystallographic transformation) in order to reveal a dynamic segregation phenomenon. Indeed, during this oxidation, an important modification of the chemical composition of the first layers of the material has been revealed: below 350 °C, the titanium ferrites surface becomes richer in iron and poorer in titanium. But, if the reaction is extended above 400 °C, some titanium can move to the surface. This phenomenon has been interpreted on the basis of the differences of mobility of the different ions which are present in the material. Finally,…

Initial stages of TiO2 thin films MOCVD growth studied by in situ surface analyses

Abstract In situ chemical surface analyses using X-ray photoelectron spectroscopy (XPS) were performed to understand the initial stages of TiO 2 thin-film MOCVD growth. Deposits on Si (1 0 0), a few nanometres thick, were obtained at a fixed temperature of 650 °C and for two different pressures, 2.9 and 0.05 mbar, using titanium tetraisopropoxide (TTIP) as precursor. Pressure lowering led to a higher deposit growth rate. Reduction of titanium with respect to stoichiometric titanium dioxide and oxidation of the wet-cleaned silicon substrate are observed from decomposition of the Ti 2p and Si 2p peaks. The formation of a TiSi x O y mixed oxide is also pointed out and confirmed by the presence…

Reactivity between molybdenum and TiO2(110) surfaces: evidence of a sub-monolayer mode and a multilayer mode

Small amounts of molybdenum (from 0.03 to 1.3 eqML) were deposited on non-stoichiometric TiO 2 (1 1 0) surface. The deposits were investigated by means of LEED and X-ray/UV photoemission using synchrotron radiation. For the smallest coverage (<0.2 eqML), deposition leads to oxidation of molybdenum into species close to Mo 4+ .In such a case, states appearing in TiO 2 band gap are mainly due to reduced titanium. For higher coverages, metallic behaviour of molybdenum is observed. This phenomenon was explained, thanks to first principle calculations, as a decrease of the Mo-O interactions for the benefit of the Mo-Mo interactions as the surface molybdenum atom density increases.

Stabilization of polar solid oxide surfaces: competition between adsorption and reconstruction

Multi-cationic spinel compounds are solids that exhibit polar faces. X-ray Photoelectron spectroscopy revealed the main phenomena allowing the stabilization of these faces, carried out as a function of the material treatment, particularly the cooling rate after thermal treatment at a high temperature (1200°C). This study showed that, whatever the cooling rate, each sample is subject to a significant hydroxylation that reduces the polarity. Nevertheless, it appears that the hydroxyl group content at the surface is a strong function of the cooling rate. Indeed, whereas quenched materials are subject to high levels of hydroxylation, slowly cooled samples are sparingly hydroxylated. This phenom…

MOCVD growth of TiO2 thin films on single crystal GaAs substrates

Abstract TiO 2 thin films have been grown on (100)GaAs and (111)GaAs substrates by low-pressure metal organic chemical vapour deposition (LP-MOCVD). Titanium(IV) isopropoxide, Ti{OCH(CH 3 ) 2 } 4 , was used as a precursor and TiO 2 films were obtained without an additional oxygen flux. Scanning electron microscopy (SEM) experiments have shown a well ordered rod-like crystallisation in the films grown on (100)GaAs. This ordered crystallisation was favoured by a high deposition temperature ( T d =700°C). By contrast, no distinct order was observed in the films grown on (111)GaAs substrates. X-ray diffraction patterns revealed a mainly rutile structure for the TiO 2 films deposited on (100)GaA…

Growth of titanium oxynitride layers by short pulsed Nd:YAG laser treatment of Ti plates: Influence of the cumulated laser fluence.

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 wh…

Wavelength influence on nitrogen insertion into titanium by nanosecond pulsed laser irradiation in air

Abstract We studied in this work the influence of the wavelength (532 vs. 1064 nm) on the insertion of nitrogen in titanium targets by surface laser treatments in air. The laser pulses were of 5 ns and the irradiance was lower than 25 × 10 12  W/m 2 . Results obtained using a frequency-doubled Nd:YAG laser at 532 nm were compared with those previously reported for laser treatments at 1064 nm. Nuclear reaction analysis and micro-Raman spectroscopy were used for determining the composition and the structure of the surface layers, respectively. Results showed the lower efficiency of irradiation at 532 nm for nitrogen insertion, which is possible only above threshold conditions depending on bot…

Growth, Structure, and Stability of KxWO3 Nanorods on Mica Substrate

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 di…

Structure and properties of GaNxOy films grown by nitridation of GaAs (100) substrates

GaAs (100) substrates have been heat-treated in a metal-organic chemical vapor deposition reactor under flows of NH 3 and an oxygen organo-metallic precursor at temperatures between 650°C and 750°C. Yellowish films formed at the surface of all the samples. Gallium, nitrogen and oxygen were detected by EDX analysis of the films. The oxygen content was estimated in the range of at 5-10 at% depending on the heat-treatment temperature. X-ray diffraction and HRTEM results indicate that the structure of the films corresponds to the hexagonal wurtzite phase of GaN with an expanded unit cell. Raman spectra show hands corresponding to the Raman active GaN modes as well as disorder-activated broad ba…

Dynamic segregation during ferrite oxidation revealed by XPS

Dynamic segregation phenomena were revealed by XPS during the oxidation of some ferrites (Fe 2.5 Ti 0.5 O 4 , Fe 2.5 Ni 0.5 O 4 , Fe 2 CrO 4 and FeCr 2 O 4 ). This kind of phenomenon induces, at a low temperature (below room temperature), drastic changes in the cationic composition of the most external layers. Dynamic segregation is a function of the cationic composition, the oxidation capability and the morphology of these ferrites. Although dynamic segregation seems to be a quite frequent phenomenon that often can be observed during ferrite oxidation, there are materials in existence where it does not appear, such as molybdenum ferrite.

Photoemission study of the reactivity of barium towards SiOx thermal films

Abstract Barium was deposited at room temperature on a thermal silicon oxide layer and the interfacial reaction was monitored by synchrotron induced photoemission (both core level and valence band). The first step of the growth consists of an interfacial reaction which leads to the formation of an interfacial silicate layer. The next step consists in formation of barium oxide while metallic barium occurs subsequently. The deposit can be also homogenized by annealing above 575 K. This results in the formation of several layers of silicate by consumption of silicon oxide. In the case of fractional coverage, subsequent annealing at 975 K induces the decomposition of barium silicate. However, s…

Thermal effects on the growth by metal organic chemical vapour deposition of TiO2 thin films on (100) GaAs substrates

Abstract TiO 2 thin films were deposited on (100) GaAs substrates by LP-MOCVD with deposition temperatures ( T d ) ranking from 450 to 750 °C. The structure of these layers was studied by X-ray diffraction (XRD) and Raman spectroscopy. The growth of the TiO 2 anatase phase was observed for T d T d >600 °C. Finally, X-ray photoelectron spectrometry (XPS) and secondary ion mass spectroscopy (SIMS) experiments showed the presence of small quantities of Ga and As through the whole film thickness, slightly increasing at the surface of the layers. This result was related to the SEM observations and explained by considering the growth conditions.

In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

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.

Interfacial reaction between deposited molybdenum and TiO2(110) surface: role of the substrate bulk stoichiometry

Abstract The interfacial reaction between deposited molybdenum and three different TiO2(1 1 0) substrates (a bulk and surface stoichiometric TiO2; a bulk stoichiometric and surface reduced crystal; a bulk and surface slightly reduced crystal) was investigated by means of X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). While the interfacial reaction is not a function of the substrate at room temperature (in any case, molybdenum layers grow with oxygen dissolved in), this study clearly reveals a strong effect of the substrate bulk stoichiometry on the chemical state of the deposit after annealing up to 750 °C whereas the substrate surface stoichiome…

From tungsten hexacarbonyl adsorption on TiO2(1 1 0) surface to supported tungsten oxide phases.

Abstract 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…

Excess Electrons at Oxide Surfaces

Excess electrons profoundly affect the properties of oxide surfaces. The present review deals with excess charges on rutile and anatase. These much studied titania polymorphs open with strong prospects regarding (photo)catalysis and dye-sensitized solar cells. In the complex landscape of the mechanisms of electron trapping and electron transfer toward adsorbates, excess electrons open with flexible model systems which are the focus of an extensive research effort.

WOx phase growth on SiO2/Si by decomposition of tungsten hexacarbonyl:Influence of potassium on supported tungsten oxide phases

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 p…

Structural and Chemical Characterization of Cerium Oxide Thin Layers Grown on Silicon Substrate

In this study, we report transmission electron microscopy and electron energy loss spectroscopy study of cerium oxide thin layers deposited on silicon substrate. Transmission electron microscopy experiments have revealed the flat morphology of the deposited layers. In addition, studies of high resolution images have indicated the presence of mainly ceria crystallized nanoparticles. Energy electron loss spectroscopy measurements were also performed in scanning mode to study the evolution of the cerium valence. In addition to Ce4+ inside the layer, the presence of amorphous cerium silicate with valence +3 is pointed out at the vicinity of the substrate.

QUADRUPOLAR CHARACTER OF THE Ti K-EDGE PREPEAKS IN TiO2 BY RESONANT AUGER

Resonant spectroscopies offer a new opportunity to get more insight into excited electronic states by studying line shapes and intensities of decay processes. For photon excitations in the pre-K-edge region, the Ti KL 2,3 L 2,3 Auger spectra in TiO 2 show additional peaks when an electron is promoted in localized d-like states via a quadrupolar transition. This resonant process is used to unravel the respective contributions of quadrupolar and dipolar transitions to the absorption edge prepeaks.

Titanium dioxide surface stoichiometry and ordering studied by resonant photoemission spectroscopy

Abstract 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 v…

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

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 …

Correlation Between the Electrical Properties and the Morphology of Low-Pressure MOCVD Titanium Oxynitride Thin Films Grown at Various Temperatures

Titanium oxynitride (TiN x O y ) thin films were deposited by low-pressure metal-organic CVD (LP-MOCVD) on (100) silicon, sapphire, and polycrystalline alumina substrates. Titanium isopropoxide (TIP) and ammonia were used as precursors. The influence of the growth temperature, ranking from 450°C to 750°C, was investigated by scanning electron microscopy (SEM), and electrical DC measurements. Rutherford back-scattering (RBS) measurements were used to determine the N/O ratio in the films. The surface observations of the deposited films showed two morphological transitions. The resistivity decreased with the growth temperature, while the nitrogen content increased. Moreover, for the highest de…

Amorphous TiO2 in LP-OMCVD TiNxOy thin films revealed by XPS

Abstract TiN(O)–TiO 2 thin films were prepared on Si(1 0 0) by the low pressure organo metallic chemical vapor deposition (LP-OMCVD) method, using ammonia and titanium isopropoxide as precursors. In order to complete previous characterizations, an Ar + bombardment/XPS coupled study was carried out. This method is based on the fact that the behavior of a compound towards an ion bombardment is a function of its composition. In particular, Ar + bombardment of TiO 2 (whatever its form) leads to a preferential sputtering of oxygen atoms with subsequent reduction of titanium and formation of Ti 3+ and Ti 2+ easily detectable by XPS from a significant broadening of the Ti 2p lines. In the opposite…

WC-based thin films obtained by reactive radio-frequency magnetron sputtering using W target and methane gas

Abstract Deposition of tungsten carbide (WC) films was investigated by radio-frequency reactive sputtering using a tungsten target and methane gas. The effect of some processing parameters (pressure, power, CH 4 -to-Ar gas flow ratio) upon the chemical and structural properties of the films has been investigated. The evolution of the chemical composition has been analyzed by photoemission, the microstructure has been studied through electron microscopy techniques and the crystallographic structure was investigated by X-ray diffraction as well as Raman spectroscopy. This study demonstrates that the formation of tungsten carbide is highly dependent on the deposition conditions: thin films are…

Optical interfaces in GD-OES system for vacuum far ultraviolet detection

A Glow Discharge Optical Emission Spectrometry device has been designed for glove box adaptation in CEA Valduc to analyze carbon, hydrogen, nitrogen and oxygen at low concentration in nuclear materials. Vacuum ultraviolet region of the spectrum (between 120 and 160 nm) was chosen for light elements analysis with the aim to avoid optical interferences with matrix emission lines (20000 lines in the visible region for plutonium element). For this purpose, two different systems of collection have been developed: a first based on two focusing lenses and a second having an optical interface based on mirrors. In the present paper, the whole set-up integrated in a glove box is described. Optical li…

Pulsed laser growth and characterization of thin films on titanium substrates

Abstract Colored layers were obtained by laser surface treatment of Ti substrates with a pulsed Nd:YAG Q-switched laser. The changes in the morphology, structure and chemical composition of the layers were studied by SEM, EDS, XPS, SIMS and Raman spectroscopy as a function of the laser fluence in the 4–60 J cm −2 . For laser fluences lower than 25 J cm −2 , the layers are colorless or yellow. Their surface is smooth, but they display cracks which increase when the fluence increases. The O/Ti ratio, determined by XPS analysis, varies from 0.7 (colorless layers) to 1.3 (yellow layer). Moreover, XPS spectra evidence non-negligible amounts of nitrogen and carbon in these layers. Raman spectra s…

Thermal stability of Au–TiO2 nanocomposite films prepared by direct liquid injection CVD

Abstract Nanocomposite films composed of gold nanoparticles (AuNPs) embedded in a TiO 2 matrix have been prepared by direct liquid injection chemical vapor deposition process, using preformed nanoparticles and titanium isopropoxide as precursors. The spherical AuNPs about 4.1 nm in diameter were synthesized by using gold (III) chloride trihydrate and stabilized by thiol ligands. The depositions were carried out by performing at first oxide deposition, then gold nanoparticle one and capping with oxide. The morphology, structure; the chemical state and optical properties of nanocomposite films were characterized by scanning electron microscopy, Raman, X-ray photoelectron and UV–Vis absorption…

A surface EXAFS study of thin nickel deposits on (110) TiO2 surfaces

Abstract The first stages of nickel deposition on a clean (110) TiO 2 surface were studied using surface extended X-ray absorption fine structure (EXAFS). Experiments were performed on two kinds of nickel deposits, one of 0.8 equivalent monolayers and another of 1.6 equivalent monolayers. Depositions were performed on well characterized TiO 2 (110)-p(1 × 1) surfaces. The correlation of Auger experiments with EXAFS results showed that no islands were present on the surface; only two-dimensional growth of nickel was observed. Moreover, it was shown, in the case of the thinner deposit, that a model with nickel atoms forming chains in the channels determined by oxygen atoms on the surface is co…