RESUMEN
In the framework of expanding the range of copper-based compounds in the pyroxene family, we have synthesized at high pressure and high temperature a powder containing a mixture of a new phase with stoichiometry Sr5CuGe9O24 having two identified impurity phases. Electron crystallography showed that the new phase crystallizes in the monoclinic space group P2/c, with unit-cell parameters a = 11.8â Å, b = 8.1â Å, c = 10.3â Å and ß = 101.3°. We applied the recently developed low-dose electron diffraction tomography method to solve the structure by direct methods. The obtained structure model contains all 9 independent cation positions and all 13 oxygen positions. A subsequent refinement against powder X-ray diffraction data ascertained the high quality of the structure solution, in particular, the unusual structural arrangement that there are three different environments for Ge in this phase.
RESUMEN
Transmission electron microscopy, neutron diffraction, and synchrotron powder X-ray diffraction reveal a complex modulated structure on the doubly ordered perovskite NaLaCoWO6. Electron diffraction patterns as well as high-resolution transmission electron microscopy images clearly show a periodicity of 12 ap, where ap is the cell parameter of the generic perovskite, along either the [100]p or [010]p direction. Annular bright-field scanning transmission electron microscopy of slightly tilted samples shows that there is no chemical origin for the superstructure but that it is caused by geometric rearrangements. An atomic model of the superstructure is proposed on the basis of octahedral tilt twinning. At low temperature, NaLaCoWO6 undergoes a phase transition and the superstructure disappears. The compound takes on the more usual monoclinic P21 structure below the transition. Neutron powder diffraction reveals and electron diffraction confirms an unusually large temperature hysteresis, where the transition takes place at â¼180 K on cooling and at â¼320 K on heating. This hysteresis can be attributed to the necessity of rearranging the oxygen octahedra and the thus induced energy barrier for the transition.
RESUMEN
In the search for frustrated spin interactions, a YCuO2.66 phase has been synthesized by a treatment under oxygen pressure of YCuO2.5. X-ray powder diffraction and electron diffraction studies have been conducted. Electron diffraction shows that the sample is twinned on a 10â nm scale. Precession electron diffraction data obtained from a twinned crystal was treated in order to obtain intensities corresponding to only one of the orientations of the twins. From this data a structure solution was obtained where, as in YCuO2.5, the Cu atoms form triangular planes. The Cu atoms are linked in two dimensions by oxygen atoms in the present structure whereas in YCuO2.5 they are only linked in one-dimensional chains.
RESUMEN
BiCu2PO6 is a unique example of a S = 1/2 ladder where the magnetic exchanges are mainly confined in 1D ∞[BiCu2O2]3+ cationic ribbons, although the shortest Cu-Cu separation between them exists. Its original magnetic topology gives the most representative example of a frustrated quantum ladder to investigate the complex physics behind it. Herein, we report the synthesis and characterization of one high-pressure polymorph. In this new phase, the preservation of 1D ∞[BiCu2O2]3+ units somewhat restacked leads to the preservation of its gapped magnetic ground state and ladder topology. The comparison of both compounds highlights the start of a thermodynamic conjuncture, where both the stable ambient-pressure (AP) and metastable high-pressure (HP) forms display the same equilibrium volume and superposed volume dependence of the energy, leading to a first-order AP â HP transition undetected by differential thermal analysis.
RESUMEN
The compounds of the doubly ordered perovskite family NaLnCoWO6 (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) were synthesized by solid-state reaction, nine of which (Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) are new phases prepared under high-temperature and high-pressure conditions. Their structural properties were investigated at room temperature by synchrotron X-ray powder diffraction and neutron powder diffraction. All of them crystallize in monoclinic structures, especially the nine new compounds have the polar space group P21 symmetry, as confirmed by second harmonic generation measurements. The P21 polar structures were decomposed and refined in terms of symmetry modes, demonstrating that the polar mode is induced by two nonpolar modes in a manner of Hybrid Improper Ferroelectricity. The amplitudes of these three major modes all increase with decreasing the Ln cation size. The spontaneous ferroelectric polarization is estimated from the neutron diffraction data of three samples (Ln = Y, Tb, and Ho) and can be as large as â¼20 µC/cm2.
RESUMEN
The interaction of coexisting structural instabilities in multiferroic materials gives rise to intriguing coupling phenomena and extraordinarily rich phase diagrams, both in bulk materials and strained thin films. Here we investigate the multiferroic BiMnO3 with its peculiar 6s2 electrons and four interacting mechanisms: electric polarity, octahedra tilts, magnetism, and cooperative Jahn-Teller distortion. We have probed structural transitions under high pressure by synchrotron x-ray diffraction and Raman spectroscopy up to 60 GPa. We show that BiMnO3 displays under pressure a rich sequence of five phases with a great variety of structures and properties, including a metallic phase above 53 GPa and, between 37 and 53 GPa, a strongly elongated monoclinic phase that allows ferroelectricity, which contradicts the traditional expectation that ferroelectricity vanishes under pressure. Between 7 and 37 GPa, the Pnma structure remains remarkably stable but shows a reduction of the Jahn-Teller distortion in a way that differs from the behavior observed in the archetypal orthorhombic Jahn-Teller distorted perovskite LaMnO3.