D. Mannix

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.

Epitaxial TbMnO3 thin films on SrTiO3 substrates: a structural study

TbMnO(3) films have been grown under compressive strain on (001)-oriented SrTiO(3) crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression, thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4xa0nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

Nature of the magnetic order and origin of induced ferroelectricity in TbMnO3

The magnetic structures which endow TbMnO(3) with its multiferroic properties have been reassessed on the basis of a comprehensive soft x-ray resonant scattering (XRS) study. The selectivity of XRS facilitated separation of the various contributions (Mn L(2) edge, Mn 3d moments; Tb M(4) edge, Tb 4f moments), while its variation with azimuth provided information on the moment direction of distinct Fourier components. When the data are combined with a detailed group theory analysis, a new picture emerges of the ferroelectric transition at 28 K. Instead of being driven by the transition from a collinear to a noncollinear magnetic structure, as has previously been supposed, it is shown to occur between two noncollinear structures.

Effect of surface polishing and oxidization induced strain on electronic order at the Verwey transition in Fe3O4

Following the controversy between two previous publications (Lorenzo etxa0al 2008 Phys. Rev. Lett. 101 226401 and Garcia etxa0al 2009 Phys. Rev. Lett. 102 176405), we report on the influence of mechanical polishing, and subsequent sample storage, on the electronic order at the Verwey transition of highly pure magnetite, Fe(3)O(4), by resonant x-ray scattering. Contrary to expectations, mechanically polishing the surface induces an inhomogeneous micron deep dead layer, probably of powdered Fe(3)O(4). In addition, we have found that polishing the sample immediately before the experiment influences and favors the appearance of long range order electronic correlations, whereas samples polished well in advance have their electronic order quenched. Conversely, lattice distortions associated with the Verwey transition appear less affected by the surface state. We conclude that mechanical polishing induces stresses at the surface that may propagate into the core of the single crystal sample. These strains relax with time, which affects the different order parameters, as measured by x-ray resonant diffraction.

Ordering of localized electronic states in multiferroic TbMnO3: a soft x-ray resonant scattering study

Soft x-ray resonant scattering (XRS) has been used to observe directly, for the first time, the ordering of localized electronic states on both the Mn and the Tb sites in multiferroic TbMnO3. Large resonant enhancements of the x-ray scattering cross-section were observed when the incident photon energy was tuned to either the Mn L or Tb M edges which provide information on the Mn 3d and Tb 4f electronic states, respectively. The temperature dependence of the XRS signal establishes, in a model independent way, that in the high-temperature phase (28 K≤T≤42 K) the Mn 3d sublattice displays long-range order. The Tb 4f sublattices are found to order only on entering the combined ferroelectric/magnetic state below 28 K. Our results are discussed with respect to recent hard XRS experiments (sensitive to spatially extended orbitals) and neutron scattering.

Simulation of Surface Resonant X-ray Diffraction

We present an ab initio numerical tool to simulate surface resonant X-ray diffraction experiments. The crystal truncation rods and the spectra around a given X-ray absorption edge are calculated at any position of the reciprocal space. Density functional theory is used to determine the resonant scattering factor of an atom within its local environment and to calculate the diffraction peak intensities for surfaces covered with a thin film or with one or several adsorbed layers. Besides the sample geometry, the collected data also depend on several parameters, such as beam polarization and incidence and exit angles. In order to account for these factors, a numerical diffractometer mimicking the experimental operation modes has been created. Finally two case studies are presented in order to compare our simulations with experimental spectra: (i) a magnetite thin film deposited on a silver substrate and (ii) an electrochemical interface consisting of bromine atoms adsorbed on copper.

Resonant x-ray scattering investigation of magnetic ordering in NpAs1 ? xSex (x = 0.05, 0.10)

A resonant x-ray scattering investigation of the NpAs(1 - x)Se(x) system with single crystals of 5 and 10% Se content is reported. The main features of the magnetic phase diagram previously studied by neutron scattering were confirmed. The coexistence within a single domain of ferro-xa0and antiferro-components in the low-T ferrimagnetic phase was established, as well as the single-k character of the incommensurate phase and of the antiferromagnetic component of the ferrimagnetic phase. A tetragonal lattice distortion was found in the ferro-xa0and ferrimagnetic phases which is not compatible with the proposed model for the ferromagnetic phase. The study of ferromagnetism was carried out using polarization analysis of the diffracted beam to separate the scattering intensities originating from magnetism and charge, which are superimposed in reciprocal space. The magnetic character of the ferromagnetic signal calculated from the measured intensities in the polarization analysis σπ and σσ channels was confirmed by analysis of the corresponding temperature dependence.

Epitaxial TbMnO3 thin films on SrTiO3 substrates

TbMnO(3) films have been grown under compressive strain on (001)-oriented SrTiO(3) crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression, thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4xa0nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

Epitaxial TbMnO3thin films on SrTiO3substrates: a structural study

TbMnO(3) films have been grown under compressive strain on (001)-oriented SrTiO(3) crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression, thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4xa0nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

CHARGE AND ORBITAL ORDER IN THE ELECTRON DOPED MAGNANITE (Bi,Ca)MnO3

The interplay between charge, spin and orbital degrees of freedom in transition metal oxides has been a matter of much interest in recent years. In this paper we present X-ray scattering results of charge and orbital ordering in the electron doped manganite Bi0.24Ca0.76MnO3. Using High Energy X-ray Scattering (HEXS) the charge ordering, structural modulation due to the Jahn–Teller ordering and the harmonic of the structural modulation have been measured. The superlattice reflections due to the Jahn–Teller ordering are found to maximise in intensity at the Neel point. We have confirmed using resonant X-ray scattering at the K-edge of manganese and the Anisotropic Tensor of Susceptibility technique (ATS) that superlattice reflections occurring at a modulation wavevector of (0.5, 0, 0) are due to charge ordering in a Mn3+/Mn4+ ordering pattern. In addition superlattice reflections corresponding to the orbital order were measured at a modulation wavevector of (0.25, 0, 0). The temperature dependence of both the Jahn–Teller structural distortion peak (1.75, 2, 0) and the charge ordering peak (3 0 0) were observed to behave identically, gradually increasing with decreasing temperature.