High-resolution Resonant Inelastic X-ray Research Articles

Design of RIXS beamline at Shenzhen innovation light facility

An optical design of the RIXS beamline for the Shenzhen Innovation Light Facility (SILF) was reported. The beamline will cover an energy range from 200 to 1500 eV, with three endstations: a Q-RIXS for momentum-dependent high-resolution resonant inelastic x-ray scattering, an e-RIXS for high-throughput resonant inelastic x-ray scattering and an APXPS. All endstations share the same undulator, front end optics and the main branch of beamline until the deflecting mirrors after the monochromator. The Q-RIXS and e-RIXS will be located in two separate branches, while the APXPS endstation is mounted on a free port located right between the exit slit and the refocusing optics for the e-RIXS endstation. This design allows for the mounting of different techniques and the preparation of sample environments without disrupting the operation of the other branch, thus maximizing the utilization of beamtime. The combined energy resolution is expected to be better than 50 meV for Q-RIXS and better than 100 meV for e-RIXS. Once available, it will provide in-demand, versatile and high-quality soft x-ray spectroscopy techniques to users in fields of quantum, energy and surface science.

Universal Stripe Symmetry of Short-Range Charge Density Waves in Cuprate Superconductors.

The omnipresence of charge density waves (CDWs) across almost all cuprate families underpins a common organizing principle. However, a longstanding debate of whether its spatial symmetry is stripe or checkerboard remains unresolved. While CDWs in lanthanum- and yttrium-based cuprates possess a stripe symmetry, distinguishing these two scenarios is challenging for the short-range CDW in bismuth-based cuprates. Here, high-resolution resonant inelastic x-ray scattering is employed to uncover the spatial symmetry of the CDW in Bi2 Sr2 - x Lax CuO6 + δ . Across a wide range of doping and temperature, anisotropic CDW peaks with elliptical shapes are found in reciprocal space. Based on Fourier transform analysis of real-space models, the results are interpreted as evidence of unidirectional charge stripes, hosted by mutually 90°-rotated anisotropic domains. This work paves the way for a unified symmetry and microscopic description of CDW order incuprates.

Probing Lattice Oxygen Oxidation in Perovskite Electrocatalysts By Resonant Inelastic X-Ray Scattering

During water electrolysis, the hydrogen evolution reaction that generates hydrogen gas is unavoidably accompanied by the anodic reaction that generates oxygen via the oxygen evolution reaction (OER). However, under OER conditions, many electrocatalysts undergo structural degradation and can become amorphous. Lattice oxygen oxidation was proposed as one of the possible causes for amorphization of perovskite oxides. However, because lattice oxygen oxidation is notoriously challenging to probe in experiments, its unambiguous detection in oxide electrocatalysts has been elusive so far.Here, I will show how oxygen oxidation can be detected in single-crystalline (model) oxide electrocatalysts using high-resolution resonant inelastic X-ray scattering (RIXS). Specifically, I will present our case study of perovskite materials where the emergence of oxidized oxygen depends on the transition metal and the applied potential. An insight into the chemical environment of the oxidized oxygen and how it can be accommodated in the perovskite lattice will be provided based on the results of DFT and molecular dynamics. Finally, I will discuss how lattice oxygen oxidation is related to the degradation of oxide electrocatalysts during OER.

I21: an advanced high-resolution resonant inelastic X-ray scattering beamline at Diamond Light Source.

The I21 beamline at Diamond Light Source is dedicated to advanced resonant inelastic X-ray scattering (RIXS) for probing charge, orbital, spin and lattice excitations in materials across condensed matter physics, applied sciences and chemistry. Both the beamline and the RIXS spectrometer employ divergent variable-line-spacing gratings covering a broad energy range of 280-3000 eV. A combined energy resolution of ∼35 meV (16 meV) is readily achieved at 930 eV (530 eV) owing to the optimized optics and the mechanics. Considerable efforts have been paid to the design of the entire beamline, particularly the implementation of the collection mirrors, to maximize the X-ray photon throughput. The continuous rotation of the spectrometer over 150° under ultra high vacuum and a cryogenic manipulator with six degrees of freedom allow accurate mappings of low-energy excitations from solid state materials in momentum space. Most importantly, the facility features a unique combination of the high energy resolution and the high photon throughput vital for advanced RIXS applications. Together with its stability and user friendliness, I21 has become one of the most sought after RIXS beamlines in the world.

Quantum Fluctuations of Charge Order Induce Phonon Softening in a Superconducting Cuprate

Quantum phase transitions play an important role in shaping the phase diagram of high-temperature cuprate superconductors. These cuprates possess intertwined orders which interact strongly with superconductivity. However, the evidence for the quantum critical point associated with the charge order in the superconducting phase remains elusive. Here we show the short-range charge orders and the spectral signature of the quantum fluctuations in La$_{2-x}$Sr$_x$CuO$_4$ (LSCO) near the optimal doping using high-resolution resonant inelastic X-ray scattering. On performing calculations through a diagrammatic framework, we discovered that the charge correlations significantly soften several branches of phonons. These results elucidate the role of charge order in the LSCO compound, providing evidence for quantum critical scaling and discommensurations associated with charge order.

Charge Order at High Temperature in Cuprate Superconductors

The presence of different electronic orders other than superconductivity populating the phase diagram of cuprates suggests that they might be the key to disclose the mysteries of this class of materials. In particular charge order in the form of charge density waves (CDW), i.e., the incommensurate modulation of electron density in the CuO$_2$ planes, is ubiquitous across different families and presents a clear interplay with superconductivity. Until recently, CDW had been found to be confined inside a rather small region of the phase diagram, below the pseudogap temperature and the optimal doping. This occurrence might shed doubts on the possibility that such "low temperature phenomenon" actually rules the properties of cuprates either in the normal or in the superconducting states. However, recent resonant X-ray scattering (RXS) experiments are overturning this paradigm. It results that very short-ranged charge modulations permeate a much wider region of the phase diagram, coexisting with CDW at lower temperatures and persisting up to temperatures well above the pseudogap opening. Here we review the characteristics of these high temperature charge modulations, which are present in several cuprate families, with similarities and differences. A particular emphasis is put on their dynamical character and on their coupling to lattice and magnetic excitations, properties that can be determined with high resolution resonant inelastic x-ray scattering (RIXS).

Physical properties of YB66 and consideration of possible use for high-resolution X-ray optics

A combined microscopic, i.e., powder and single crystal x-ray diffraction and inelastic x-ray scattering, and macroscopic, i.e., heat capacity, characterization was carried out on YB66 between 10 and 400K. The system crystallizes in a rather large unit cell with a lattice parameter of about 23.4Å at room temperature. The volume thermal expansion coefficient is found to be 3.9×10−5K−1 at 295K. A high Debye temperature above 1000K was determined using several methods, 1043(25)K, from heat capacity measurements, 1430(59)K, from elastic constants measurements, and 1690(198)K, from thermal expansion measurements. The thermal transport is modeled as a collection of Einstein oscillators with an Einstein temperature of 194(2)K. The C11 and C44 elastic constants are above 400 and 150GPa, respectively. The average speed of sound in YB66 is estimated to be 9631(380)m/s, similar to the average speed of sound in corundum, 10000m/s. The large volume of the unit cell and the stiffness of the crystal structure make YB66 a promising candidate for high-resolution x-ray monochromatization applications. Candidate reflections for high-resolution resonant inelastic x-ray scattering are indicated and potential pitfalls relevant to the quality of crystals and multi-beam cases are mentioned.

Unusual Dynamic Charge Correlations in Simple-Tetragonal HgBa2CuO4+δ

The charge-density-wave (CDW) instability in the underdoped, pseudogap part of the cuprate phase diagram has been a major recent research focus, yet measurements of dynamic, energy-resolved CDW correlations are still in their infancy. We report a high-resolution resonant inelastic X-ray scattering (RIXS) study of the underdoped cuprate superconductor HgBa$_{2}$CuO$_{4+\delta}$ ($T_c = 70$ K). At $T=250$ K, above the CDW order temperature $T_\mathrm{CDW} \approx 200$ K, we observe significant dynamic CDW correlations at about 40 meV. This energy scale is comparable to both the superconducting gap and the previously reported low-energy pseudogap. At $T = T_c$, a strong elastic CDW peak appears, but the dynamic correlations around 40 meV remain virtually unchanged. In addition, we observe a new feature: dynamic correlations at significantly higher energy, with a characteristic scale of about 160 meV. A similar scale was previously identified in other experiments as a high-energy pseudogap. The existence of three distinct features in the charge response is highly unusual for a CDW system, and suggests that charge order in the cuprates is closely related to the pseudogap phenomenon and more complex than previously thought. We further observe the paramagnon dispersion along [1,0], across the two-dimensional CDW wavevector $\boldsymbol{q}_\mathrm{CDW}$, which is consistent with magnetic excitations measured by inelastic neutron scattering. Unlike for some other cuprates, our results point to the absence of a discernible coupling between CDW and magnetic excitations.

Spin and orbital excitations through the metal-to-insulator transition in Cd2Os2O7 probed with high-resolution resonant inelastic x-ray scattering

High-resolution resonant inelastic x-ray scattering (RIXS) measurements ($\Delta$E = 46 meV) have been performed on Cd$_2$Os$_2$O$_7$ through the metal-to-insulator transition (MIT). A magnetic excitation at 125 meV evolves continuously through the MIT, in agreement with recent Raman scattering results, and provides further confirmation for an all-in, all-out magnetic ground state. Asymmetry of this feature is likely a result of coupling between the electronic and magnetic degrees of freedom. We also observe a broad continuum of interband excitations centered at 0.3 eV energy loss. This is indicative of significant hybridization between Os 5$d$ and O 2$p$ states, and concurrent itinerant nature of the system. In turn, this suggests a possible break down of the free-ion model for Cd$_2$Os$_2$O$_7$.

Anisotropic damping and wave vector dependent susceptibility of the spin fluctuations in La2−xSrxCuO4 studied by resonant inelastic x-ray scattering

We report high-resolution resonant inelastic x-ray scattering (RIXS) measurements of the collective spin fluctuations in three compositions of the superconducting cuprate system La2-xSrxCuO4. We have mapped out the excitations throughout much of the 2-D (h,k) Brillouin zone. The spin fluctuations in La2-xSrxCuO4 are found to be fairly well-described by a damped harmonic oscillator model, thus our data allows us to determine the full wavevector dependence of the damping parameter. This parameter increases with doping and is largest along the (h, h) line, where it is peaked near (0.2,0.2). We have used a new procedure to determine the absolute wavevector-dependent susceptibility for the doped compositions La2-xSrxCuO4 (x=0.12,0.16) by normalising our data to La2CuO4 measurements made with inelastic neutron scattering (INS). We find that the evolution with doping of the intensity of high-energy excitations measured by RIXS and INS is consistent. For the doped compositions, the wavevector-dependent susceptibility is much larger at (1/4,1/4) than at (1/2,0). It increases rapidly along the (h,h) line towards the antiferromagnetic wavevector of the parent compound (1/2,1/2). Thus, the strongest magnetic excitations, and those predicted to favour superconductive pairing, occur towards the (1/2,1/2) position as observed by INS.

High-resolution resonant inelastic x-ray scattering study of the electron-phonon coupling in honeycomb α−Li2IrO3

The excitations in honeycomb $\alpha$-Li$_2$IrO$_3$ have been investigated with high-resolution resonant inelastic x-ray scattering (RIXS) at the O K edge. The low-energy response is dominated by a fully resolved ladder of excitations, which we interpret as being due to multi-phonon processes in the presence of strong electron-phonon coupling (EPC). At higher energies, the orbital excitations are shown to be dressed by phonons. The high quality of the data permits a quantitative test of the analytical model for the RIXS cross-section, which has been proposed to describe EPC in transition metal oxides (TMOs). We find that the magnitude of the EPC is comparable to that found for a range of 3d TMOs. This indicates that EPC may be of equal importance in determining the phenomenology displayed by corresponding 5d based systems.

Resonant inelastic x-ray scattering investigation of the crystal-field splitting ofSm3+inSmB6

The crystal-field (CF) splitting of the $^6H_{5/2}$ Hund's rule ground state of Sm$^{3+}$ in the strongly correlated topological insulator SmB$_6$ has been determined with high resolution resonant inelastic x-ray scattering (RIXS) at the Sm M$_5$ edge. The valence selectivity of RIXS allows isolating the crystal-field-split excited multiplets of the Sm$^{3+}$ (4$f^5$) configuration from those of Sm$^{2+}$ (4$f^6$) in intermediate valent SmB$_6$. The very large energy range of RIXS allows the crystal-field analysis of a high lying multiplet at about 2.4\,eV that has the same total angular momentum $J$ as the ground state so that ambiguities due to the elastic tail can be avoided. We find that the $\Gamma_7$ doublet and $\Gamma_8$ quartet of the $^6H_{5/2}$ Hund's rule ground state are split by $\Delta^{CF}_{^6H_{5/2}}$\,=\,20$\pm$10\,meV which sets an upper limit for the 4$f$ band width. This indicates an extremely large mass renormalization from the band structure value, pointing out the need to consider the coefficients of fractional parentage for the hopping of the 4$f$ electrons.

Polarization-resolved Cu L3 -edge resonant inelastic x-ray scattering of orbital and spin excitations in NdBa2Cu3O7−δ

High resolution resonant inelastic x-ray scattering (RIXS) has proven particularly effective in the determination of crystal field and spin excitations in cuprates. Its strength lies in the large Cu $L_{3}$ resonance and in the fact that the scattering cross section follows quite closely the single-ion model predictions, both in the insulating parent compounds and in the superconducting doped materials. However, the spectra become increasingly broader with (hole) doping, hence resolving and assigning spectral features has proven challenging even with the highest energy resolution experimentally achievable. Here we have overcome this limitation by measuring the complete polarization dependence of the RIXS spectra as function of momentum transfer and doping in thin films of NdBa$_{2}$Cu$_{3}$O$_{7-\delta}$. Besides confirming the previous assignment of $dd$ and spin excitations (magnon, bimagnon) in the antiferromagnetic insulating parent compound, we unequivocally single out the actual spin-flip contribution at all dopings. We also demonstrate that the softening of $dd$ excitations is mainly attributed to the shift of the $xy$ peak to lower energy loss. These results provide a definitive assessment of the RIXS spectra of cuprates and demonstrate that RIXS measurements with full polarization control are practically feasible and highly informative.

Resonant inelastic x-ray scattering study of bond order and spin excitations in nickelate thin-film structures

The rare-earth nickelates ($R$NiO${}_{3}$) have been subject to intense investigation, mostly because of their rich phase diagrams, comprising a sharp temperature-driven metal-to-insulator transition and an unusual antiferromagnetic ground state. Here, the authors use high-resolution resonant inelastic x-ray scattering (RIXS) at the Ni ${L}_{3}$ edge to study simultaneously the bond and magnetic orders controlled via heterostructuring. The results show that RIXS gives valuable insights into the interplay of different collective ordering phenomena in a prototypical 3$d$ transition-metal oxide

Direct observation of spin-orbit-induced 3d hybridization via resonant inelastic extreme ultraviolet scattering on an edge-sharing cuprate

Author(s): Malvestuto, M; Caretta, A; Casarin, B; Ciprian, R; Dell'Angela, M; Laterza, S; Chuang, YD; Wurth, W; Revcolevschi, A; Wray, LA; Parmigiani, F | Abstract: Using high resolution resonant inelastic x-ray scattering measurements, we have observed that the orbital excitations of the quasi-1D spin chain compound CuGeO3 has nontrivial and noticeable orbital mixing effects from 3d valence spin-orbit coupling. In particular, the SOC leads to a significant correction of dz2 state, which has a direct interplay with the low energy physics of cuprates. Guided by atomic multiplet based modeling, our results strongly support a 3d spin-orbit mixing scenario and explore in detail the nature of these excitations.

Probing the energy gap of high-temperature cuprate superconductors by resonant inelastic x-ray scattering

The determination of the symmetry of the energy gap is crucial for research on the microscopic mechanisms of unconventional superconductivity. Here, we demonstrate experimentally that high-resolution resonant inelastic X-ray scattering at the Cu L3 edge can serve as a momentum-resolved, bulk-sensitive probe of the superconducting gap. We studied two optimally doped cuprates Bi2Sr2CaCu2O8+δ and Bi2Sr2Ca2Cu3O10+δ, in which we observe a strongly momentum dependent reduction of the spectral weight upon entering the superconducting state, with a maximum for momenta connecting antinodal regions of the Fermi surface. Based on a comparison with the calculated charge susceptibility and electronic Raman scattering data, we interpret our observation as a renormalization of the non-local charge susceptibility due to the superconducting gap opening. Our data demonstrate the methodological potential of resonant inelastic X-ray scattering as a versatile probe of the energy gap of high-temperature superconductors, including buried interfaces in heterostructures which are inaccessible to angle-resolved photoemission spectroscopy.

Site-Selective Probe of Magnetic Excitations in Rare-Earth Nickelates Using Resonant Inelastic X-ray Scattering

We use high-resolution resonant inelastic x-ray scattering (RIXS) to study a thin film of NdNiO3, a compound whose unusual spin- and bond-ordered electronic ground state has been of long-standing interest. Below the magnetic ordering temperature, we observe well-defined collective magnon excitations along different high-symmetry directions in momentum space. The magnetic spectra depend strongly on the incident photon energy, which we attribute to RIXS coupling to different local electronic configurations of the expanded and compressed NiO6 octahedra in the bond-ordered state. Both the noncollinear magnetic ground state and the observed site-dependent magnon excitations are well described by a model that assumes strong competition between the antiferromagnetic superexchange and ferromagnetic double-exchange interactions. Our study provides direct insight into the magnetic dynamics and exchange interactions of the rare-earth nickelates and demonstrates that RIXS can serve as a site-selective probe of magnetism in these and other materials.Received 3 August 2017Revised 20 June 2018DOI:https://doi.org/10.1103/PhysRevX.8.031014Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasAntiferromagnetismExchange interactionMagnonsSpin wavesPhysical SystemsComplex materialsStrongly correlated systemsTechniquesExact diagonalizationHeisenberg modelResonant inelastic x-ray scatteringX-ray absorption spectroscopyCondensed Matter, Materials & Applied Physics

The beamline ID32 at the ESRF for soft X-ray high energy resolution resonant inelastic X-ray scattering and polarisation dependent X-ray absorption spectroscopy

The ID32 Soft X-ray Beamline line is an ESRF upgrade beamline for X-ray absorption (XAS) and Resonant Inelastic X-ray Scattering (RIXS) spectroscopic studies. It was opened to Users in October 2014 and provides polarised soft X-rays in the 400–1600 eV energy range. It has two branches: One branch has been designed for X-ray magnetic dichroism experiments, both linear (XMLD) and circular (XMCD), with high sensitivity, reproducibility, flexibility, user friendliness and the capability for fast energy scanning. The X-ray beam is available in two experimental areas, one with a dedicated superconducting high field magnet and a sample preparation facility, the second area being open for User instruments. The other branch is dedicated to very high energy resolution Resonant Inelastic X-ray Scattering experiments with a combined resolving power up to 30 000 around 930 eV. A scattering arm which is continuously variable under UHV vacuum over 100 degrees and a four-circle sample goniometer allows accurate positioning of the sample to enable 3D mapping of q space. Combined with the possibility of polarisation analysis of the outgoing photons the beamline provides a state-of-the-art soft X-ray RIXS facility.

Performance of quartz- and sapphire-based double-crystal high-resolution (∼10 meV) RIXS monochromators under varying power loads.

In the context of a novel, high-resolution resonant inelastic X-ray scattering spectrometer, a flat-crystal-based quartz analyzer system has recently been demonstrated to provide an unprecedented intrinsic-energy resolution of 3.9 meV at the Ir L3 absorption edge (11.215 keV) [Kim et al. (2018) Sci. Rep. 8, 1958]. However, the overall instrument resolution was limited to 9.7 meV because of an 8.9 meV incident band pass, generated by the available high-resolution four-bounce Si(844) monochromator. In order to better match the potent resolving power of the novel analyzer with the energy band pass of the incident beam, a quartz(309)-based double-bounce, high-resolution monochromator was designed and implemented, expected to yield an overall instrument resolution of 6.0 meV. The choice of lower-symmetry quartz is very attractive because of its wealth of suitable near-backscattering reflections. However, it was found that during room-temperature operation typical levels of incident power, barely affecting the Si monochromator, caused substantial thermal distortions in the first crystal of the quartz monochromator, rendering it practically unusable. Finite-element analyses and heat-flow analyses corroborate this finding. As a high-flux, lower resolution (15.8 meV) alternative, a two-bounce sapphire(078) version was also tested and found to be less affected than quartz, but notably more than silicon.

Observation of heavy spin-orbit excitons propagating in a nonmagnetic background: The case of (Ba,Sr)2YIrO6

We present a combined experimental and theoretical study of the elementary magnetic excitations in ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$ and ${\mathrm{Sr}}_{2}{\mathrm{YIrO}}_{6}$---the two most intensively discussed candidates for a new type of magnetic instability caused by exciton condensation. For both materials, high-resolution resonant inelastic x-ray scattering (RIXS) at the Ir ${L}_{3}$ edge reveals sharp excitations around 370 and 650 meV energy loss, which we identify as triplet and quintet spin-orbit excitons. While the momentum-dependent RIXS spectra reveal that both the triplet and the quintet propagate coherently within the nonmagnetic background of the singlet sites, these modes remain fully gapped. The Ir-Ir exchange interactions in both double perovskites are therefore not strong enough to overcome the magnetic gap and, hence, our results exclude an intrinsic magnetic instability due to a condensation of magnetic excitations for both ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$ and ${\mathrm{Sr}}_{2}{\mathrm{YIrO}}_{6}$.