Thin films preparation by rf-sputtering of copper/iron ceramic targets with Cu/Fe=1: From nanocomposites to delafossite compounds

In the Cu–Fe–O phase diagram, delafossite CuFeO2 is obtained for the CuI oxidation state and for the Cu/Fe=1 ratio. By decreasing the oxygen content, copper/spinel oxide composite can be obtained because of the reduction and the disproponation of cuprous ions. Many physical properties as for instance, electrical, optical, catalytic properties can then be affected by the control of the oxygen stoichiometry. In rf-sputtering technique, the bombardment energies on the substrate can be controlled by the deposition conditions leading to different oxygen stoichiometry in the growing layers. By this technique, thin films have been prepared from two ceramic targets: CuFeO2 and CuO+CuFe2O4. We thus synthesized either Cu0/ CuxFe1−xO4 nanocomposites thin films with various Cu0 quantities or CuFeO2-based thin films. Two-probes conductivity measurements were permitted to comparatively evaluate the Cu0 content, while optical microscopy evidenced a selfassembly phenomenon during thermal annealing

L'enseignement de la cristallographie en sciences des matériaux

La cristallographie est une discipline scientifique clé à l’interface de nombreuses spécialités enseignées dans l’enseignement supérieur. Dans le cadre des formations « Matériaux » de l’Université Paul Sabatier Toulouse III, l’enseignement de cette discipline vise principalement à donner aux étudiants les moyens d’appréhender les problèmes liés aux aspects structuraux et microstructuraux de la matière. Leur mise en pratique via des méthodes actuelles d’analyse est au centre de ces enseignements et fait l’objet des quelques illustrations de cet article. Crystallography teaching in material sciences Crystallography is a key scientific discipline at the interface of many specialties taught in higher education. In the frame of the training in material sciences at the University Paul Sabatier Toulouse III, the teaching of this discipline is primarily intended to provide students with the means to understand the problems related to structural and microstructural aspects of the material. Their implementation via current methods of analysis is at the heart of this teaching and is the subject of this article through few illustrations

Structural study and phase transition investigation in a simple synthesis of porous architected-ZnO nanopowder

In this work, zinc oxide powder with a rectangular-shaped porous architecture, made of numerous spherical nanometric particles,was obtained. Asimple precipitation/decomposition procedure was used comprising a zinc oxalate intermediate, obtained from zinc sulfate and oxalic acid without any additives. Detailed studies on zinc oxalate dehydration, decomposition and zinc oxide formation, were carried out using in-situ temperature X-ray diffraction and thermogravimetric analysis. During the investigation, the temperature dependence of particle sizes, lattice parameters and crystal structures of ZnC2O4·2H2O, ZnC2O4 and ZnO nanopowders were analyzed from room temperature to 450 °C. Structural transitions were also discussed. The structure and morphology of the as-prepared ZnO nanopowder were investigated by electron microscopy and compared to the crystalline rectangular shape of ZnC2O4·2H2O. The calcination temperature, counter ion and precipitate agent were found to be related to the product's shape and diameter. Spherical ZnO nanoparticleswith diameters of less than 20 nm and a maximum specific surface of 53 m2/g were obtained using thismethod

CO2 sensing properties of semiconducting copper oxide and spinel ferrite nanocomposite thin film

A new active layer for CO2 sensing based on semiconducting CuO–CuxFe3−xO4 (with 0 ≤ x ≤ 1) nanocomposite was prepared by radiofrequency sputtering from a delafossite CuFeO2 target using a specific in situ reduction method followed by post annealing treatment in air. The tenorite–spinel ferrite nanocomposite layer was deposited on a simplified test device and the response in a carbon dioxide atmosphere was measured by varying the concentration up to 5000 ppm, at different working temperatures (130–475 °C) and frequencies (0.5–250 kHz). The results showed a high response of 50% (Rair/RCO2=1.9) at 250 °C and 700 Hz for a CO2 concentration of 5000 ppm

Sol–gel processing and characterization of (RE-Y)-zirconia powders for thermal barrier coatings

The effect of doping on the structural, morphological and thermal properties of ZrO2–XO1.5 (X=Y, La, Sm, Er) solid solutions for thermal barrier (TBC) applications was investigated. Oxide powders of various compositions from 9.7 to 40 mol% XO1.5 (X=Y, La, Sm, Er) were synthesised by the sol–gel route. The structural analysis of the powders was performed using X-ray diffraction analysis coupled with Rietveld refinements and the measurement of their specific surface area with the BET method. For each rare earth dopant, the morphology of the powders varies from monoliths to agglomerates of thinner particles when the doping amount increases. In order to determine the specific heat, the thermal diffusivity at room temperature and the thermal expansion coefficient of some selected compositions, DSC, laser thermal diffusivity and hightemperature dilatometry measurements were performed on samples densified by Spark Plasma Sintering. Working thermal characterisation indicated that zirconia doped with 30 mol% SmO1.5 and ErO1.5 have better insulation properties and a lower thermal expansion coefficient than our reference YSZ ceramic. These various compositions are very promising for the elaboration of multilayer TBCs by the sol–gel process

Nanocomposites of metallic copper and spinel ferrite films: Growth and self-assembly of copper particles

Nanocomposites of metallic copper and iron oxides films have been prepared by RF-sputtering of pure CuFeO2 delafossite target. The films are made of copper and spinel ferrite crystallites of less than 10 nm in diameter. The content of metallic copper and the ferrite composition depend on the sputtering conditions. For the shortest substrate-target distances, films are made of copper and copper substituted magnetite with low copper content. The formation of the metallic and spinel phases is due to the loss of a small quantity of oxygen during sputtering. When annealed under inert atmosphere, nanometric copper particles located in the upper part of the film, move on the surface and grow due to coalescence phenomena. The particle motion can be stopped by small grooves allowing the self-assembly of copper particles

Copper and iron based thin film nanocomposites prepared by radio frequency sputtering. Part I: elaboration and characterization of metal/oxide thin film nanocomposites using controlled in situ reduction process

Copper and iron based thin films were prepared on glass substrate by radio-frequency sputtering technique from a delafossite CuFeO2 target. After deposition, the structure and microstructure of the films were examined using grazing incidence X-ray diffraction, Raman spectroscopy, electron probe micro-analysis and transmission electron microscopy coupled with EDS mapping. Target to substrate distance and sputtering gas pressure were varied to obtain films having different amount and distribution of copper nanoparticles and different composition of oxide matrix. The overall reaction process, which starts from CuFeO2 target and ends with the formation of films having different proportion of copper, copper oxide and iron oxide, was described by a combination of balanced chemical reactions. A direct relationship between the composition of the metal/oxide nanocomposite thin film and the sputtering parameters was established. This empirical relationship can further be used to control the composition of the metal/oxide nanocomposite thin films, i.e. the in situ reduction of copper ions in the target

Mössbauer characterisations and magnetic properties of iron cobaltites CoxFe3−xO4 (1 ≤ x ≤ 2.46) before and after spinodal decomposition

Iron cobaltite powders CoxFe3_xO4 (1 ≤ x ≤ 2.46) were synthesized with compositions in between the cobalt errite CoFe2 O4 and Co2.46Fe0.54O4. The cationic distribution of pure spinel phases was determined by Mossbauer spectroscopy: as Co content increases in the spinel oxide, Co3+ cations replace Fe3+ cations in the octahedral sites and Co2+ cations migrate from octahedral to tetrahedral sites. Saturation magnetizations MS measured at 5 K by a SQUID magnetometer were consistent with the values calculated from the cationic distribution. MS decreases as diamagnetic Co3+ cations replace strongly magnetic Fe3+ cations. Two spinel phases were formed by spinodal decomposition of Co1.73Fe1.27O4 phase submitted to a subsequent thermal treatment, one with a high amount of iron Co1.16Fe1.84O4 and one other containing mostly cobalt Co2.69Fe0.31O4. Increase of the experimental MS value obtained after the spinodal decomposition is in accordance with the calculated value deduced from the cationic distribution of the two phases

Copper and iron based thin film nanocomposites prepared by radio-frequency sputtering. Part II: elaboration and characterization of oxide/oxide thin film nanocomposites using controlled ex-situ oxidation process

CuO/CuFe2O4 thin films were obtained on glass substrate by ex situ oxidation in air at 450°C for 12 h from various starting metal/oxide nanocomposites by radio-frequency sputtering technique. The structure and microstructure of the films were examined using grazing incidence X-ray diffraction, Raman spectroscopy, scanning and transmission electronmicroscopies, X-ray photoelectron spectroscopy, and electron probe microanalysis. These studies reveal that a selforganized bi-layered microstructure with CuO (surface layer) and CuFe2O4 (heart layer) was systematically obtained. Due to the porosity of the upper layer formed during annealing, an increase in total thickness of the film was observed and is directly correlated to the oxidation of the metallic copper content initially present in the as-deposited sample. A selforganization in twostacked layers CuO/CuFe2O4with various void fractions ranging from 0 to 41 % can be obtained by controlling the as-deposited elaboration step described in the part I of this paper. The highest porosities were observed for films deposited at low argon pressure and low target-to-substrate distance. Due to their specific self-organization in p- and n-type layers associated with their high porosity, such structured films exhibited the best electrical sensitivity to CO2 gas sensing. The obtained results demonstrated the importance of microstructure control to improve the response of sensing layers

Structural study of metastable tetragonal YSZ powders produced via a sol-gel route

Sol-gel yttria stabilized zirconia (YSZ) is investigated in this paper. The final aim is to process YSZ powders into stable slurries in order to prepare thick coatings for thermal barrier to be applied on hot turboengine components. In fact, this system is well-known for its excellent thermomechanical resistance at elevated temperatures but the relationship between these performances and the structural and microstructural characteristics of these materials is not fully understood. This paper reports a preliminary study concerning recent progress on the structural properties control of YSZ powders synthesized by solâ��gel process and the main advantages of this process compared to conventional methods. As a first step towards this understanding, structural investigations of ZrO2 doped with various xmol%YO1.5 coatings, have been performed using X-ray diffraction, structural Rietveld refinement, Raman spectra analysis and transmission electron microscopy. The evolution of the crystallographic structure of YSZ powders after air annealing at various temperatures 1100 °C, 1200 °C and 1400 °C was studied to well understand the conditions of the formation of desired metastable tetragonal phase (t). Then, this work should allow to correlate chemical and thermomechanical parameters as YSZ formulation and sol-gel elaboration conditions, temperature and t phase performances