0000000000201317
AUTHOR
M.c. Marco De Lucas
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…
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…
Modelling nanoparticles formation in the plasma plume induced by nanosecond pulsed lasers
International audience; Nanoparticles formation in a laser-induced plasma plume in the ambient air has been investigated by using numerical simulations and physical models. For high irradiances, or for ultrashort laser pulses, nanoparticles are formed by condensation, as fine powders, in the expanding plasma for very high pairs of temperature and pressure. At lower irradiances, or nanosecond laser pulses, another thermodynamic paths are possible, which cross the liquid-gas transition curve while laser is still heating the target and the induced plasma. In this work, we explore the growth of nanoparticles in the plasma plume induced by nanosecond pulsed lasers as a function of the laser irra…
Study of the structural changes induced by air oxidation in Ti–Si–N hard coatings.
International audience; 3-μm thick Ti–Si–N coatings were deposited on polished X38CrMoV5 substrates by sputtering a composite Ti–Si target in Ar–N2 reactive mixture. Oxidation tests were performed in air at 700 °C during 2 h. Whatever the silicon content in the range 0–4 at.%, no silicon containing compound was detected by XRD before air oxidation and only the TiN phase was evidenced. The mean grain size estimated from the full width at half maximum of the TiN (111) diffraction peak was close to 10 nm. As commonly reported for Ti–Si–N films, the hardness showed a maximum at 51 GPa versus the Si content. After oxidation of the TiN film, XRD and micro-Raman analyses revealed the occurrence of…
Stabilisation of tetragonal zirconia in oxidised ZrSiN nanocomposite coatings
Abstract ZrSiN coatings were deposited on steel and silicon substrates by reactive sputtering of a composite ZrSi target. The coatings were oxidised in air in the 600–750 °C temperature range. As-deposited and oxidised films were characterised by X-ray diffraction, micro-Raman spectroscopy, X-ray photoemission spectroscopy and glow discharge optical emission spectroscopy. The oxidation behaviour of ZrSiN coatings was compared to that of ZrN ones. It was demonstrated that addition of silicon in the 3–5 at.% range into ZrN-based coatings promotes the onset of oxidation by nearly 100 °C. The structure of the oxide layer was strongly dependent on the film’s silicon content: monoclinic zirc…
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…
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…
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.
Improving the high temperature oxidation resistance of pure titanium by shot-peening treatments
International audience; Shot-peening (SP) treatments have shown their capacity to improve the oxidation resistance of titanium and zirconium thanks to the large compressive stresses and the surface hardening induced by this mechanical process. However, shot-peening treatments can produce a surface chemical deposit, which can modify the high temperature oxidation resistance. Here, we study pure titanium samples shot-peened with different type of balls: tungsten carbide, alumina or glass. The oxidation behavior was studied at 700 °C in dry air by thermo gravimetric analysis for short isotherm oxidation periods up to 100 h. Also, long oxidation tests (3000 h) at 700 °C were performed with an i…
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…
Micro-Raman study of red decorations in French faiences of the 18th and 19th centuries
Obtaining the red color was a technical and economic challenge for the French faience manufactories in the 18th and 19th centuries. The tendency of the red hematite to turn into drab brown during the firing process explains the difficulty in obtaining this color. Red decorations in shards coming from the four production centers of faience manufacturing during this period—Rouen (northwest), Nevers (central), Thiviers (southwest) and Argonne (northeast)—have been studied by means of micro-Raman spectroscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Among them, Thiviers appears to be the leader thanks to a particular reddish sandstone called ‘Gres de T…
Effect of germanium addition on the properties of reactively sputtered ZrN films
For the first time, Zr-Ge-N films were deposited on silicon and steel substrates by sputtering a Zr-Ge composite target in reactive Ar-N2 mixture. The films were characterised by electron probe microanalysis, X-ray diffraction, micro-Raman spectroscopy and depth-sensing indentation. The effects of the Ge content and substrate bias voltage on the films' structure, internal stress, hardness and oxidation resistance were investigated. Substrate bias strongly influenced the chemical composition of the films being observed by means of a steep decrease in the Ge content for negative bias voltages higher than -80 V. In these cases, a significant hardness improvement was registered. For -100 V bias…
Vibrational Properties of CuO and Cu4O3 from First-Principles Calculations, and Raman and Infrared Spectroscopy
International audience; A combined experimental and theoretical study is reported on the vibrational properties of tenorite CuO and paramelaconite Cu4O3. The optically active modes have been measured by Raman scattering and infrared absorption spectroscopy. First-principles calculations have been carried out with the LDA+U approach to account for strong electron correlation in the copper oxides. The vibrational properties have been computed ab initio using the so-called direct method. Excellent agreement is found between the measured Raman and infrared peak positions and the calculated phonon frequencies at the Brillouin zone center, which allows the assignment of all prominent peaks of the…
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…
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…
Structural study of gallium oxynitrides prepared by ammonolysis of different oxide precursors
International audience; A comparative structural study has been carried out on gallium oxynitride powders using XRD and Raman spectroscopy. Gallium oxynitrides have been prepared by ammonolysis of either NiGa2O4 ternary oxide or the citrate method-derived amorphous oxide. Their crystal chemistry is different and appears to be influenced by the nature of the oxide precursor: whereas gallium oxynitride obtained from amorphous gallium oxide crystallizes with the common wurtzite structure, gallium oxynitride obtained from NiGa2O4 crystallizes with an original structure that we have identified as the carborundum II (B6) structure type or 6H-SiC. As far as we know, this is the first 6H-SiC struct…
Structural and conductivity study of the proton conductor BaCe(0.9−x)ZrxY0.1O(3−ı) at intermediate temperatures.
International audience; The perovskite BaCe(0.9−x)ZrxY0.1O(3−ı) is prepared by solid-state reaction at 1400 ◦C and sintering at 1700 ◦C. It is characterised using X-ray diffraction, Raman spectroscopy and electrical measurements. A distortion fromthe cubic structure at roomtemperature is noticeable in the Raman spectra for 0.2 < x < 0.8, but not in the X-ray diffraction patterns. This work points out the rhombohedral nature of this distortion. Phase transitions are studied up to 600 ◦C. The direct current conductivity is measured as a function of oxygen partial pressure, and at a water vapour partial pressure of 0.015 atm. The total conductivity is resolved into an ionic and a p-type compon…
Simple model for the vibrations of embedded elastically cubic nanocrystals
The purpose of this work is to calculate the vibrational modes of an elastically anisotropic sphere embedded in an isotropic matrix. This has important application to understanding the spectra of low-frequency Raman scattering from nanoparticles embedded in a glass matrix. First some low frequency vibrational modes of a free cubically elastic sphere are found to be nearly independent of one combination of elastic constants. This is then exploited to obtain an isotropic approximation for these modes which enables to take into account the surrounding isotropic matrix. This method is then used to quantatively explain recent spectra of gold and copper nanocrystals in glasses.
Vibrations of free and embedded anisotropic elastic spheres:Application to low-frequency Raman scattering of silicon nanoparticles in silica
Vibrational mode frequencies and damping are calculated for an elastic sphere embedded in an infinite, homogeneous, isotropic elastic medium. Anisotropic elasticity of the sphere significantly shifts the frequencies in comparison to simplified calculations that assume isotropy. New low-frequency Raman light scattering data are presented for silicon spheres grown in a ${\mathrm{SiO}}_{2}$ glass matrix. Principal features of the Raman spectrum are not correctly described by a simple model of the nanoparticle as a free, isotropic sphere, but require both matrix effects and the anisotropy of the silicon to be taken into account. Libration, not vibration, is the dominant mechanism.
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 …
Alumina particle reinforced TiO2 composite films grown by direct liquid injection MOCVD
Abstract The use of a liquid injection delivery system to form composite films containing nanoparticles was investigated. Al 2 O 3 –TiO 2 films were grown on silicon substrates by direct liquid injection MOCVD (DLI-MOCVD) at 400 °C. The α-Al 2 O 3 nanoparticles (α-Al 2 O 3 NPs) dispersed in TiO 2 films resulted from co-deposition using colloidal α-Al 2 O 3 solution and titanium tetraisopropoxide as titanium precursor. Scanning electron microscopy coupled with EDS as well as Raman spectroscopy confirmed the presence of α-Al 2 O 3 NPs aggregates embedded in the TiO 2 matrix. The liquid injection system coupled with CVD technique can be promising to form composite films containing preformed na…
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…
Electronic structure, lattice dynamics and thermodynamic stability of paramelaconite Cu4O3
Abstract An ab initio study of the electronic structure, lattice dynamic and thermodynamic properties of paramelaconite Cu 4 O 3 is reported. The insulating, mixed-valence character of Cu 4 O 3 is elucidated by analyzing the band structure and the spin-orbital symmetry of the Cu-3 d hole states. Exchange coupling constants between Cu 2+ ions are computed which confirm the frustrated antiferromagnetism of the spin lattice. The lattice dynamics is studied from first principles and main features of the vibrational spectrum are assigned to the different chemical species Cu + , Cu 2+ and O. The thermodynamic stability of Cu 4 O 3 is investigated by calculating the free energy of the decompositio…
Optical and Acoustic Vibrations Confined in Anatase TiO2 Nanoparticles under High-Pressure
International audience; The effect of an applied high pressure on the optical and acoustic vibrations of small anatase TiO2 nanoparticles is studied using Raman scattering. All the Raman peaks show a significant variation of their frequency with pressure, except for the low-frequency peak which is due to acoustic vibrations confined in the nanoparticles. These variations (or lack thereof) are compared to first-principles calculations of the stiffness tensor and phonons of bulk anatase TiO2 as a function of pressure. In particular, the variation of the shape of the low-frequency peak is explained by the increase of the elastic anisotropy of anatase TiO2 as pressure is increased.
Growth and size distribution of Au nanoparticles in annealed Au/TiO2 thin films
Abstract Nanocomposites consisting of noble metal nanoparticles (NPs) embedded in TiO2 thin films are of great interest for applications in optoelectronics, photocatalysis and solar-cells for which the plasmonic properties of the metal NPs play a major role. This work investigates the first stages of the formation of gold NPs by thermal annealing of Au-doped TiO2 thin films grown by magnetron sputtering. A low concentration of gold in the films is considered (5 at.%) in order to study the first stages of the formation of the NPs. Raman spectroscopy is used to follow the crystallization of TiO2 when increasing the annealing temperature. In addition, low-frequency Raman scattering (LFRS) is u…
Quasi-free nanoparticle vibrations in a highly-compressed ZrO2 nanopowder
Several-nanometer-size mechanical oscillators, or nanoresonators, may complement electronic and optical technologies in future terahertz devices, but they can be useful only if they can be made to ...
TiO2 anatase films obtained by direct liquid injection atomic layer deposition at low temperature
International audience; TiO2 thin films were grown by direct liquid injection atomic layer deposition (DLI-ALD) with infrared rapid thermal heating using titanium tetraisopropoxide and water as precursors. This titanium tetraisopropoxide/water process exhibited a growth rate of 0.018 nm/cycle in a self-limited ALD growth mode at 280 degrees C. Scanning electron microscopy and atomic force microscopy analyses have shown a smooth surface with a low roughness. XPS results demonstrated that the films were pure and close to the TiO2 stoichiometric composition in depth. Raman spectroscopy revealed that the films were crystallized to the anatase structure in the as-deposited state at low temperatu…
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…
Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate
International audience; Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such “magic-size” clusters can be both stab…
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…
Microstructural and tribological study of Nd:YAG laser treated titanium plates.
Abstract In this work, the fretting behaviour of pure Ti plates laser treated with a Nd:YAG pulsed laser was compared to that of untreated Ti plates. Fretting tests were done at room temperature without lubrication. The contact geometry was a cylinder (bearing steel) on a plane. The evolution of both the ratio, μ = Q / P , between the normal and the tangential forces, and the Fouvry's energy criterion ( A ) were recorded as a function of the number of fretting cycles, N . Energy dispersive spectrometry and micro-Raman spectroscopy were used to analyse the fretting scars. The oxidized layer formed by the laser treatment displayed a mixed slip regime as a function of N , and a smaller frettin…
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…
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…
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.
THz nanocrystal acoustic vibrations from ZrO2 3D supercrystals
International audience; We report sharp low-frequency Raman spectral features of supercrystals synthesized via the "benzyl alcohol route" and consisting of either yttrium-stabilized or pure zirconia (ZrO2) nanocrystals. In situ formed benzoate species control the nanocrystal growth and act as organic glue leading to the assembly of the nanocrystals in highly ordered 3D supercrystals. We attribute some Raman peaks to THz acoustic vibrations of individual nanocrystals which are only weakly coupled due to the strong acoustic mismatch between the capping ligands and the nanocrystals. Peak positions are consistent with nanocrystal sizes estimated from transmission electron microscopy and X-ray p…
Optical properties of nanocrystalline-coatedY2O3:Er3+, Yb3+ obtained by mechano-chemical and combustion synthesis.
International audience; Y2O3:Er3+, Yb3+ nanocrystals have been obtained by ball milling and using a combustion synthesis procedure. In both cases the nanocrystals have been successfully coated with SiO2 following the Stöber method. The average size of the as-synthesized nanoparticles has been estimated from X-ray diffraction patterns and transmission electron microscopy images. The dependence of the optical properties of these samples on synthesis procedure or dopant concentration has been investigated. Emission, excitation and lifetime measurements have been carried out. Upconversion luminescence has been detected in all samples and an enhancement of the red to green emission ratio has bee…
Influence of the composition of titanium oxynitride layers on the fretting behavior of functionalized titanium substrates: PVD films versus surface laser treatments
International audience; Abstract In this work we compared the fretting behavior of pure titanium plates functionalized with titanium oxynitride surface layers, obtained by two methods: a Physical Vapor Deposition (PVD) method, reactive magnetron sputtering, and Surface Laser Treatments (SLT), under different mixtures of oxygen and nitrogen. The composition of the layers was determined by nuclear reaction analysis (NRA) and their structure was analyzed by Raman spectroscopy. PVD layers were TiN-like fcc layers, with an oxygen concentration going from 36 to 50 at.%. Three SLT layers were studied. The first one was a TiN-like layer containing ~28 at.% of oxygen. The second one was formed of di…
Structural analysis of W3O/WO3 and TiO/TiO2 periodic multilayer thin films sputter deposited by the reactive gas pulsing process
International audience; DC reactive sputtering was used to deposit titanium and tungsten-based metal/oxide periodic nanometric multilayers using pure metallic targets and Ar + O-2 gas mixture as reactive atmosphere. The innovative technique namely, the reactive gas pulsing process allows switching between the metal and oxide to prepare a periodic multilayered structure with various metalloid concentrations and nanometric dimensions. The same pulsing period was used for each deposition to produce metal-oxide periodic alternations close to 10 nm. Structure, crystallinity and chemical composition of these films were systematically investigated by Raman spectroscopy, X-ray diffraction and Energ…
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…
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…