A compact spectrometer for medium-resolution resonant and non-resonant X-ray emission spectroscopy in von Hámos geometry is described. The main motivation for the design and construction of the spectrometer is to allow for acquisition of non-resonant X-ray emission spectra while measuring non-resonant X-ray Raman scattering spectra at beamline ID20 of the European Synchrotron Radiation Facility. Technical details are provided and the performance and possible use of the spectrometer are demonstrated by presenting results of several X-ray spectroscopic methods on various compounds.

An algorithm to simultaneously increase the spatial and statistical accuracy of X-ray Raman scattering (XRS) based tomographic images is presented. Tomography that utilizes XRS spectroscopy signals as a contrast for the images is a new and promising tool for investigating local atomic structure and chemistry in heterogeneous samples. The algorithm enables the spatial resolution to be increased based on a deconvolution of the optical response function of the spectrometer and, most importantly, it allows for the combination of data collected from multiple analyzers and thus enhances the statistical accuracy of the measured images.

A method to separate the non-resonant inelastic X-ray scattering signal of a micro-metric sample contained inside a diamond anvil cell (DAC) from the signal originating from the high-pressure sample environment is described. Especially for high-pressure experiments, the parasitic signal originating from the diamond anvils, the gasket and/or the pressure medium can easily obscure the sample signal or even render the experiment impossible. Another severe complication for high-pressure non-resonant inelastic X-ray measurements, such as X-ray Raman scattering spectroscopy, can be the proximity of the desired sample edge energy to an absorption edge energy of elements constituting the DAC. It is shown that recording the scattered signal in a spatially resolved manner allows these problems to be overcome by separating the sample signal from the spurious scattering of the DAC without constraints on the solid angle of detection. Furthermore, simple machine learning algorithms facilitate finding the corresponding detector pixels that record the sample signal. The outlined experimental technique and data analysis approach are demonstrated by presenting spectra of the Si L2,3-edge and O K-edge of compressed α-quartz. The spectra are of unprecedented quality and both the O K-edge and the Si L2,3-edge clearly show the existence of a pressure-induced phase transition between 10 and 24 GPa.

A compilation of procedures for planning and performing X-ray Raman scattering (XRS) experiments and analyzing data obtained from them is presented. In particular, it is demonstrated how to predict the overall shape of the spectra, estimate detection limits for dilute samples, and how to normalize the recorded spectra to absolute units. In addition, methods for processing data from multiple-crystal XRS spectrometers with imaging capability are presented, including a super-resolution method that can be used for direct tomography using XRS spectra as the contrast. An open-source software package with these procedures implemented is also made available.

We present simulations of X-ray resonant magnetic reflectivity (XRMR) spectra of the surface magnetic dead layer in La1−x Sr x MnO3 (LSMO) films that take in account the effect of different forms of roughness that can be encountered experimentally. The results demonstrate a method to distinguish between surface (morphological) roughness, and two generic kinds of magnetic roughness at the buried interface between the surface dead layer and the fully magnetic bulk part of the film. We show that the XRMR technique can distinguish between different types of magnetic roughness at the dead layer/bulk interface only if the sample surface is nearly atomically flat (the morphological roughness is one unit cell or less). Furthermore, to distinguish between the two types of magnetic roughness, the simulations show that fitting of XRMR spectra out to very high incidence angles must be performed. In the specific case of LSMO films with a dead layer with average thickness of 4 unit cells, this corresponds to an incidence angle > 50∘.

H. Ehrke, R. I. Tobey, S. Wall, S. A. Cavill, M. Först, V. Khanna, Th. Garl, N. Stojanovic, D. Prabhakaran, A. T. Boothroyd, M. Gensch, A. Mirone, P. Reutler, A. Revcolevschi, S. S. Dhesi,* and A. Cavalleri Department of Physics, Clarendon Laboratory, University of Oxford, Oxford, United Kingdom Diamond Light Source, Chilton, Didcot, OX11 0QX, United Kingdom Max Planck Research Department for Structural Dynamics, University of Hamburg-CFEL, Hamburg, Germany Department of Physical Chemistry, Fritz Haber Institute, 14195 Berlin, Germany HASYLAB at DESY, Notkestrasse 85, 22607 Hamburg, Germany Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01328 Dresden, Germany European Synchrotron Radiation Facility, B.P. 220, F-38043 Grenoble, France Laboratoire de Physico-Chimie de l’Etat Solide, Centre Université Paris Sud, F-91405 Orsay Cedex, France (Received 11 January 2011; published 25 May 2011)

We used ultrafast resonant soft x-ray diffraction to probe the picosecond dynamics of spin and orbital order in La(0.5)Sr(1.5)MnO(4) after photoexcitation with a femtosecond pulse of 1.5 eV radiation. Complete melting of antiferromagnetic spin order is evidenced by the disappearance of a (1/4,1/4,1/2) diffraction peak. On the other hand, the (1/4,1/4,0) diffraction peak, reflecting orbital order, is only partially reduced. We interpret the results as evidence of destabilization in the short-range exchange pattern with no significant relaxation of the long-range Jahn-Teller distortions. Cluster calculations are used to analyze different possible magnetically ordered states in the long-lived metastable phase. Nonthermal coupling between light and magnetism emerges as a primary aspect of photoinduced phase transitions in manganites.

The performance of manganite-based magnetic tunnel junctions (MTJs) has suffered from reduced magnetization present at the junction interfaces that is ultimately responsible for the spin polarization of injected currents; this behavior has been attributed to a magnetic "dead layer" that typically extends a few unit cells into the manganite. X-ray magnetic scattering in resonant conditions (XRMS) is one of the most innovative and effective techniques to extract surface or interfacial magnetization profiles with subnanometer resolution, and has only recently been applied to oxide heterostructures. Here we present our approach to characterizing the surface and interfacial magnetization of such heterostructures using the XRMS technique, conducted at the BEAR beamline (Elettra synchrotron, Trieste). Measurements were carried out in specular reflectivity geometry, switching the left/right elliptical polarization of light as well as the magnetization direction in the scattering plane. Spectra were collected across the Mn L2,3 edge for at least four different grazing angles to better analyse the interference phenomena. The resulting reflectivity spectra have been carefully fit to obtain the magnetization profiles, minimizing the number of free parameters as much as possible. Optical constants of the samples (real and imaginary part of the refractive index) in the interested frequency range are obtained through absorption measurements in two magnetization states and subsequent Kramers–Krönig transformation, allowing quantitative fits of the magnetization profile at different temperatures. We apply this method to the study of air-exposed surfaces of epitaxial La2/3Sr1/3MnO3 (0 0 1) films grown on SrTiO3 (0 0 1) substrates.

Bisphthalocyaninato terbium complexes show a long magnetization relaxation time at relatively high temperatures-which makes them very interesting as magnets at single-molecule level. Their technological exploitation, however, requires the addressing of the individual molecules, therefore the deposition of single-molecule magnets on surfaces is a topic of great interest as the interaction with the substrate can play a crucial role in the definition of the molecule properties. In this work we investigate the electronic and magnetic properties of anionic and neutral forms of a bis(phthalocyaninato)terbium derivative deposited on graphite by means of x-ray absorption spectroscopy and x-ray magnetic circular dichroism, performed at low temperature and high magnetic field at the M(4,5) edge of Tb. We were able to reproduce the experimental spectra by means of multiplet calculations and to validate the applicability of sum rules to the present case. Sum rules were then used for determining the orbital and spin moments of thick (several monolayers) and of thin films (submonolayer range). Calculations of spectra as a function of the molecule orientation with respect to the impinging x-ray beam, allowed us to ascertain the adsorption geometry of molecules. For both compounds, molecules stay essentially flat when adsorbing as thin film on graphite. This result is also confirmed by scanning probe microscopy, which also finds a very interesting ordered arrangement for the molecules of the neutral form. In the thick film of the neutral compound the molecules keep the same orientational order, arranging almost flat as well. On the contrary, in the thick film of the anionic compound their orientation appears to be random. The origin of this different behavior can be related to the hindrance of the counterion moiety and/or to the different solvent used for each compound. Finally, the comparison of the magnetization values and their dependence on the external magnetic field and temperature suggest that the magnetic properties of molecules are preserved when adsorbed onto the graphite surface.

The doping dependence of the occupied $3d$ states at the Mn sites of ${\text{La}}_{1\ensuremath{-}x}{\text{Sr}}_{1+x}{\text{MnO}}_{4}$ ($x=0$, 0.3, and 0.5) was studied by means of nonresonant hard x-ray emission spectroscopy. For the single-crystalline samples, we observe a linear dichroism of the $\text{Mn}\text{ }K\ensuremath{\beta}$ main lines ($3p$ to $1s$ transitions) that is strongest for $x=0$ and decreases with increasing hole doping $x$. At the same time, the $\text{Mn}\text{ }K\ensuremath{\beta}$ main lines of polycrystalline samples, i.e., the angular-integrated spectra, remain almost unchanged upon hole doping. The linear dichroism in the single crystals and the invariance of the $K\ensuremath{\beta}$ lines in polycrystals lead to the conclusion that hole doping causes a spatial redistribution of the $3d$ electrons without reducing the total charge and spin density at the manganese sites. This implies that the doped holes in ${\text{La}}_{1\ensuremath{-}x}{\text{Sr}}_{1+x}{\text{MnO}}_{4}$ must have a strong oxygen $2p$ character. Many-body cluster calculations are presented that support these findings.

We present a systematic study of the electronic structure in A-site ordered manganites as function of doping and temperature. The energy dependencies observed with soft x-ray resonant diffraction (SXRD) at the Mn L_{2,3} edges are compared with structural investigations using neutron powder diffraction as well as with cluster calculations. The crystal structures obtained with neutron powder diffraction reflect the various orbital and charge ordered phases and show an increase of the Mn-O-Mn bond angle as function of doping and temperature. Cluster calculations show that the observed spectral changes in SXRD as a function of doping are more pronounced than expected from an increase in bandwitdh due to the increase in Mn-O-Mn bond angle, and are best described by holes that are distributed at the neighbouring oxygen ions. These holes are not directly added to the Mn 3d shell, but centered at the Mn site. In contrast, the spectral changes in SXRD as function of temperature are best described by an increase of magnetic correlations. This demonstrates the strong correlations between orbitals and magnetic moments of the 3d states.

Using the surface, interface, and element specificity of x-ray resonant magnetic scattering in combination with x-ray magnetic circular dichroism, we have spatially resolved the polarization, and hence the spin accumulation in Mn high susceptibility material in close proximity to a ferromagnetic layer. The magnetic polarization of Mn and Cu 3d electrons in paramagnetic CuMn layers is detected in a Co/Cu(x)/CuMn structure for varying copper layer thicknesses (x). The size of the Mn and Cu L2–3-edge dichroism shows a decrease in the polarization for increasing copper thickness indicating the dominant interfacial nature of the Cu and Mn spin polarization. The Mn polarization appears to be much higher than that of Cu.

We report x-ray absorption and x-ray linear dichroism measurements at the Fe L-2,L-3 edges of the geometrically frustrated systems of potassium and hydronium iron jarosite. Comparison with simulated spectra, involving ligand-field multiplet calculations modeling the 3d-2p hybridization between the iron ion and the oxygen ligands, has yielded accurate estimates for the ligand metal-ion hybridization and the resulting single-ion crystal-field anisotropy energy. Using this method we provide an experimentally verified scenario for the appearance of a single-ion anisotropy in this nominally high-spin 3d(5) orbital singlet S-6 system, which accounts for features of the spin-wave dispersion in the long-range-ordered ground state of potassium iron jarosite.

A detailed study of the angular, energy and polarization dependences of the electric dipolar (E1: 2p -> 5d) and quadrupolar (E2: 2p -> 4f) contributions to the x-ray scattering cross-section is presented for holmium in its basal plane spiral antiferromagnetic phase at the L-3 edge. The corresponding E1 and E2 scattering factors have been extracted from fits to the experimental energy line shapes, taking into account for the first time a split dipole resonance. Using the imaginary part of the resonant scattering factors to retrieve the XMCD spectrum, we find qualitative agreement with the dichroic spectrum measured in transmission through a holmium foil.

We report the doping dependence of the ground state of A-site ordered manganites below and above half doping. Energy and polarization dependence of the orbital reflection, taken by resonant soft-x-ray powder diffraction, at both Mn L(2,3) and O K edges, provides direct evidence for orbital order at Mn(3+) and oxygen sites and absence of Zener polaron formation. For x > or = 0.2 anomalous melting of the orbital order is observed, which is coupled neither to magnetic ordering nor to a structural transition, indicating a two-dimensional character of the interactions.

Antiferromagnetic coupling in magnetic multilayers with few nanometer thick metallic spacers has been intensively studied in the last years so that, nowadays, the fundamental aspects of the physics of the process are well established [1]. In addition, the application of the peculiar electronic transport properties of some of these systems to the design of spin-valve type read heads of hard disks has lead to a big increase in their sensitivity and, consequently, to a marked increase of the areal density of information recorded in commercial hard disk drives [1]. However, the case of the magnetic coupling in multilayers with semiconducting spacers has been much less studied. As a consequence, in spite of the strong technological interest of semiconductor materials like Si, the role of this type of spacers in the magnetic coupling is not fully understood.

We have used the x-ray resonant magnetic reflectivity technique to obtain the profile of the induced uranium magnetic moment for selected U/Fe multilayer samples. This study extends the use of x-ray magnetic scattering for induced moment systems to the 5f actinide metals. The spatial dependence of the U magnetization shows that the predominant fraction of the polarization is present at the interfacial boundaries, decaying rapidly towards the center of the uranium layer, in good agreement with predictions.

Skutterudite based materials are important for thermoelectric applications. In order to be able to tune the thermoelectric properties, it is necessary to understand the mechanism of thermal conductivity, which, in turn, is strongly influenced by the lattice dynamics. The lattice dynamics of the skutterudite parent compound CoSb(3) have been investigated by inelastic x-ray scattering experiments on single crystals. The experimental results are compared to predictions of different lattice dynamical calculations. The best description of the dispersion of the normal modes in the skutterudite lattice is obtained on the basis of an ab initio approach.

We have performed nonresonant x-ray diffraction, resonant soft and hard x-ray magnetic diffraction, soft x-ray absorption, and x-ray magnetic circular dichroism measurements to clarify the electronic and magnetic high-spin (HS) state at the states of the Co3+, ions in GdBaCo2O5.5. Our data are consistent with a Co-Py(3+) pyramidal sites and a Co-Oc(3+), low-spin (LS) state at the octahedral sites. The structural distortion with a doubling of the a axis (2a(p)X2a(p)X2a(p) cell) shows alternating elongations and contractions of the pyramids, and indicates that the metal-insulator transition is associated with orbital order in the t(2g) orbitals of the Co-Py(3+) HS state. This distortion corresponds to an alternating ordering of xz and yz orbitals along the a and c axes for the Co-Py(3+). The orbital ordering and pyramidal distortion lead to deformation of the octahedra but the Co-Oc(3+) LS state does not allow an orbital order to occur for the Co-Oc(3+), ions. The soft x-ray magnetic diffraction results indicate that the magnetic moments are aligned in the ab plane but are not parallel to the crystallographic a or b axes. The orbital order and the doubling of the magnetic unit cell along the c axis support a noncollinear magnetic structure. The x-ray magnetic circular dichroism data indicate that there is a large orbital magnetic contribution to the total ordered Co moment.

Soft x-ray resonant magnetic scattering (SXRMS) has been used to probe the interlayer coupling in amorphous ferromagnetic/semiconductor multilayers. It is shown that the [Co(73)Si(27) (50 angstrom)/Si (30 angstrom)] system exhibits an antiferromagnetic (AF) coupling at low fields. Moreover, another aspect of SXRMS effect is reported. Using circularly polarized photons, a shift in the AF order Bragg peaks' position is observed and related to two opposite AF states with the spin direction longitudinally aligned. As a consequence, the sensitivity of SXRMS to AF domains having the same spin axis but opposite senses is shown. A physical explanation for the origin of this effect is provided in terms of magnetic-resonant-refraction corrections to Bragg's angle, taking into account the phase shifts between layers with opposite magnetization directions at different in-depth positions. Numerical simulations are performed that reproduced the experimental observations.