Florence Porcher

Systematical, experimental investigations on LiMgZ (Z = P, As, Sb) wide band gap semiconductors

This work reports on the experimental investigation of wide band gap compounds LiMgZ (Z = P, As, Sb), which are promising candidates for opto-electronics and anode materials for lithium batteries. The compounds crystallize in the cubic (C1b) MgAgAs structure (space group ). The polycrystalline samples are synthesized by solid-state reaction methods. X-ray and neutron diffraction measurements show homogeneous, single-phased samples. The electronic properties are studied using the direct current method. Additionally, UV–Vis diffuse reflectance spectra are recorded in order to investigate the band gap nature. The measurements show that all compounds exhibit semiconducting behaviour with direct band gaps of 1.0–2.3 eV depending on the Z element. A decrease in the peak widths in the static 7Li nuclear magnetic resonance spectra with increasing temperature is observed, which can be directly related to an increase in Li ion mobility.

Highly Transparent BaAl4O7 Polycrystalline Ceramic Obtained by Full Crystallization from Glass

Transparent polycrystalline ceramics are an emerging class of photonic quality materials competing with single crystal technology for a diverse range of applications including high-energy lasers, scintillating devices, optical lenses, and transparent armour. Polycrystalline ceramics offer several advantages, particularly in the fabrication of complex shapes and large-scale industrial production, and enable greater and more homogenous doping of optically active ions than is possible in single crystals. A limited number of either cubic or nanocrystalline transparent polycrystalline ceramics are known, but require complex and time-consuming synthetic approaches. Here, we show for the fi rst time that fully dense transparent polycrystalline ceramics can be simply obtained by direct and complete crystallization from glass. This is demonstrated for the previously unreported composition, BaAl 4 O 7 , which exhibits two orthorhombic polymorphs with micrometer grain size, both optically transparent in the visible range. This innovative synthetic route to transparent polycrystalline ceramics should facilitate the discovery of new, cost-effective chemical methods for transparent ceramic applications. Conventional optically transparent single crystal materials are widely used in numerous photonic applications. However, these materials face several technological and economical challenges, including a restricted list of appropriate single crystal compounds, limitations on the type and level of chemical doping, and mechanical and manufacturing requirements for large and complex physical shapes. Many of these obstacles can be avoided through the use of ceramic materials, which afford a wider range

IM-19: a new flexible microporous gallium based-MOF framework with pressure- and temperature-dependent openings.

Five metal-organic frameworks (MOFs) based on the same three-dimensional gallium terephthalate network (IM-19) are described, and an incommensurate structure (for the as-synthesized form) as well as two remarkable guest-free polymorphs (open and closed) are highlighted.

Miscibility gap in the U-Nd-O phase diagram: a new approach of nuclear oxides in the environment?

To some extent, rare-earth-doped UO(2) is representative of an irradiated nuclear fuel. The two phases we observed previously in neodymium-doped UO(2) are now interpreted as the existence of a miscibility gap in the U-Nd-O phase diagram using new results obtained with Raman spectroscopy. Extrapolating the miscibility gap in the U-Nd-O phase diagram to irradiated UO(2) opens the path to a new understanding of nuclear oxides in the environment.

Unprecedented robust antiferromagnetism in fluorinated hexagonal perovskites.

The diversification of antiferromagnetic (AFM) oxides with high Néel temperature is of fundamental as well as technical interest if one considers the need for robust AFM in the field of spin-tronics (exchange bias, multiferroics, etc.). Within the broad series of so-called hexagonal perovskites (HP), the existence of face-sharing octahedral units drastically lowers the strength of magnetic exchanges as compared to corner-sharing octahedral edifices. Here, we show that the partial introduction of F(-) in several Fe-based HP types leads to a drastic increase of the AFM ordering close to the highest values reported in iron oxides (T(N) ≈ 700 K). Our experimental results are supported by ab initio calculations. The T(N) increase is explained by the structural effect of the aliovalent F(-) for O(2-) substitution occurring in preferred anionic positions: it leads to local changes of the Fe-O-Fe connectivity and to chemical reduction into predominant Fe(3+), both responsible for drastic magnetic changes.

The role of the Pb2+ 6s lone pair in the structure of the double perovskite Pb2ScSbO6

The new double perovskite Pb2ScSbO6 was synthesized by standard ceramic procedures; the Rietveld refinement of room temperature neutron powder diffraction data shows that the crystal structure is well defined in the space group Fm3[combining macron]m. It contains a completely ordered array of alternating ScO6 and SbO6 octahedra sharing corners; the PbO12 polyhedra present an off-center displacement of the lead atoms along the [111] direction, due to the electrostatic repulsion between the Pb2+ 6s lone pair and the Pb-O bonds of the cuboctahedron. Dielectric permittivity measurements show a peak near 343 K, with a Curie-Weiss response above this temperature, which suggests an antiferroelectric behavior. Finally we present a DFT study of the electronic structure of Pb2ScSbO6, showing a great difference between the electronic density within SbO6 and ScO6 octahedra.

Epitaxial growth of zeolite X on zeolite A and twinning in zeolite A: structural and topological analysis

Abstract Synthesis of large zeolite A and X crystals by a modified Charnell’s method led to the formation of twinned zeolite NaA crystals, overgrowth of NaX onto NaA and co-crystallization of another phase analysed by electron microprobe as a Na aluminosilicate but not yet identified. Single crystals of NaA have a perfect cubic habit with a 100 μm edge. Twinned crystals of NaA are of the same size and correspond to an intergrowth of two cubes like that found in twinned fluorite crystals. NaX single crystals are octahedral, 220 μm along the [100] direction. Based on the difference in morphology of A and X crystals, epitaxial growth of NaX zeolite on NaA was also clearly identified by scanning electron micrographs. The object of this contribution is to provide topological and structural information on the twinning and epitaxy.

Refinement of framework disorder in dehydrated CaA zeolite from single-crystal synchrotron data

An accurate knowledge of zeolite structure is required for understanding their selective sorption capacities and their catalytic properties. In particular, the positions of the exchangeable cations and their interactions with the framework are essential. The present study deals with the accurate crystal structure determination of a fully exchanged and fully dehydrated CaA zeolite (Ca(48)Al(96)Si(96)O(384), Fm3c, a = 24.47 A) using single-crystal high-resolution synchrotron X-ray diffraction [(sin straight theta/lambda)(max) = 1.4 A(-1)]. It is shown that cation exchange severely distorts the skeleton, especially around the O2 atom. The high-resolution synchrotron data reveal that this latter O atom is disordered and lies out of the mirror plane it occupies in other A-type zeolites. This feature is related to that observed for Ca(2+) cations.

Charge density research: from inorganic and molecular materials to proteins

Abstract This paper intends to present applications of experimental charge density research in physics, chemistry and biology. It describes briefly most methods for modelling the charge density and calculating and analyzing derived properties (electrostatic potential, topological properties). These methods are illustrated through examples ranging from material science and coordination chemistry to biocrystallography, like the estimation of electrostatic energy in a zeolite-like material or the relation between electrostatic energy and spin density to macroscopic magnetic properties in a ferrimagnetic molecular material. The accurate structure and charge density of a coordination compound exhibiting LIESST effect is also described, together with an exemple of transferability of charge density methods to macromolecular science and protein crystallography.

Study of the magnetic and electronic properties of nanocrystalline PrCo3 by neutron powder diffraction and density functional theory

Nanocrystalline PrCo(3) powder has been synthesized by high-energy milling and was subsequently annealed from 873 to 1273 K for 30 min to optimize the extrinsic properties. The structure and magnetic properties of the nanocrystalline PrCo(3) have been investigated by means of x-ray and neutron diffraction as well as magnetization measurements. All compounds crystallize in the same PuNi(3) type structure, with grain sizes between 28 and 47 nm. As the annealing temperature increases, a maximum coercive field of 12 kOe at 300 K (55 kOe at 10 K) was obtained by annealing at 1023 K for a grain size of 35 nm. The refinement of the neutron powder diffraction patterns (NPD) of PrCo(3) from 1.8 to 300 K shows an expansion of the parameter a and a contraction of the parameter c, leading to a decrease of the ratio c/a. The evolution of the Co and Pr magnetic sublattices measured by NPD indicates that this compound is a highly anisotropic uniaxial ferromagnet with the easy magnetization axis parallel to c(-->). This experimental study has been completed by a theoretical investigation of the electronic structure of the PrCo(x) (x = 2, 3 and 5) compounds. Band structure calculations with collinear spin polarization were performed by using the local approximation of the density functional theory scheme implemented in the projector-augmented wave method. The electronic structure of PrCo(3) compound in both directions of spin shows that the majority of occupied states are dominated by the 3d states of Co, with a strong electronic charge transfer from Pr to Co. The PrCo(3) electronic structure can be explained by a superimposition of those of PrCo(2) and PrCo(5), as expected from its crystal structure. The magnetic anisotropy has been confirmed for PrCo(3), as a non-collinear spin calculation with the polarization along the c axis is shown to be more stable than with the polarization in the (a(-->),b(-->)) plane.