Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)

The temperature-composition phase diagram of barium calcium titanate zirconate (x(Ba0.7Ca0.3TiO3)(1-x)(BaZr0.2Ti0.8O3); BCTZ) has been reinvestigated using high-resolution synchrotron x-ray powder diffraction. Contrary to previous reports of an unusual rhombohedral-tetragonal phase transition in this system, we have observed an intermediate orthorhombic phase, isostructural to that present in the parent phase, BaTiO3, and we identify the previously assigned T-R transition as a T-O transition. We also observe the O-R transition coalescing with the previously observed triple point, forming a phase convergence region. The implication of the orthorhombic phase in reconciling the exceptional piezoelectric properties with the surrounding phase diagram is discussed

Resonant X-ray diffraction studies on the charge ordering in magnetite

Here we show that the low temperature phase of magnetite is associated with an effective, although fractional, ordering of the charge. Evidence and a quantitative evaluation of the atomic charges are achieved by using resonant x-ray diffraction (RXD) experiments whose results are further analyzed with the help of ab initio calculations of the scattering factors involved. By confirming the results obtained from X-ray crystallography we have shown that RXD is able to probe quantitatively the electronic structure in very complex oxides, whose importance covers a wide domain of applications.Comment: 4 pages 4 figures, accepted for publication in PR

Step by step capping and strain state of GaN/AlN quantum dots studied by grazing incidence diffraction anomalous fine structure

The investigation of small size embedded nanostructures, by a combination of complementary anomalous diffraction techniques, is reported. GaN Quantum Dots (QDs), grown by molecular beam epitaxy in a modified Stranski-Krastanow mode, are studied in terms of strain and local environment, as a function of the AlN cap layer thickness, by means of grazing incidence anomalous diffraction. That is, the X-ray photons energy is tuned across the Ga absorption K-edge which makes diffraction chemically selective. Measurement of \textit{hkl}-scans, close to the AlN (30-30) Bragg reflection, at several energies across the Ga K-edge, allows the extraction of the Ga partial structure factor, from which the in-plane strain of GaN QDs is deduced. From the fixed-Q energy-dependent diffracted intensity spectra, measured for diffraction-selected iso-strain regions corresponding to the average in-plane strain state of the QDs, quantitative information regarding composition and the out-of-plane strain has been obtained. We recover the in-plane and out-of-plane strains in the dots. The comparison to the biaxial elastic strain in a pseudomorphic layer indicates a tendency to an over-strained regime.Comment: submitted to PR

Low-temperature structure of magnetite studied using resonant x-ray scattering

13 pagesInternational audienceWe propose a model for the Fe atomic displacements in the low-temperature phase of magnetite Fe3O4 , based on the analysis of the photon energy dependence of the scattered intensity of selected reflections in a resonant x-ray scattering experiment. The symmetry of the displacement pattern is forced to be consistent with the Cc space group, long time claimed to be the actual symmetry of the low-temperature phase. Fe positions at octahedral sites and the corresponding charges are accounted for by a fitting procedure comparing simulations and experiment.We found a pattern of small distortions in the a-b plane. An independent sensitivity to the charge occupancy permits to refine the model of charge ordering previously proposed. Finally we have computed the electric moment of the combined charge displacements to be 1.5 C/cm2

Structural and magnetic properties of CoPt mixed clusters

In this present work, we report a structural and magnetic study of mixed Co58Pt42 clusters. MgO, Nb and Si matrix can be used to embed clusters, avoiding any magnetic interactions between particles. Transmission Electron Microscopy (TEM) observations show that Co58Pt42 supported isolated clusters are about 2nm in diameter and crystallized in the A1 fcc chemically disordered phase. Grazing Incidence Small Angle X-ray Scattering (GISAXS) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) reveal that buried clusters conserve these properties, interaction with matrix atoms being limited to their first atomic layers. Considering that 60% of particle atoms are located at surface, this interactions leads to a drastic change in magnetic properties which were investigated with conventional magnetometry and X-Ray Magnetic Circular Dichro\"{i}sm (XMCD). Magnetization and blocking temperature are weaker for clusters embedded in Nb than in MgO, and totally vanish in silicon as silicides are formed. Magnetic volume of clusters embedded in MgO is close to the crystallized volume determined by GIWAXS experiments. Cluster can be seen as a pure ferromagnetic CoPt crystallized core surrounded by a cluster-matrix mixed shell. The outer shell plays a predominant role in magnetic properties, especially for clusters embedded in niobium which have a blocking temperature 3 times smaller than clusters embedded in MgO

Microdiffraction et microtomographie in situ des transformations hétérogènes du C sous haute pression et haute température

Le diagramme des phases du C60 continue d'être un sujet de discussion et de controverse, malgré la grande quantité de travaux expérimentaux et théoriques fait au fil des ans. Ceci est principalement dû au manque d'études in situ, a l'existence d états désordonnés présentant des pics de diffraction très mal résolus et à la coexistence de plusieurs polytypes de faible densité. Ce manuscrit présente une étude systématique in situ des transformations hétérogènes du C60 sous haute pression et haute température dans la gamme 1-10 GPa et 300-1200 K. Afin de discriminer les poly(a)morphes de densité similaire dans des échantillons hétérogènes, nous avons utilisé une combinaison de micro-diffraction et micro-tomographie. Les échantillons ont été synthétisés dans une cellule Paris-Edimbourg et caractérisés à l'aide de diffraction des rayons X in situ en dispersion angulaire. Des images tridimensionnels à haute résolution ont été obtenus sur des échantillons trempés par la méthode de micro-tomographie de diffraction/diffusion. Cette méthode permet l'analyse 3D de l'intensité de diffusion reconstruite à partir de séries de projections 2D. Une telle analyse est non destructive et offre une grande sensibilité (0,1% en volume), une haute résolution spatiale ( m3) et peut être multimodale, fournissant des données quantitatives sur la morphologie, la densité, la composition élémentaire ou la structure des matériaux. En outre, nous décrivons le développement d un système de micro-tomographie in situ sous haute pression et haute température en utilisant une nouvelle cellule rotative Paris-Edimbourg (RoToPEC), combinée avec le rayonnement synchrotron. La capacité à tourner complètement la chambre de l'échantillon sous charge, surmonte la contrainte d'ouverture angulaire limitée des cellules ordinaires et permet l'acquisition de projections tomographiques pour l'imagerie de plein champ ainsi que pour l'imagerie par micro-diffraction. Cette méthode innovante permet l étude des matériaux sous conditions extrêmes de pression, température ou stress, et pourra être appliquée dans des domaines variés tels que la physique, la chimie, la science des matériaux ou la géologie. Le potentiel de cette nouvelle technique expérimentale est démontré par l'étude de la polymérisation de C60 sous haute-pression et haute température. Mots-clés: C60, diagramme de phase, diffraction, micro-tomographie, haute pression et haute températureThe C60 reaction diagram continues to be a subject of discussion and controversy, despite the vast amount of experimental and theoretical work done over the years. This is mainly due the lack of in situ studies, the highly disordered-states showing poorly resolved diffraction peaks and the coexistence of several low-density polytypes. This manuscript presents a systematic in situ study of high-pressure high-temperature forms C60 in the range of 1-10 GPa and 300-1200 K. In order to discriminate poly(a)morphs with similar densities in heterogeneous samples, we used a combination of microdiffraction and microtromography. The samples were synthesized in a Paris-Edinburgh cell and characterized using in situ angular dispersive X-ray diffraction. Three-dimensional submicron images were obtained on quenched samples using diffraction/scattering microtomography. This method provides 3D analysis of the scattering intensity reconstructed from sets of 2D microdiffraction projections. Such analysis is non-destructive and provides high sensitivity (0.1% volume), high spatial resolution ( m3) and can be multi-modal providing quantitative information on the morphology, density, elemental composition or structure of materials. Additionally, we describe the development of in situ high-pressure high-temperature microtomography using a new rotating Paris-Edinburgh cell (RoToPEC) combined with synchrotron radiation. The ability to fully rotate the sample chamber under load, overcomes the limited angular aperture of ordinary high-pressure cells for acquiring tomographic projections in both, full-field imaging or microdiffraction modes. This innovative method enables dynamic studies of materials under extreme pressure-temperature-stress conditions, impacting areas such as physics, chemistry, materials science or geology. The potential of this new experimental technique is demonstrated on the in situ investigation of of high-pressure high-temperature polymerization of C60 . Keywords: C60, phase diagram, diffraction, microtomography, high-pressure high-temperatureSAVOIE-SCD - Bib.électronique (730659901) / SudocGRENOBLE1/INP-Bib.électronique (384210012) / SudocGRENOBLE2/3-Bib.électronique (384219901) / SudocSudocFranceF

X-ray anomalous scattering investigations on the charge order in α′\alpha^\prime-NaV2_2O5_5

Anomalous x-ray diffraction studies show that the charge ordering in $\alpha^\prime$-NaV$_2$O$_5$ is of zig-zag type in all vanadium ladders. We have found that there are two models of the stacking of layers along \emph{c-}direction, each of them consisting of 2 degenerated patterns, and that the experimental data is well reproduced if the 2 patterns appears simultaneously. We believe that the low temperature structure contains stacking faults separating regions corresponding to the four possible patterns.Comment: Submitted to Phys. Rev. Lett., 4 pages, 4 eps figures inserted in the tex

X-Ray Scattering Measurements of the Transient Structure of a Driven Charge-Density-Wave

We report time-resolved x-ray scattering measurements of the transient structural response of the sliding {\bf Q}$_{1}$ charge-density-wave (CDW) in NbSe$_{3}$ to a reversal of the driving electric field. The observed time scale characterizing this response at 70K varies from $\sim$ 15 msec for driving fields near threshold to $\sim$ 2 msec for fields well above threshold. The position and time-dependent strain of the CDW is analyzed in terms of a phenomenological equation of motion for the phase of the CDW order parameter. The value of the damping constant, $\gamma = (3.2 \pm 0.7) \times 10^{-19}$ eV $\cdot$ seconds $\cdot$ \AA$^{-3}$, is in excellent agreement with the value determined from transport measurements. As the driving field approaches threshold from above, the line shape becomes bimodal, suggesting that the CDW does not depin throughout the entire sample at one well-defined voltage.Comment: revtex 3.0, 7 figure

Interplay of inequivalent atomic positions in resonant x-ray diffraction of Fe3BO6

'Forbidden' Bragg reflections of iron orthoborate Fe3BO6 were studied theoretically and experimentally in the vicinity of the iron K edge. Their energy spectra are explained as resulting from the interference of x-rays scattered from two inequivalent crystallographic sites occupied by iron ions. This particular structure property gives rise to complex azimuthal dependences of the reflection intensities in the pre-edge region as they result from the interplay of site specific dipole-quadrupole and quadrupole-quadrupole resonant scattering. Also evidenced is an isotropic character of the absorption spectrum. Self-absorption correction to the diffraction data, as well as possible contributions of thermal vibrations and magnetic order, are discussed. Particular care is given to extracting clean spectra from the data, and it is demonstrated that excellent results can be obtained even from measurements that appear corrupted by several effects such as poor crystal quality and multiple scattering.Comment: 12 page