Resonant Soft X-ray Research Articles

Characterization of latent image of electron beam resist via critical-dimension resonant soft X-ray scattering

Characterization of latent image of electron beam resist via critical-dimension resonant soft X-ray scattering

Local and Symmetry-Resolved Electronic Structure of Liquid Dimethyl Sulfoxide from Resonant Inelastic Soft X-ray Scattering.

Dimethyl sulfoxide (DMSO) is an important polar solvent that derives its unique properties from the lone pair and the strong polar bond at the sulfinyl functional group. To derive the local and symmetry-resolved electronic structure of liquid DMSO, we have used resonant inelastic soft X-ray scattering (RIXS) maps at the S L2,3, C K, and O K edges. The experimental data are compared to calculations of spectra based on density functional theory, which allows a detailed analysis of the molecular orbitals throughout the molecule. In the RIXS maps, we find the signature of molecular-field splitting of the S 2p core levels, vibronic coupling, and ultrafast nuclear dynamics on the time scale of the RIXS process.

High-transmission spectrometer for rapid resonant inelastic soft X-ray scattering (rRIXS) maps.

The design and first results of a high-transmission soft X-ray spectrometer operated at the X-SPEC double-undulator beamline of the KIT Light Source are presented. As a unique feature, particular emphasis was placed on optimizing the spectrometer transmission by maximizing the solid angle and the efficiencies of spectrometer gratings and detector. A CMOS detector, optimized for soft X-rays, allows for quantum efficiencies of 90% or above over the full energy range of the spectrometer, while simultaneously offering short readout times. Combining an optimized control system at the X-SPEC beamline with continuous energy scans (as opposed to step scans), the high transmission of the spectrometer, and the fast readout of the CMOS camera, enable the collection of entire rapid resonant inelastic soft X-ray scattering maps in less than 1 min. Series of spectra at a fixed energy can be taken with a frequency of up to 5 Hz. Furthermore, the use of higher-order reflections allows a very wide energy range (45 to 2000 eV) to be covered with only two blazed gratings, while keeping the efficiency high and the resolving power E/ΔE above 1500 and 3000 with low- and high-energy gratings, respectively.

Applicability of energy-theta mapping in resonant soft X-ray reflectometry to probe depth dependence of oxidation state and crystallographic environment in iron oxide multilayers

In the present paper we discuss applicability of the synchrotron method of resonant x-ray reflectometry to non-destructive depth profiling of multilayer heterostructures with low optical contrast between the sublayers. The two-dimensional mapping approach comprising evaluation and measurement of reflectance as a function of photon energy and grazing angle is shown to provide a convenient way to effectively utilize the enhancement of optical contrast between the sublayers that exists at the absorption edges of chemical elements due to particular spectral shape peculiarities related to oxidation state, crystallographic environment and magnetization. In the present study the evaluation of the resonant X-ray reflectivity maps is performed using a specially developed modeling and fitting software. Estimation of the photon energy / grazing angle combinations at which the reflectance is most sensitive to the minor changes in the physical properties of the sublayers is illustrated by the example of ferroic-on-semiconductor nanoscale heterostructures composed of nanoscale film of metallic iron oxidized from either top or bottom side. The subtle differences in resonant soft x-ray reflectance caused by variation of the oxide film thickness, oxidation state and crystallographic environment are discussed. The presented approach is applicable to a large class of heterostructures composed of sublayers that can be distinguished only by the differences in their near edge X-ray absorption fine structure.

(Invited) Probing Electrochemical Interfaces in Catalytic and Energy Materials and Process Using Operando Soft X-Ray Spectroscopy

Advanced energy technology arises from the understanding in fundamental science, thus rest in large on in-situ/operando characterization tools for observing the physical and chemical interfacial processes. Synchrotron based X-ray spectroscopic techniques offers unique characterization in many important energy materials of energy conversion, energy storage and catalysis in regards to the functionality, complexity of material architecture, chemistry and interactions among constituents within. However, it is challenging to reveal the real mechanism of the chemical processes.In the operando soft X-ray spectroscopy characterization of interfacial phenomena in energy materials and devices, it has been found that the microstructure and composition of materials as well as the microstructure evolution process have a great influence on performances in a variety of fields, e.g., energy conversion and energy storage materials, chemical and catalytic processes. This presentation will show how to best use the in-situ/operando soft X-ray spectroscopy characterization techniques, including soft x-ray absorption spectroscopy (XAS) and resonant inelastic soft X-ray scattering (RIXS) to investigate the real electrochemical mechanism during the operation. The experimental results show how in-situ/operando soft X-ray spectra characterization techniques uncover the phase conversion, chemical and environmental change of elements and other very important information of solid/gas and solid/liquid interfaces in real time, thus further enhance the understanding of real reaction mechanism.

Two distinct charge density waves in the quasi-one-dimensional metal Sr0.95NbO3.37 revealed by resonant soft X-ray scattering

The interplay of electron-electron and electron-lattice interactions plays an important role in determining exotic properties in strongly correlated electron systems. Of particular interest is quasi-one-dimensional SrNbOx metals, which are perovskite-related layered Carpy-Galy phases. Quasi-one-dimensional metals often exhibit a charge density wave (CDW) accompanied by lattice distortion; however, to date, the presence of a CDW in a quasi-one-dimensional metallic Carpy-Galy phase has not been detected. Here, we report the discovery of two distinct and simultaneous commensurate CDWs in Sr0.95NbO3.37 using resonant soft X-ray scattering (RSXS), namely, an electronic-(001) superlattice below ~ 200 K and an electronic-(002) Bragg peak. We also observe a non-electronic-(002) Bragg peak showing lattice distortion below ~ 150 K. Through the temperature dependence and resonance profile of these CDWs and the lattice distortion, as well as the relationship between the wavelength and charge density, these CDWs are determined to be Wigner crystals and Peierls-like instabilities, respectively. The electron‒electron interaction is strong and dominant even up to 350 K, and upon cooling, it drives the electron–lattice interaction. The correlation length of the electronic-(001) superlattice is surprisingly larger than that of the electronic-(002) Bragg peak, and the superlattice is highly anisotropic. Supported by theoretical calculations, the CDWs are determined by the charge anisotropy and redistribution between the O-2p and Nb-4d orbitals, and the strength of the electronic-(001) superlattice is within the strong coupling limit.

Self-Assembly of Hierarchical High-χ Fluorinated Block Copolymers with an Orthogonal Smectic-within-Lamellae 3 nm Sublattice and Vertical Surface Orientation.

Hierarchical structure-within-structure assemblies offer a route toward increasingly complex and multifunctional materials while pushing the limits of block copolymer self-assembly. We present a detailed study of the self-assembly of a series of fluorinated high-χ block copolymers (BCPs) prepared via postmodification of a single poly(styrene)-block-poly(glycidyl methacrylate) (S-b-G) parent polymer with the fluorinated alkylthiol pendent groups containing 1, 6, or 8 fluorinated carbons (termed trifluoro-ethanethiol (TFET), perfluoro-octylthiol (PFOT), and perfluoro-decylthiol (PFDT), respectively). Bulk X-ray scattering of thermally annealed samples demonstrates hierarchical molecular assembly with phase separation between the two blocks and within the fluorinated block. The degree of ordering within the fluorinated block is highly sensitive to synthetic variation; a lamellar sublattice was formed for S-b-GPFOT and S-b-GPFDT. Thermal analyses of S-b-GPFOT reveal that the fluorinated block exhibits liquid crystal-like ordering. The complex thin-film self-assembly behavior of an S-b-GPFOT polymer was investigated using real-space (atomic force microscopy and scanning electron microscopy) and reciprocal-space (resonant soft X-ray scattering (RSoXS), grazing incidence small- and wide-angle scattering) measurements. After thermal annealing in nitrogen or vacuum, films thicker than 1.5 times the primary lattice spacing exhibit a 90-degree grain boundary, exposing a thin layer of vertical lamellae at the free interface, while exhibiting horizontal lamellae on the preferential (polystyrene brush) substrate. RSoXS measurements reveal the near-perfect orthogonality between the primary and sublattice orientations, demonstrating hierarchical patterning at the nanoscale.

Molecular Weight-Independent "Polysoap" Nanostructure Characterized via In Situ Resonant Soft X-ray Scattering.

Studying polymer micelle structure and loading dynamics under environmental conditions is critical for nanocarrier applications but challenging due to a lack of in situ nanoprobes. Here, the structure and loading of amphiphilic polyelectrolyte copolymer micelles, formed by 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and n-dodecyl acrylamide (DDAM), were investigated using a multimodal approach centered around in situ resonant soft X-ray scattering (RSoXS). We observe aqueous micelles formed from polymers of wide-ranging molecular weights and aqueous concentrations. Despite no measurable critical micelle concentration (CMC), structural analyses point toward multimeric structures for most molecular weights, with the lowest molecular weight micelles containing mixed coronas and forming loose micelle clusters that enhance hydrocarbon uptake. The sizes of the micelle substructures are independent of both the concentration and molecular weight. Combining these results with a measured molecular weight-invariant surface charge and zeta potential strengthens the link between the nanoparticle size and ionic charge in solution that governs the polysoap micelle structure. Such control would be critical for nanocarrier applications, such as drug delivery and water remediation.

Electronic structure of superconducting VN(111) films

Vanadium nitride (VN) is a transition-metal nitride with remarkable properties that have prompted extensive experimental and theoretical investigations in recent years. However, there is a current paucity of experimental research investigating the temperature-dependent electronic structure of single-crystalline VN. In this study, high-quality VN(111) films were successfully synthesized on α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document}-Al2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}O3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}(0001) substrates using magnetron sputtering. The crystal and electronic structures of the VN films were characterized by a combination of high-resolution X-ray diffraction, low-energy electron diffraction, resonant soft X-ray absorption spectroscopy, and ultraviolet photoelectron spectroscopy. The electrical transport measurements indicate that the superconducting critical temperature of the VN films is around 8.1 K. Intriguingly, the temperature-dependent photoelectron spectroscopy measurements demonstrate a weak temperature dependence in the electronic structure of the VN films, which is significant for understanding the ground state of VN compounds.

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes.

Resonant inelastic x-ray scattering (RIXS) is a major method for investigation of electronic structure and dynamics, with applications ranging from basic atomic physics to materials science. In RIXS applied to inversion-symmetric systems, it has generally been accepted that strict parity selectivity applies in the sub-kilo-electron volt region. In contrast, we show that the parity selection rule is violated in the RIXS spectra of the free homonuclear diatomic O2 molecule. By analyzing the spectral dependence on scattering angle, we demonstrate that the violation is due to the phase difference in coherent scattering at the two atomic sites, in analogy with Young's double-slit experiment. The result also implies that the interpretation of x-ray absorption spectra for inversion symmetric molecules in this energy range must be revised.

Absence of 3a0 charge density wave order in the infinite-layer nickelate NdNiO2

A hallmark of many unconventional superconductors is the presence of many-body interactions that give rise to broken-symmetry states intertwined with superconductivity. Recent resonant soft X-ray scattering experiments report commensurate 3a0 charge density wave order in infinite-layer nickelates, which has important implications regarding the universal interplay between charge order and superconductivity in both cuprates and nickelates. Here we present X-ray scattering and spectroscopy measurements on a series of NdNiO2+x samples, which reveal that the signatures of charge density wave order are absent in fully reduced, single-phase NdNiO2. The 3a0 superlattice peak instead originates from a partially reduced impurity phase where excess apical oxygens form ordered rows with three-unit-cell periodicity. The absence of any observable charge density wave order in NdNiO2 highlights a crucial difference between the phase diagrams of cuprate and nickelate superconductors.

Discovering a Wigner-like crystal and soft x-ray correlated plasmons and their couplings in a transition metal dichalcogenide

Low-dimensional systems host many exotic physical properties. Using extended resonant soft x-ray scattering supported with theoretical calculations, we observe concomitantly a Wigner-like crystal in a stripe-like QHKL = (001) superlattice with surprisingly long coherence lengths and new soft x-ray correlated plasmons in WS2. A new electronic transition is found at 125 K upon cooling, which is a transition from two-dimensional ordering to three-dimensional ordering, a result of p–d hybridization anisotropy and electronic correlations. Our result shows the importance of the interplay of long-range electron–electron correlation and short-range electronic screening in determining electronics and optical properties of transition metal dichalcogenides.

A low noise CMOS camera system for 2D resonant inelastic soft X-ray scattering

Resonant Inelastic X-ray Scattering (RIXS) is a powerful spectroscopic technique to study quantum properties of materials in the bulk. A novel variant of RIXS, called 2D RIXS, enables concurrent measurement of the scattered X-ray spectrum for a wide range of input energies, improving on the typically low throughput of 1D RIXS. In the soft X-ray domain, 2D RIXS demands an X-ray camera system with small pixels, large area, high quantum efficiency and low noise to limit the false detection rate in long duration exposures. We designed and implemented a 7.5 Megapixel back-illuminated CMOS detector with 5 μm pixels and high quantum efficiency in the 200–1,000 eV X-ray energy range for the QERLIN 2D RIXS spectrometer at the Advanced Light Source. The QERLIN beamline and detector are currently in commissioning. The camera noise from in-situ 3 s long dark exposures is 7e− or less and the leakage current is 6.5 × 10−3 e−/(pixel ∙ s). For individual 500 eV X-rays, the expected efficiency is greater than 75% and the false detection rate is ∼1 × 10−5 per pixel.

Pure Chiral Polar Vortex Phase in PbTiO3/SrTiO3 Superlattices with Tunable Circular Dichroism.

Nontrivial polarization textures have been demonstrated in ferroelectric/dielectric superlattices, where the electrostatic, elastic, and different gradient energies compete in a delicate balance. When PbTiO3/SrTiO3 superlattices are grown on DyScO3, the coexistence of ferroelectric domains and vortex structure is observed for n = 12-20 unit cells. Here, we report an approach to achieve single-phase vortex structures in superlattices by controlling the epitaxial strain using Sr1.04Al0.12Ga0.35Ta0.50O3 substrates. The domain width follows Kittel's law with the thickness of the ferroelectric PbTiO3 layers. A phase transition from vortex to a disordered phase with temperature is characterized by the correlation length. Resonant soft X-ray diffraction circular dichroism at the titanium L-edge reveals enhanced chirality with the thickness of the ferroelectric layer. These results are supported by second-principles simulations, which demonstrate that the integrated helicity increases with n. The stabilization of chiral single-phase polar vortices in ferroelectric/dielectric superlattices can enable novel optoelectronic devices with enhanced ferroelectric-light interaction.

Composition Dictates Molecular Orientation at the Heterointerfaces of Vapor-Deposited Glasses.

Physical vapor deposition (PVD) can prepare organic glasses with a preferred molecular orientation. The relationships between deposition conditions and orientation have been extensively investigated in the film bulk. The role of interfaces on the structure is less well understood and remains a key knowledge gap, as the interfacial region can govern glass stability and optoelectronic properties. Robust experimental characterization has remained elusive due to complexities in interrogating molecular organization in amorphous, organic materials. Polarized soft X-rays are sensitive to both the composition and the orientation of transition dipole moments in the film, making them uniquely suited to probe molecular orientation in amorphous soft matter. Here, we utilize polarized resonant soft X-ray reflectivity (P-RSoXR) to simultaneously depth profile the composition and molecular orientation of a bilayer prepared through the physical vapor deposition of 1,4-di-[4-(N,N-diphenyl)amino]styryl-benzene (DSA-Ph) on a film of aluminum-tris(8-hydroxyquinoline) (Alq3). The bulk orientation of the DSA-Ph layer is controlled by varying deposition conditions. Utilizing P-RSoXR to depth profile the films enables determination of both the bulk orientation of DSA-Ph and the orientation near the Alq3 interface. At the Alq3 surface, DSA-Ph always lies with its long axis parallel to the interface, before transitioning into the bulk orientation. This is likely due to the lower mobility and higher glass transition of Alq3, as the first several monolayers of DSA-Ph deposited on Alq3 appear to behave as a blend. We further show how orientation at the interface correlates with the bulk behavior of a codeposited glass of similar blend composition, demonstrating a straightforward approach to predicting molecular orientation at heterointerfaces. This work provides key insights into how molecules orient during vapor deposition and offers methods to predict this property, a critical step toward controlling interfacial behavior in soft matter.

Spatial Distribution Analysis of Polymers in Resist Thin Film by Reflection-mode Resonant Soft X-ray Scattering

Spatial Distribution Analysis of Polymers in Resist Thin Film by Reflection-mode Resonant Soft X-ray Scattering

Upper critical solution temperature polymer assemblies via variable temperature liquid phase transmission electron microscopy and liquid resonant soft X-ray scattering

Here, we study the upper critical solution temperature triggered phase transition of thermally responsive poly(ethylene glycol)-block-poly(ethylene glycol) methyl ether acrylate-co-poly(ethylene glycol) phenyl ether acrylate-block-polystyrene nanoassemblies in isopropanol. To gain mechanistic insight into the organic solution-phase dynamics of the upper critical solution temperature polymer, we leverage variable temperature liquid-cell transmission electron microscopy correlated with variable temperature liquid resonant soft X-ray scattering. Heating above the upper critical solution temperature triggers a reduction in particle size and a morphological transition from a spherical core shell particle with a complex, multiphase core to a micelle with a uniform core and Gaussian polymer chains attached to the surface. These correlated solution phase methods, coupled with mass spectral validation and modeling, provide unique insight into these thermoresponsive materials. Moreover, we detail a generalizable workflow for studying complex, solution-phase nanomaterials via correlative methods.

Coexistence of surface oxygen vacancy and interface conducting states in LaAlO3/SrTiO3 revealed by grazing-angle resonant soft x-ray scattering

Oxide heterostructures have shown rich physics phenomena, particularly in the conjunction of exotic insulator–metal transition (IMT) at the interface between polar insulator LaAlO3 and non-polar insulator SrTiO3 (LaAlO3/SrTiO3). The polarization catastrophe model has suggested an electronic reconstruction, yielding to metallicity at both the interface and surface. Another scenario is the occurrence of surface oxygen vacancy at LaAlO3 (surface-Ov), which has predicted surface-to-interface charge transfer, yielding metallic interface but insulating surface. To clarify the origin of IMT, one should probe surface-Ov and the associated electronic structures at both the surface and the buried interface simultaneously. Here, using grazing-angle resonant soft x-ray scattering (GA-RSXS) supported with first-principles calculations, we reveal the co-existence of the surface-Ov state and the interface conducting state only in conducting LaAlO3/SrTiO3 (001) films. Interestingly, both the surface-Ov state and the interface conducting state are absent for the insulating film. As a function of Ov density, while the surface-Ov state is responsible for the IMT, the spatial charge distribution is found responsible for a transition from two-dimensional-like to three-dimensional-like conductivity accompanied by spectral weight transfer, revealing the importance of electronic correlation. Our results show the importance of surface-Ov in determining interface properties and provide a new strategy in utilizing GA-RSXS to directly probe the surface and buried interface electronic properties in complex oxide heterostructures.

CyRSoXS: a GPU-accelerated virtual instrument for polarized resonant soft X-ray scattering.

Polarized resonant soft X-ray scattering (P-RSoXS) has emerged as a powerful synchrotron-based tool that combines the principles of X-ray scattering and X-ray spectroscopy. P-RSoXS provides unique sensitivity to molecular orientation and chemical heterogeneity in soft materials such as polymers and biomaterials. Quantitative extraction of orientation information from P-RSoXS pattern data is challenging, however, because the scattering processes originate from sample properties that must be represented as energy-dependent three-dimensional tensors with heterogeneities at nanometre to sub-nanometre length scales. This challenge is overcome here by developing an open-source virtual instrument that uses graphical processing units (GPUs) to simulate P-RSoXS patterns from real-space material representations with nanoscale resolution. This computational framework - called CyRSoXS (https://github.com/usnistgov/cyrsoxs) - is designed to maximize GPU performance, including algorithms that minimize both communication and memory footprints. The accuracy and robustness of the approach are demonstrated by validating against an extensive set of test cases, which include both analytical solutions and numerical comparisons, demonstrating an acceleration of over three orders of magnitude relative to the current state-of-the-art P-RSoXS simulation software. Such fast simulations open up a variety of applications that were previously computationally unfeasible, including pattern fitting, co-simulation with the physical instrument for operando analytics, data exploration and decision support, data creation and integration into machine learning workflows, and utilization in multi-modal data assimilation approaches. Finally, the complexity of the computational framework is abstracted away from the end user by exposing CyRSoXS to Python using Pybind. This eliminates input/output requirements for large-scale parameter exploration and inverse design, and democratizes usage by enabling seamless integration with a Python ecosystem (https://github.com/usnistgov/nrss) that can include parametric morphology generation, simulation result reduction, comparison with experiment and data fitting approaches.

Versatile tabletop setup for picosecond time-resolved resonant soft x-ray scattering and spectroscopy

Versatile tabletop setup for picosecond time-resolved resonant soft x-ray scattering and spectroscopy