FORTE - a multipurpose high-vacuum diffractometer for tender X-ray diffraction and spectroscopy at the SIRIUS beamline of Synchrotron SOLEIL.

A new high-vacuum multipurpose diffractometer (called FORTE from the French acronyms of the project) has recently been installed at the tender/hard X-ray SIRIUS beamline of Synchrotron SOLEIL, France. The geometry chosen allows one to work either in the classical Eulerian four-circle geometry for bulk X-ray diffraction (XRD) or in the z-axis geometry for surface XRD. The diffractometer nicely fits the characteristics of the SIRIUS beamline, optimized to work in the 1.1-4.5 keV range, and allows one to perform unprecedented diffraction anomalous fine structure (DAFS) experiments in the tender X-ray region, also around non-specular reflections, covering a large reciprocal-space volume. Installation of an X-ray fluorescence detector on a dedicated flange allows simultaneous DAFS and X-ray absorption (XAS) measurements. The access to the tender X-ray region paves the way to resonant investigations around the L-edges of second-row transition elements which are constituents of functional oxide materials. It also enables access to several edges of interest for semiconductors. Finally, the control architecture based on synchronized Delta Tau units opens up exciting perspectives for improvement of the mechanical sphere of confusion.

Strain engineering of perovskite thin films using a single substrate.

Combining temperature-dependent x-ray diffraction, Raman spectroscopy and first-principles-based effective Hamiltonian calculations, we show that varying the thickness of (Ba0.8Sr0.2)TiO3 (BST) thin films deposited on the same single substrate (namely, MgO) enables us to change not only the magnitude but also the sign of the misfit strain. Such previously overlooked control of the strain allows several properties of these films (e.g. Curie temperature, symmetry of ferroelectric phases, dielectric response) to be tuned and even optimized. Surprisingly, such desired control of the strain (and of the resulting properties) originates from an effect that is commonly believed to be detrimental to functionalities of films, namely the existence of misfit dislocations. The present study therefore provides a novel route to strain engineering, as well as leading us to revisit common beliefs.

Structure and magnetism of epitaxial PrVO3 films.

The interplay between charge, spin, orbital and lattice degrees of freedom in transition metal oxides has motivated extensive research aiming to understand the coupling phenomena in these multifunctional materials. Among them, rare earth vanadates are Mott insulators characterized by spin and orbital orderings strongly influenced by lattice distortions. Using epitaxial strain as a means to tailor the unit cell deformation, we report here on the first thin films of PrVO3 grown on (001)-oriented SrTiO3 substrate by pulsed laser deposition. An extensive structural characterization of the PrVO3 films, combining x-ray diffraction and high-resolution transmission electron microscopy studies, reveals the presence of oriented domains and a unit cell deformation tailored by the growth conditions. We have also investigated the physical properties of the PrVO3 films. We show that, while PrVO3 exhibits an insulating character, magnetic measurements indicate low-temperature hard-ferromagnetic behavior below 80 K. We discuss these properties in view of the thin-film structure.

Orthorhombic polar Nd-doped BiFeO3 thin film on MgO substrate.

A Nd-doped BiFeO(3) thin film deposited on MgO substrate was studied by synchrotron diffraction. The ferroelectric nature of the film is proven by in-plane remanent polarization measurement. The highest possible symmetry of the film is determined to be orthorhombic, within the Fm2m space group. Such a structure is rotated by 45° with respect to the substrate and is consistent with tilts of oxygen octahedra doubling the unit cell. This polar structure presents a rather unusual strain-accommodation mechanism.

High-pressure effect on PbTiO3: an investigation by Raman and x-ray scattering up to 63 GPa.

We report a room-temperature high-pressure x-ray and Raman scattering investigation of lead titanate (PbTiO3) up to 63 GPa. Three continuous phase transitions at 13, 20, and 45 GPa between tetragonal-like phases occur. As a result, no evidence is found for a pressure-induced morphotropic phase boundary. Our study provides experimental evidence that PbTiO3 presents a complex sequence of phases accommodating pressure through mechanisms involving oxygen octahedra tilting and reentrance of ferroelectricity.

Phase diagram of pb(Zr,Ti)O3 solid solutions from first principles.

A first-principles-derived scheme that incorporates ferroelectric and antiferrodistortive degrees of freedom is developed to study finite-temperature properties of Pb(Zr1-xTix)O3 solid solution near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.

Ferroelectricity of perovskites under pressure.

Ab initio simulations and experimental techniques are combined to reveal that, unlike what was commonly accepted for more than 30 years, perovskites and related materials enhance their ferroelectricity as hydrostatic pressure increases above a critical value. This unexpected high-pressure ferroelectricity is different in nature from conventional ferroelectricity because it is driven by an original electronic effect rather by long-range interactions.