A high-energy-resolution resonant inelastic X-ray scattering spectrometer at ID20 of the European Synchrotron Radiation Facility.

An end-station for resonant inelastic X-ray scattering and (resonant) X-ray emission spectroscopy at beamline ID20 of ESRF - The European Synchrotron is presented. The spectrometer hosts five crystal analysers in Rowland geometry for large solid angle collection and is mounted on a rotatable arm for scattering in both the horizontal and vertical planes. The spectrometer is optimized for high-energy-resolution applications, including partial fluorescence yield or high-energy-resolution fluorescence detected X-ray absorption spectroscopy and the study of elementary electronic excitations in solids. In addition, it can be used for non-resonant inelastic X-ray scattering measurements of valence electron excitations.

A large-solid-angle X-ray Raman scattering spectrometer at ID20 of the European Synchrotron Radiation Facility.

An end-station for X-ray Raman scattering spectroscopy at beamline ID20 of the European Synchrotron Radiation Facility is described. This end-station is dedicated to the study of shallow core electronic excitations using non-resonant inelastic X-ray scattering. The spectrometer has 72 spherically bent analyzer crystals arranged in six modular groups of 12 analyzer crystals each for a combined maximum flexibility and large solid angle of detection. Each of the six analyzer modules houses one pixelated area detector allowing for X-ray Raman scattering based imaging and efficient separation of the desired signal from the sample and spurious scattering from the often used complicated sample environments. This new end-station provides an unprecedented instrument for X-ray Raman scattering, which is a spectroscopic tool of great interest for the study of low-energy X-ray absorption spectra in materials under in situ conditions, such as in operando batteries and fuel cells, in situ catalytic reactions, and extreme pressure and temperature conditions.

Relaxor Ferroelectrics: Back to the Single-Soft-Mode Picture.

The fluctuations of electric polarization in a disordered ferroelectric substance, relaxor crystal PbMg_{1/3}Nb_{2/3}O_{3} (PMN), were studied using a nonlinear inelastic light-scattering technique, hyper-Raman scattering, within a 5-100 cm^{-1} spectral interval and in a broad temperature range from 20 to 900 K. The split ferroelectric mode reveals a local anisotropy of up to about 400 K. Spectral anomalies observed at higher temperatures are explained as due to avoided crossing of the single primary polar soft mode with a temperature-independent, nonpolar spectral feature near 45 cm^{-1}, known from Raman scattering. The temperature changes of the vibrational modes involved in the measured fluctuation spectra of PMN were captured in a simple model that accounts for the temperature dependence of the dielectric permittivity as well. The observed slowing down of the relaxational dynamics directly correlates with the huge increase of the dielectric permittivity.

Persistent Paramagnons Deep in the Metallic Phase of Sr_{2-x}La_{x}IrO_{4}.

We have studied the magnetic excitations of electron-doped Sr_{2-x}La_{x}IrO_{4} (0≤x≤0.10) using resonant inelastic x-ray scattering at the Ir L_{3} edge. The long-range magnetic order is rapidly lost with increasing x, but two-dimensional short-range order (SRO) and dispersive magnon excitations with nearly undiminished spectral weight persist well into the metallic part of the phase diagram. The magnons in the SRO phase are heavily damped and exhibit anisotropic softening. Their dispersions are well described by a pseudospin-1/2 Heisenberg model with exchange interactions whose spatial range increases with doping. We also find a doping-independent high-energy magnetic continuum, which is not described by this model. The spin-orbit excitons arising from the pseudospin-3/2 manifold of the Ir ions broaden substantially in the SRO phase, but remain largely separated from the low-energy magnons. Pseudospin-1/2 models are therefore a good starting point for the theoretical description of the low-energy magnetic dynamics of doped iridates.

CaIrO3: a spin-orbit Mott insulator beyond the j(eff) ground state.

In CaIrO3, electronic correlation, spin-orbit coupling, and tetragonal crystal field splitting are predicted to be of comparable strength. However, the nature of its ground state is still an object of debate, with contradictory experimental and theoretical results. We probe the ground state of CaIrO3 and assess the effective tetragonal crystal field splitting and spin-orbit coupling at play in this system by means of resonant inelastic x-ray scattering. We conclude that insulating CaIrO3 is not a j(eff) = 1/2 iridate and discuss the consequences of our finding to the interpretation of previous experiments. In particular, we clarify how the Mott insulating state in iridates can be readily extended beyond the j(eff) = 1/2 ground state.

Role of zinc and niobium in the giant piezoelectric response of PbZn(1/3)Nb(2/3)O(3).

Relaxor ferroelectric perovskites are highly polarizable and can exhibit giant coupling between elastic strain and an applied electric field. Here, we report an in situ extended X-ray absorption fine structure (EXAFS) study of a PbZn1/3Nb2/3O3 (PZN) single crystal as a function of the electric field. We show that the strong dipoles in the NbO6 octahedra bonds are aligned along the four ⟨011⟩ directions close to the orientation of the electric field, while a small reversible polar shift occurs for Zn in the direction of the electric field, i.e., positive or negative. This reversible Zn-O polar shift is proposed to play an important role in both the "easy" switching of the ferroelectric polarization and the giant piezoelectric effect in PZN.

Study of the electronic and magnetic properties as a function of isoelectronic substitution in SmFe(1-x)RuxAsO0.85F0.15.

We have studied the electronic and magnetic properties of SmFe(1-x)RuxAsO0.85F0.15 (x = 0, 0.05, 0.25, 0.33, 0.5) by high-resolution x-ray absorption and x-ray emission spectroscopy. The local Fe magnetic moment (µ) tends to decrease for a small Ru substitution, but it shows a clear increase with further substitution. It appears that impurity scattering prevails in reducing the µ with small Ru substitution due to an extended Ru d-band. A nanoscale phase separation, that decouples the FeAs layers from the spacer layers, drives the increase of µ at higher Ru substitution. The results provide important information on nanoscale phase separation due to isoelectronic substitution in the active layers of iron-based 1111-superconductors and its effect on the local magnetic properties.

Hyper-Raman and Raman scattering from the polar modes of PbMg1/3Nb2/3O3.

Microhyper-Raman spectroscopy of PbMg(1/3)Nb(2/3)O(3) (PMN) single crystal is performed at room temperature. The use of an optical microscope working in backscattering geometry significantly reduces the LO signal, highlighting thereby the weak contributions underneath. We clearly identify the highest frequency transverse optic mode (TO3) in addition to the previously observed soft TO-doublet at low frequency and TO2 at intermediate frequency. TO3 exhibits strong inhomogeneous broadening but perfectly fulfils the hyper-Raman cubic selection rules. The analysis shows that hyper-Raman spectroscopy is sensitive to all the vibrations of the average cubic Pm3¯m symmetry group of PMN, the three polar F1u- and the silent F2u-symmetry modes. All these vibrations can be identified in the Raman spectra alongside other vibrational bands likely arising from symmetry breaking in polar nanoregions.

Soft mode doublet in PbMg{1/3}Nb{2/3}O{3} relaxor investigated with hyper-Raman scattering.

Hyper-Raman scattering experiments suggest that a splitting of the lowest F{1u}-symmetry mode of PbMg{1/3}Nb{2/3}O{3} crystal occurs in a wide temperature range around its Burns temperature T{d}≈630 K. The upper-frequency component, earlier investigated by inelastic neutron scattering experiments above T{d}, appears to be underdamped even hundred of degrees below T{d}. The lower-frequency component, known below T{d} from far-IR spectroscopy, actually becomes underdamped above T{d}. This suggests that the lower-frequency mode is the "primary" polar soft mode of PbMg{1/3}Nb{2/3}O{3}, responsible for the Curie-Weiss behavior of its dielectric permittivity above T{d}.

Pressure-induced structural transition in LuFe2O4: towards a new charge ordered state.

The electronic ferroelectric lutetium ferrite (LuFe(2)O(4)) was studied by x-ray diffraction as a function of pressure. Pressure is shown to induce an irreversible rhombohedral to orthorhombic transition leading to a supercell determined by the combination of electron and synchrotron x-ray diffraction. This new configuration is proposed to be charge ordered in agreement with the results of resistivity measurements.

High-pressure structural and vibrational study of PbZr0.40Ti0.60O3.

The high-pressure structure and dynamics of PbZr0.40Ti0.60O3 were investigated by means of neutron diffraction, X-ray diffraction, and resonance Raman spectroscopy. The complex (P4mm, Cm, Cc, F1, F1) phase transition sequence is characterized by these techniques. On the basis of the results of structure refinements, the high-pressure behavior of the spontaneous polarization, the (Zr,Ti)O6 rotation angles, and the polarization rotation angle are obtained. Moreover, resonance Raman spectra combined with previous Raman data in the literature provide evidence that the pressure-induced transition to the monoclinic Cm space group and the above transition sequence terminating in a paraelectric state are general features of Pb(Zr(1-x)Ti(x))O3 (0.48 < or = x < or = 1).