meV Resolution Research Articles

Advances in hard X-ray RIXS toward meV resolution in the study of 5d transition metal materials

Resonant inelastic X-ray scattering (RIXS) has played a pivotal role in advancing our understanding of spin-orbit physics in 5d transition metal materials. The progress in RIXS techniques has closely paralleled improvements in energy resolution, which have enabled the study of very low-lying excitations and led to the discovery of numerous new phenomena with significant scientific and technological implications. The multi-bend achromat (MBA) lattice upgrade of third-generation synchrotron sources, such as the Advanced Photon Source (APS), heralds a transformative era by introducing enhancements in brilliance and emittance. These advancements provide an opportunity to push the boundaries of RIXS techniques, meeting the challenges at the research frontiers of material science. This article aims to highlight key instrumental and technical advancements that enable the achievement of meV resolution in RIXS and discuss the impact of such high-resolution RIXS on exploring spin-orbit physics in 5d transition metal materials.

A setup for hard x-ray time-resolved resonant inelastic x-ray scattering at SwissFEL.

We present a new setup for resonant inelastic hard x-ray scattering at the Bernina beamline of SwissFEL with energy, momentum, and temporal resolution. The compact R = 0.5 m Johann-type spectrometer can be equipped with up to three crystal analyzers and allows efficient collection of RIXS spectra. Optical pumping for time-resolved studies can be realized with a broad span of optical wavelengths. We demonstrate the performance of the setup at an overall ∼180 meV resolution in a study of ground-state and photoexcited (at 400 nm) honeycomb 5d iridate α-Li2IrO3. Steady-state RIXS spectra at the iridium L3-edge (11.214 keV) have been collected and are in very good agreement with data collected at synchrotrons. The time-resolved RIXS transients exhibit changes in the energy loss region <2 eV, whose features mostly result from the hopping nature of 5d electrons in the honeycomb lattice. These changes are ascribed to modulations of the Ir-to-Ir inter-site transition scattering efficiency, which we associate to a transient screening of the on-site Coulomb interaction.

Characterisation of a high granularity multi-channel prompt γ-ray detection system prototype for proton range verification based on the PETsys TOFPET2 ASIC

Proton therapy requires range verification in order to exploit its full potential. One of the most promising approaches is to monitor prompt gamma-rays produced by nuclear interactions of the therapeutic particles in the patient tissues. A detector with a wide energy range from 100 keV to 15 MeV and excellent time resolution is required to achieve millimetric precision in proton range. During patient treatment, the detector count rates are usually above 106 s-1 and the fraction of pile-up events is very high for commonly used fast inorganic scintillators. We are investigating a full acceptance approach with increased granularity in order to reduce the size of the scintillators and consequently the count rate per channel. Stacking the scintillators in matrices requires suitable multi-channel photo-multipliers and a fitting acquisition system. Here, we present two geometries of CeBr3 crystals 5×5×20 mm3 and 10×10×30 mm3, together with modern silicon photo-multipliers (SiPM) adapted to work with the PETsys TOFPET2 ASIC. The TOFPET2 ASIC was developed for Time-of-Flight Positron Emission Tomography (TOF-PET) applications. Here we show its potential for higher gamma-ray energies and future hybrid imaging. First results of energy resolution of 6.1%–7.8% are achieved at 3.42 MeV using a 241Am9Be source. The time resolution was found to be below 100 ps and studies of the count rates and the dead time of the full system were performed. Different SiPM models are analysed for their impact on the coincidence time resolution.

Transmission electron microscopy of thick polymer and biological specimens

We explore the properties of elastic and inelastic scattering in a thick organic specimen, together with the mechanisms that provide contrast in a transmission electron microscope (TEM) and scanning-transmission electron microscope (STEM). Experimental data recorded from amorphous carbon are used to predict the bright-field image intensity, mass-thickness contrast and dose-limited resolution as a function of thickness, objective-aperture size, and primary-electron energy E0. Combining this information with estimates of chromatic aberration, objective-aperture diffraction and beam broadening in the specimen, we calculate the achievable TEM and STEM resolution to be around 4 nm at E0 = 300 keV (or below 3 nm at MeV energies) for a 10 µm-diameter objective aperture and 1 – 2 µm thickness of hydrated biological tissue. The 3 MeV resolution for a 10-μm tissue sample is probably closer to 10 nm. We also comment on the error involved in quadrature addition of resolution factors, when one or more of the point-spread functions are non-Gaussian.

A flexible proton beam imaging energy spectrometer (PROBIES) for high repetition rate or single-shot high energy density (HED) experiments (invited).

The PROBIES diagnostic is a new, highly flexible, imaging and energy spectrometer designed for laser-accelerated protons. The diagnostic can detect low-mode spatial variations in the proton beam profile while resolving multiple energies on a single detector or more. When a radiochromic film stack is employed for "single-shot mode," the energy resolution of the stack can be greatly increased while reducing the need for large numbers of films; for example, a recently deployed version allowed for 180 unique energy measurements spanning ∼3 to 75MeV with <0.4MeV resolution using just 20 films vs 180 for a comparable traditional film and filter stack. When utilized with a scintillator, the diagnostic can be run in high-rep-rate (>Hz rate) mode to recover nine proton energy bins. We also demonstrate a deep learning-based method to analyze data from synthetic PROBIES images with greater than 95% accuracy on sub-millisecond timescales and retrained with experimental data to analyze real-world images on sub-millisecond time-scales with comparable accuracy.

Evolution of static charge density wave order, amplitude mode dynamics, and suppression of Kohn anomalies at the hysteretic transition in EuTe4

Charge density wave (CDW) induces periodic spatial modulation of the charge density that is commensurate or incommensurate with the host lattice periodicity, and leads to partial or complete electronic band-gap opening at the Fermi level (${E}_{\mathrm{F}}$). The recent finding of unconventional hysteresis within the CDW phase of ${\mathrm{EuTe}}_{4}$, not observable in other rare-earth tellurides $R{\mathrm{Te}}_{n}$ ($n=2$, 3), has highlighted the role of the relative phase of CDW distortion in weakly coupled Te layers. However, detailed structural and dynamical characterization of CDW distortion on the hysteretic transition is lacking. Here we report on the static CDW order, dynamics of the amplitude mode, and their evolution on the hysteretic transition using meV resolution elastic and inelastic x-ray scattering. We discover previously unidentified multiple commensurate and incommensurate CDW wave vectors ${\mathbf{q}}_{\mathrm{CDW}}$ along all three crystallographic axes. Importantly, we find that the previously reported $b$-axis CDW peak is coupled with the interlayer CDW phase and consequently co-occurs with the doubling of the unit cell along the $c$ axis. We confirm the presence of the competing $a$-axis CDW order but found it to be four orders of magnitude weaker than the $b$-axis CDW. Furthermore, we observe multiple Kohn anomalies at ${\mathbf{q}}_{\mathrm{CDW}}$ driven by Fermi surface nesting and hidden nesting, confirming earlier reports based on electronic and lattice susceptibility simulations. The amplitude mode and Kohn anomalies are found to suppress on unconventional hysteretic transition, suggesting the presence of nondegenerate metastable states, which we identify from the x-ray scattering measurements and simulations.

Dynamical spin susceptibility in La2CuO4 studied by resonant inelastic x-ray scattering

Resonant inelastic x-ray scattering (RIXS) is a powerful probe of elementary excitations in solids. It is now widely applied to study magnetic excitations. However, its complex cross section means that RIXS has been more difficult to interpret than inelastic neutron scattering (INS). Here we report $\ensuremath{\sim}37$ meV resolution RIXS measurements of the magnetic excitations in ${\mathrm{La}}_{2}{\mathrm{CuO}}_{4}$, the antiferromagnetic parent of one system of high-temperature superconductors. At high energies ($\ensuremath{\sim}2$ eV), the RIXS spectra show angular-dependent $dd$ orbital excitations in agreement with previous RIXS studies but show new structure. They are interpreted with single-site multiplet calculations. At low energies ($\ensuremath{\lesssim}0.3$ eV), we model the wave-vector-dependent single magnon RIXS intensity as the product of the calculated single-ion spin-flip RIXS cross section and the dynamical structure factor $S(\mathbf{Q},\ensuremath{\omega})$ of the spin-wave excitations. When $S(\mathbf{Q},\ensuremath{\omega})$ is extracted from our data, the wave-vector-dependence of the single-magnon pole intensity shows a similar variation to that observed by INS. Our results confirm that suitably corrected RIXS data can yield the genuine wave-vector and energy dependence of $S(\mathbf{Q},\ensuremath{\omega})$ for a cuprate antiferromagnet. In addition to spin waves, our data show structured multimagnon excitations with dispersing peaks in the intensity at energies higher than the single-magnon excitations.

Giant phonon anomalies in the proximate Kitaev quantum spin liquid \u03b1-RuCl3

The Kitaev quantum spin liquid epitomizes an entangled topological state, for which two flavors of fractionalized low-energy excitations are predicted: the itinerant Majorana fermion and the Z2 gauge flux. It was proposed recently that fingerprints of fractional excitations are encoded in the phonon spectra of Kitaev quantum spin liquids through a novel fractional-excitation-phonon coupling. Here, we detect anomalous phonon effects in α-RuCl3 using inelastic X-ray scattering with meV resolution. At high temperature, we discover interlaced optical phonons intercepting a transverse acoustic phonon between 3 and 7 meV. Upon decreasing temperature, the optical phonons display a large intensity enhancement near the Kitaev energy, JK~8 meV, that coincides with a giant acoustic phonon softening near the Z2 gauge flux energy scale. These phonon anomalies signify the coupling of phonon and Kitaev magnetic excitations in α-RuCl3 and demonstrates a proof-of-principle method to detect anomalous excitations in topological quantum materials.

Toward Å-fs-meV resolution in electron microscopy: systematic simulation of the temporal spread of single-electron packets.

Though efforts to improve the temporal resolution of transmission electron microscopes (TEMs) have waxed and waned for decades, with relatively recent advances routinely reaching sub-picosecond scales, fundamental and practical challenges have hindered the advance of combined Å-fs-meV resolutions, particularly for core-loss spectroscopy and real-space imaging. This is due in no small part to the complexity of the approach required to access timescales upon which electrons, atoms, molecules, and materials first begin to respond and transform - attoseconds to picoseconds. Here we present part of a larger effort devoted to systematically mapping the instrument parameter space of a TEM modified to reach ultrafast timescales. With General Particle Tracer, we studied the statistical temporal distributions of single-electron packets as a function of various fs pulsed-laser parameters and electron-gun configurations and fields for the exact architecture and dimensions of a Thermo Fisher Tecnai Femto ultrafast electron microscope. We focused on easily-adjustable parameters, such as laser pulse duration, laser spot size, photon energy, Wehnelt aperture diameter, and photocathode size. In addition to establishing trends and dispersion behaviors, we identify regimes within which packet duration can be 100s of fs and approach the 300 fs laser limit employed here. Overall, the results provide a detailed picture of the temporal behavior of single-electron packets in the Tecnai Femto gun region, forming the initial contribution of a larger effort.

Probing free carrier plasmons in doped semiconductors using spatially resolved electron energy loss spectroscopy

We report spatially resolved measurements of free carrier collective excitations in a doped semiconductor. Using $\ensuremath{\sim}10$ meV resolution electron energy loss spectroscopy (EELS) in an electron microscope with $\AA{}$ spatial resolution, we identify both surface and bulk carrier plasmons at infrared energies in a freestanding film of indium tin oxide (ITO). The interference patterns of long wavelength propagating surface carrier plasmons are revealed using spatially resolved EELS, from which we extract a dispersion relation. We further show that the energies of these plasmons vary near the surfaces and grain boundaries of the film due to band bending. Modeling based on dielectric theory agrees very well with experimental results. Finally, carrier plasmons in amorphous and crystalline ITO films are compared. These results should also be helpful for understanding the free carrier plasmons in other doped semiconductors in nanoscale volumes.

Advanced Electron Microscopy of Multi-Valent Cathode Materials

Recent progress in the field of scanning/transmission electron microscopy (S/TEM) has resulted in intense electron probes providing an ultra-high spatial (e.g. sub-Å) and energy (3 meV) resolution, with a previously unattainable signal-to-noise ratio. Furthermore, the STEM-based methods: direct imaging of both heavy and light elements, and both the energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies are becoming the most promising characterization tools for battery materials, providing an unprecedented opportunity to probe the evolution of structure and electronic state of the cathodes following their electrochemical activity. The current talk will focus on the electron microscopy characterization of various materials that are considered as potential cathodes for the multivalent batteries, including transition metal (TM) oxides and polyanionic compounds. Materials were characterized using aberration-corrected JEOL JEM-ARM200CF, equipped with a cold field emission and operated at 200 kV, in pristine, cycled, and in-situ irradiated phases exploring their structure, chemistry, and electronic states. The in-situ technique mimics the electrochemical cell and allows for single-particle tracking of the dynamic processes occurring upon oxygen loss from the material providing helpful knowledge to further strengthen the understanding of the electrochemical activity of the cathodes. Several imaging modes, including high/low angle annular dark field (H/LAADF) and annular bright field (ABF), in conjunction with EELS/EDX, were used extensively for the analysis. Various parameters such as TM valence, phase transition, oxygen deficiency, and multivalent ion intercalation will be discussed.

Dynamic Spin Correlations in the Honeycomb Lattice Na2IrO3 Measured by Resonant Inelastic x-Ray Scattering

A Kitaev quantum spin liquid is a prime example of novel quantum magnetism of spin-orbit entangled pseudospin-1/2 moments in a honeycomb lattice. Most candidate materials such as Na2IrO3 have many competing exchange interactions beyond the minimal Kitaev-Heisenberg model whose small variations in the strength of the interactions produce huge differences in low-energy dynamics. Our incomplete knowledge of dynamic spin correlations hampers identification of a minimal model and quantification of the proximity to the Kitaev quantum spin-liquid phase. Here, we report momentum- and energy-resolved magnetic excitation spectra in a honeycomb lattice Na2IrO3 measured using a resonant inelastic x-ray scattering spectrometer capable of 12 meV resolution. Measured spectra at a low temperature show that the dynamic response lacks resolution-limited coherent spin waves in most parts of the Brillouin zone but has a discernible dispersion and spectral weight distribution within the energy window of 60 meV. A systematic investigation using the exact diagonalization method and direct comparison of high-resolution experimental spectra and theoretical simulations allow us to confine a parameter regime in which the extended Kitaev-Heisenberg model reasonably reproduces the main feature of the observed magnetic excitations. Hidden Kitaev quantum spin-liquid and Heisenberg phases found in the complex parameter space are used as references to propose the picture of renormalized magnons as explaining the incoherent nature of magnetic excitations. Magnetic excitation spectra are taken at elevated temperatures to follow the temperature evolution of the resonant inelastic x-ray scattering dynamic response in the paramagnetic state. Whereas the low-energy excitation progressively diminishes as the zigzag order disappears, the broad high-energy excitation maintains its spectral weight up to a much higher temperature of 160 K. We suggest that the dominant nearest-neighbor interactions keep short-range correlations up to quite high temperatures with a specific short-range dynamics which has a possible connection to a proximate spinliquid phase.

Resonant inelastic x-ray scattering study of -RuCl3: a progress report

Ru M3-edge resonant inelastic x-ray scattering (RIXS) measurements of with 27 meV resolution reveals a spin–orbit exciton without noticeable splitting. We extract values for the spin–orbit coupling constant ( meV) and trigonal distortion field energy ( meV) which support the nature of . We demonstrate the feasibility of M-edge RIXS for 4d systems, which allows ultra high-resolution RIXS of 4d systems until instrumentation for L-edge RIXS improves.

Extreme ultraviolet time- and angle-resolved photoemission setup with 21.5 meV resolution using high-order harmonic generation from a turn-key Yb:KGW amplifier.

Characterizing and controlling electronic properties of quantum materials require direct measurements of nonequilibrium electronic band structures over large regions of momentum space. Here, we demonstrate an experimental apparatus for time- and angle-resolved photoemission spectroscopy using high-order harmonic probe pulses generated by a robust, moderately high power (20 W) Yb:KGW amplifier with a tunable repetition rate between 50 and 150 kHz. By driving high-order harmonic generation (HHG) with the second harmonic of the fundamental 1025 nm laser pulses, we show that single-harmonic probe pulses at 21.8 eV photon energy can be effectively isolated without the use of a monochromator. The on-target photon flux can reach 5 × 1010 photons/s at 50 kHz, and the time resolution is measured to be 320 fs. The relatively long pulse duration of the Yb-driven HHG source allows us to reach an excellent energy resolution of 21.5 meV, which is achieved by suppressing the space-charge broadening using a low photon flux of 1.5 × 108 photons/s at a higher repetition rate of 150 kHz. The capabilities of the setup are demonstrated through measurements in the topological semimetal ZrSiS and the topological insulator Sb2-xGdxTe3.

Probing quantum optical excitations with fast electrons

Probing optical excitations with nanometer resolution is important for understanding their dynamics and interactions down to the atomic scale. Electron microscopes currently offer the unparalleled ability of rendering spatially-resolved electron spectra with combined meV and sub-nm resolution, while the use of ultrafast optical pulses enables fs temporal resolution and exposure of the electrons to ultraintense confined optical fields. Here, we theoretically investigate fundamental aspects of the interaction of fast electrons with localized optical modes that are made possible by these advances. We use a quantum-optics description of the optical field to predict that the resulting electron spectra strongly depend on the statistics of the sample excitations (bosonic or fermionic) and their population (Fock, coherent, or thermal), whose autocorrelation functions are directly retrieved from the ratios of electron gain intensities. We further explore feasible experimental scenarios to probe the quantum characteristics of the sampled excitations and their populations.

Progress Towards a Universal Approach for Prediction of the Superconducting Transition Temperature

A suite of density functional theory (DFT) approaches that provide accurate and reliable superconductivity parameters without post-calculation corrections is presented. The sensitivity of phonon dispersion (PD) outputs to slight variations in calculation and external parameters enables identification of the most electron-coupled phonon mode(s). These mode(s) are directly linked, in a range of superconductors, to specific band structure characteristics and to the response of electrons to deformation potentials. These approaches are applied successfully to MgB2 under a wide range of variable external conditions, including isotopic state, metal substitutions, pressure, and temperature. This approach has also been extended to other chemical systems with significantly different composition and crystal symmetry, such as YB6, H3S under pressure, B-doped diamond, B-doped silicon, and A15 compounds, to name a few. The effectiveness of these approaches that link both PDs and electronic band structures (EBSs) is largely dependent on reliable and accurate DFT results at the meV range that resolve Fermi surface (FS) detail in close reciprocal space proximity. Such a level of meV resolution is possible only by using extremely fine k-grids and large cutoff radii, much smaller and larger, respectively, to what has typically been used in DFT calculations reported in the literature.

Electron Diagnostics for Extreme High Brightness Nano-Blade Field Emission Cathodes

Electron beams are essential tools in modern science. They are ubiquitous in fields ranging from microscopy to the creation of coherent ultra-fast X-rays to lithography. To keep pace with demand, electron beam brightness must be continually increased. One of the main strategic aims of the Center for Bright Beams (CBB), a National Science Foundation Science and Technology Center, is to increase brightness from photocathodes by two orders of magnitude. Improving the state-of-the-art for photoemission-based cathodes is one possibility. Several factors have led to an alternative design becoming an increasing necessity; the nanoscale structure. Field emission sources from nano-tips would be an ideal candidate were it not for their low current and damage threshold. A 1-dimensional extended nano-fabricated blade, i.e., a projected tip, can solve the problems inherent in both designs. The novel geometry has been demonstrated to produce extremely high brightness electron beam bunches and is significantly more robust and easier to manufacture than traditional photocathodes. Theory indicates electron emission up to keV energies. We thus present a system of diagnostics capable of analyzing the cathodes and assessing their viability. The diagnostics are designed to measure the electron spectrum up to keV energies, with sub meV resolution at &lt;100 eV, mean transverse energy (MTE), emission uniformity, and cathode lifetime. We also report preliminary data on total extracted charge and maximum detectable electron energy with a simplified retarding field spectrometer.

Photoionization of tungsten ions: experiment and theory for W5+

Experimental and theoretical cross sections are reported for single-photon single ionization of W5+ ions. Absolute measurements were conducted employing the photon–ion merged-beams technique. Detailed photon-energy scans were performed at (67 ± 10) meV resolution in the 20–160 eV range. In contrast to photoionization of tungsten ions in lower charge states, the cross section is dominated by narrow, densely-spaced resonances. Theoretical results were obtained from a Dirac–Coulomb R-matrix approach employing a basis set of 457 levels providing cross sections for photoionization of W5+ ions in the ground level as well as the and metastable excited levels. Considering the complexity of the electronic structure of tungsten ions in low charge states, the agreement between theory and experiment is satisfactory.

Time-resolved\xa0XUV ARPES with tunable 24\u201333\u2009eV laser pulses at 30\u2009meV resolution

High harmonic generation of ultrafast laser pulses can be used to perform angle-resolved photoemission spectroscopy (ARPES) to map the electronic band structure of materials with femtosecond time resolution. However, currently it is difficult to reach high momenta with narrow energy resolution. Here, we combine a gas phase extreme ultraviolet (XUV) femtosecond light source, an XUV monochromator, and a time-of-flight electron analyzer to develop XUV-based time-resolved ARPES. Our technique can produce tunable photon energy between 24–33 eV with an unprecedented energy resolution of 30 meV and time resolution of 200 fs. This technique enables time-, energy- and momentum-resolved investigation of the nonequilibrium dynamics of electrons in materials with a full access to their first Brillouin zone. We evaluate the performance of this setup through exemplary measurements on various quantum materials, including WTe2, WSe2, TiSe2, and Bi2Sr2CaCu2O8+δ.

Electron energy analysis by phase-space shaping with THz field cycles.

Time-resolved electron energy analysis and loss spectroscopy can reveal a wealth of information about material properties and dynamical light-matter interactions. Here, we report an all-optical concept for measuring energy spectra of femtosecond electron pulses with sub-eV resolution. Laser-generated terahertz radiation is used to measure arrival time differences within electron pulses with few-femtosecond precision. Controlled dispersion and subsequent compression of the electron pulses provide almost any desired compromise of energy resolution, signal strength, and time resolution. A proof-of-concept experiment on aluminum reveals an energy resolution of <3.5 eV (rms) at 70-keV after a drift distance of only 0.5 m. Simulations of a two-stage scheme reveal that pre-stretched pulses can be used to achieve <10 meV resolution, independent of the source's initial energy spread and limited only by the achievable THz field strength and measuring time.