X-ray Photon Correlation Spectroscopy Research Articles

New pathways to control the evolution of the atomic motion in metallic glasses

Metallic glass formers are a relatively new entry in glass physics, which has attracted large interest in both physics and materials science communities due to the unique mechanical and structural properties of these materials. Physical aging is however one of the main obstacle to their widespread use as it affects their properties at all length scales. The knowledge of the microscopic mechanisms inducing aging and relaxation is therefore extremely important for both fundamental and applied sciences. In this article we present a review of the recent advances made with the X-ray photon correlation spectroscopy technique on the study of the collective particle motion and physical aging in metallic glasses at the atomic level. We show that a careful tuning of the sample preparation or the application of specific thermal protocols have the potential to drive the glass into more aged or rejuvenated microscopic configurations with different stabilities.

A new experimental setup for combined fast differential scanning calorimetry and X-ray photon correlation spectroscopy.

Synchrotron-radiation-based techniques are a powerful tool for the investigation of materials. In particular, the availability of highly brilliant sources has opened the possibility to develop techniques sensitive to dynamics at the atomic scale such as X-ray photon correlation spectroscopy (XPCS). XPCS is particularly relevant in the study of glasses, which have been often investigated at the macroscopic scale by, for example, differential scanning calorimetry. Here, we show how to adapt a Flash calorimeter to combine XPCS and calorimetric scans. This setup paves the way to novel experiments requiring dynamical and thermodynamic information, ranging from the study of the crystallization kinetics to the study of the glass transition in systems that can be vitrified thanks to the high cooling rates reachable with an ultrafast calorimeter.

Real-time swelling-collapse kinetics of nanogels driven by XFEL pulses.

Stimuli-responsive polymers are an important class of materials with many applications in nanotechnology and drug delivery. The most prominent one is poly-N-isopropylacrylamide (PNIPAm). The characterization of the kinetics of its change after a temperature jump is still a lively research topic, especially at nanometer-length scales where it is not possible to rely on conventional microscopic techniques. Here, we measured in real time the collapse of a PNIPAm shell on silica nanoparticles with megahertz x-ray photon correlation spectroscopy at the European XFEL. We characterize the changes of the particles diffusion constant as a function of time and consequently local temperature on sub-microsecond timescales. We developed a phenomenological model to describe the observed data and extract the characteristic times associated to the swelling and collapse processes. Different from previous studies tracking the turbidity of PNIPAm dispersions and using laser heating, we find collapse times below microsecond timescales and two to three orders of magnitude slower swelling times.

High-pressure X-ray photon correlation spectroscopy at fourth-generation synchrotron sources.

A new experimental setup combining X-ray photon correlation spectroscopy (XPCS) in the hard X-ray regime and a high-pressure sample environment has been developed to monitor the pressure dependence of the internal motion of complex systems down to the atomic scale in the multi-gigapascal range, from room temperature to 600 K. The high flux of coherent high-energy X-rays at fourth-generation synchrotron sources solves the problems caused by the absorption of diamond anvil cells used to generate high pressure, enabling the measurement of the intermediate scattering function over six orders of magnitude in time, from 10-3 s to 103 s. The constraints posed by the high-pressure generation such as the preservation of X-ray coherence, as well as the sample, pressure and temperature stability, are discussed, and the feasibility of high-pressure XPCS is demonstrated through results obtained on metallic glasses.

Particle Dynamics in a Diblock-Copolymer-Based Dodecagonal Quasicrystal and Its Periodic Approximant by X-Ray Photon Correlation Spectroscopy.

Temperature-dependent x-ray photon correlation spectroscopy (XPCS) measurements are reported for a binary diblock-copolymer blend that self-assembles into an aperiodic dodecagonal quasicrystal and a periodic Frank-Kasper σ phase approximant. The measured structural relaxation times are Bragg scattering wavevector independent and are 5 times faster in the dodecagonal quasicrystal than the σ phase, with minimal temperature dependence. The underlying dynamical relaxations are ascribed to differences in particle motion at the grain boundaries within each of these tetrahedrally close-packed assemblies. These results identify unprecedented particle dynamics measurements of tetrahedrally coordinated micellar block polymers, thus expanding the application of XPCS to ordered soft materials.

Real-time tracking of curing process of an epoxy adhesive by X-ray photon correlation spectroscopy

Introduction: Cross-linkable polymers are in widespread use in a variety of industries because of their thermomechanical toughness, chemical resistance, and adhesive strength. But traditional methods to characterize these materials are insufficient for fully capturing the complex chemical and physical mechanisms of the crosslinking reaction. In this study, in situ X-ray photon correlation spectroscopy (XPCS) was used to investigate the crosslinking kinetics of a two-component epoxy resin adhesive.Materials and methods: With XPCS, we tracked the temporally resolved dynamics of silica filler particles, which served as probes of the internal dynamics of the thermoset network and allowed us to study the crosslinking process. The epoxy was cured isothermally at 40 °C and 80 °C to study the effects of curing temperature on the epoxy’s crosslinking reaction. XPCS results were compared to dielectric analysis (DEA) results, to demonstrate the similarities between a traditional technique and XPCS, and highlight the additional information gained with XPCS.Results and discussion: The epoxy resin was found to be highly sensitive to temperature. The epoxy samples exhibited different relaxation processes depending on isothermal cure temperature, indicating a complex relationship between applied temperature and the development of stress/relaxation conditions associated with formation of the thermoset network. Heating to the isothermal temperature setpoint at the start of curing promoted gelation, but the vitrification process was not completed during the isothermal curing stage. Instead, cooling the sample to room temperature facilitated the final vitrification process. This paper contextualizes this epoxy’s results within the broader field of thermoset study via XPCS, and advocates for XPCS as a fundamental technique for the study of complex polymers.

Coherent diffractive imaging with twisted X-rays: Principles, applications, and outlook

Recent technological breakthroughs in synchrotron and x-ray free electron laser facilities have revolutionized nanoscale structural and dynamic analyses in condensed matter systems. This review provides a comprehensive overview of the advancements in coherent scattering and diffractive imaging techniques, which are now at the forefront of exploring materials science complexities. These techniques, notably Bragg coherent diffractive imaging and x-ray photon correlation spectroscopy, x-ray magnetic dichroism, and x-ray correlation analysis leverage beam coherence to achieve volumetric three-dimensional imaging at unprecedented sub-nanometer resolutions and explore dynamic phenomena within sub-millisecond timeframes. Such capabilities are critical in understanding and developing advanced materials and technologies. Simultaneously, the emergence of chiral crystals—characterized by their unique absence of standard inversion, mirror, or other roto-inversion symmetries—presents both challenges and opportunities. These materials exhibit distinctive interactions with light, leading to phenomena such as molecular optical activity, chiral photonic waveguides, and valley-specific light emissions, which are pivotal in the burgeoning fields of photonic and spintronic devices. This review elucidates how novel x-ray probes can be leveraged to unravel these properties and their implications for future technological applications. A significant focus of this review is the exploration of new avenues in research, particularly the shift from conventional methods to more innovative approaches in studying these chiral materials. Inspired by structured optical beams, the potential of coherent scattering techniques utilizing twisted x-ray beams is examined. This promising direction not only offers higher spatial resolution but also opens the door to previously unattainable insights in materials science. By contextualizing these advancements within the broader scientific landscape and highlighting their practical applications, this review aims to chart a course for future research in this rapidly evolving field.

Efficient end-to-end simulation of time-dependent coherent X-ray scattering experiments.

Physical optics simulations for beamlines and experiments allow users to test experiment feasibility and optimize beamline settings ahead of beam time in order to optimize valuable beam time at synchrotron light sources like NSLS-II. Further, such simulations also help to develop and test experimental data processing methods and software in advance. The Synchrotron Radiation Workshop (SRW) software package supports such complex simulations. We demonstrate how recent developments in SRW significantly improve the efficiency of physical optics simulations, such as end-to-end simulations of time-dependent X-ray photon correlation spectroscopy experiments with partially coherent undulator radiation (UR). The molecular dynamics simulation code LAMMPS was chosen to model the sample: a solution of silica nanoparticles in water at room temperature. Real-space distributions of nanoparticles produced by LAMMPS were imported into SRW and used to simulate scattering patterns of partially coherent hard X-ray UR from such a sample at the detector. The partially coherent UR illuminating the sample can be represented by a set of orthogonal coherent modes obtained by simulation of emission and propagation of this radiation through the coherent hard X-ray (CHX) scattering beamline followed by a coherent-mode decomposition. GPU acceleration is added for several key functions of SRW used in propagation from sample to detector, further improving the speed of the calculations. The accuracy of this simulation is benchmarked by comparison with experimental data.

Bridging length scales in organic mixed ionic-electronic conductors through internal strain and mesoscale dynamics.

Understanding the structural and dynamic properties of disordered systems at the mesoscale is crucial. This is particularly important in organic mixed ionic-electronic conductors (OMIECs), which undergo significant and complex structural changes when operated in an electrolyte. In this study, we investigate the mesoscale strain, reversibility and dynamics of a model OMIEC material under external electrochemical potential using operando X-ray photon correlation spectroscopy. Our results reveal that strain and structural hysteresis depend on the sample's cycling history, establishing a comprehensive kinetic sequence bridging the macroscopic and microscopic behaviours of OMIECs. Furthermore, we uncover the equilibrium and non-equilibrium dynamics of charge carriers and material-doping states, highlighting the unexpected coupling between charge carrier dynamics and mesoscale order. These findings advance our understanding of the structure-dynamics-function relationships in OMIECs, opening pathways for designing and engineering materials with improved performance and functionality in non-equilibrium states during device operation.

Atomic cluster dynamics causes intermittent aging of metallic glasses

In the past two decades, numerous relaxation or physical aging experiments of metallic glasses have revealed signatures of intermittent atomic-scale processes. Revealed via intensity cross-correlations from coherent scattering using X-ray photon correlation spectroscopy (XPCS), the observed abrupt changes in the time-domain of atomic motion does not fit the picture of gradual slowing down of relaxation times and their origin continues to remain unclear. Using a binary Lennard-Jones model glass subjected to microsecond-long isotherms, we show here that temporally and spatially heterogeneous atomic-cluster activity at different length-scales drive the emergence of highly non-monotonous intensity cross-correlations. The simulated XPCS experiments reveal a variety of time-dependent intensity-cross correlations that, depending on both the structural evolution and the q-space sampling, give detailed insights into the possible structural origins of intermittent aging measured with XPCS.

Unveiling the Structural Origins of Dynamic Diversity in Pd-Based Metallic Glasses.

The β-relaxation is one of the major dynamic behaviors in metallic glasses (MGs) and exhibits diverse features. Despite decades of efforts, the understanding of its structural origin and contribution to the overall dynamics of MG systems is still unclear. Here two palladium-based Pd─Cu─P and Pd─Ni─P MGs are reported with distinct different β-relaxation behaviors and reveal the structural origins for the difference using the advanced X-ray photon correlation spectroscopy and absorption fine structure techniques together with the first-principles calculations. The pronounced β-relaxation and fast atomic dynamics in the Pd─Cu─P MG mainly come from the strong mobility of Cu atoms and their locally favored structures. In contrast, the motion of Ni atoms is constrained by P atoms in the Pd─Ni─P MG, leading to the weakened β-relaxation peak and sluggish dynamics. The correlation of atomic dynamics with microscopic structures provides a way to understand the structural origins of different dynamic behaviors as well as the nature of aging in disordered materials.

Coherent X-ray Spectroscopy Elucidates Nanoscale Dynamics of Plasma-Enhanced Thin-Film Growth.

Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

AbstractThe structure and dynamics of polystyrene (PS)‐b‐poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase‐separated cylindrical and lamellar morphologies. Structural dynamics are measured with X‐ray photon correlation spectroscopy in the small‐angle regime. Morphologies and domain sizes are evaluated using small‐angle X‐ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (Tg) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near Tg of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 Tg of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS Tg (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out‐of‐equilibrium state of PS dominates the structural dynamics of these strongly phase‐segregated BCPs.

Dynamics of anisotropic colloidal systems: What to choose, DLS, DDM or XPCS?

Investigation of the dynamics of colloids in bulk can be hindered by issues such as multiple scattering and sample opacity. These challenges are exacerbated when dealing with inorganic materials. In this study, we employed a model system of Akaganeite colloidal rods to assess three leading dynamics measurement techniques: 3D-(depolarized) dynamic light scattering (3D-(D)DLS), polarized-differential dynamic microscopy (P-DDM), and x-ray photon correlation spectroscopy (XPCS). Our analysis revealed that the translational and rotational diffusion coefficients captured by these methods show a remarkable alignment. Additionally, by examining the q-ranges and maximum volume fractions for each approach, we offer insights into the best technique for investigating the dynamics of anisotropic systems at the colloidal scale.

Improvement of ultra-small-angle XPCS with the Extremely Brilliant Source.

Recent technical developments and the performance of the X-ray photon correlation spectroscopy (XPCS) method over the ultra-small-angle range with the Extremely Brilliant Source (EBS) at the ESRF are described. With higher monochromatic coherent photon flux (∼1012 photons s-1) provided by the EBS and the availability of a fast pixel array detector (EIGER 500K detector operating at 23000 frames s-1), XPCS has become more competitive for probing faster dynamics in relatively dilute suspensions. One of the goals of the present development is to increase the user-friendliness of the method. This is achieved by means of a Python-based graphical user interface that enables online visualization and analysis of the processed data. The improved performance of XPCS on the Time-Resolved Ultra-Small-Angle X-ray Scattering instrument (ID02 beamline) is demonstrated using dilute model colloidal suspensions in several different applications.

X-ray-induced piezoresponse during X-ray photon correlation spectroscopy of PbMg1/3Nb2/3O3.

X-ray photon correlation spectroscopy (XPCS) holds strong promise for observing atomic-scale dynamics in materials, both at equilibrium and during non-equilibrium transitions. Here an in situ XPCS study of the relaxor ferroelectric PbMg1/3Nb2/3O3 (PMN) is reported. A weak applied AC electric field generates strong response in the speckle of the diffuse scattering from the polar nanodomains, which is captured using the two-time correlation function. Correlated motions of the Bragg peak are also observed, which indicate dynamic tilting of the illuminated volume. This tilting quantitatively accounts for the observed two-time speckle correlations. The magnitude of the tilting would not be expected solely from the modest applied field, since PMN is an electrostrictive material with no linear strain response to the field. A model is developed based on non-uniform static charging of the illuminated surface spot by the incident micrometre-scale X-ray beam and the electrostrictive material response to the combination of static and dynamic fields. The model qualitatively explains the direction and magnitude of the observed tilting, and predicts that X-ray-induced piezoresponse could be an important factor in correctly interpreting results from XPCS and nanodiffraction studies of other insulating materials under applied AC field or varying X-ray illumination.

Orientational ordering and assembly of silica-nickel Janus particles in a magnetic field.

The orientation ordering and assembly behavior of silica-nickel Janus particles in a static external magnetic field were probed by ultra small-angle X-ray scattering (USAXS). Even in a weak applied field, the net magnetic moments of the individual particles aligned in the direction of the field, as indicated by the anisotropy in the recorded USAXS patterns. X-ray photon correlation spectroscopy (XPCS) measurements on these suspensions revealed that the corresponding particle dynamics are primarily Brownian diffusion [Zinn, Sharpnack & Narayanan (2023). Soft Matter, 19, 2311-2318]. At higher fields, the magnetic forces led to chain-like configurations of particles, as indicated by an additional feature in the USAXS pattern. A theoretical framework is provided for the quantitative interpretation of the observed anisotropic scattering diagrams and the corresponding degree of orientation. No anisotropy was detected when the magnetic field was applied along the beam direction, which is also replicated by the model. The method presented here could be useful for the interpretation of oriented scattering patterns from a wide variety of particulate systems. The combination of USAXS and XPCS is a powerful approach for investigating asymmetric colloidal particles in external fields.

The SparkPix-S ASIC for the sparsified readout of 1 MHz frame-rate X-ray cameras at LCLS-II: pixel design and simulation results

Exploiting the “sparse” nature of the information in XPCS (X-ray Photon Correlation Spectroscopy) and XSVS (Speckle Visibility Spectroscopy) experiments, we present the SparkPix-S, a 3-sides buttable Application Specific Integrated Circuit (ASIC) based on a sparsified readout strategy for large-format hybrid detectors. The SparkPix-S architecture, based on the successful ePix family, will be composed as follows: a front-end 2-D matrix of 384×352 square pixels with 50 µm pitch is arranged to match the dimensions of a PIN Si-sensor matrix; charge readout, signal shaping and amplitude discrimination is performed at pixel-level, by means of a low-power (<18 µW) analog processor, which, in case of an event, negotiates access to an analog bus placed every other column; on the chip periphery (balcony), the information on each bus is digitized by an array of successive approximation analog-to-digital converters (SAR-ADCs) running at 10 Msps; on the digital back-end the global logic will generate the output data stream using low-voltage differential signalling (LVDS).A first prototype of the SparkPix-S, with a reduced matrix size of 96×96 pixels, is currently under production on a 130 nm CMOS technology. Simulated performance results show an equivalent noise charge <60 el. r.m.s. at 1 MHz repetition rate, with a maximum input energy of 60 keV and capability to discriminate charge signals with equivalent energy as low as 900 eV.

A versatile pressure-cell design for studying ultrafast molecular-dynamics in supercritical fluids using coherent multi-pulse x-ray scattering.

Supercritical fluids (SCFs) can be found in a variety of environmental and industrial processes. They exhibit an anomalous thermodynamic behavior, which originates from their fluctuating heterogeneous micro-structure. Characterizing the dynamics of these fluids at high temperature and high pressure with nanometer spatial and picosecond temporal resolution has been very challenging. The advent of hard x-ray free electron lasers has enabled the development of novel multi-pulse ultrafast x-ray scattering techniques, such as x-ray photon correlation spectroscopy (XPCS) and x-ray pump x-ray probe (XPXP). These techniques offer new opportunities for resolving the ultrafast microscopic behavior in SCFs at unprecedented spatiotemporal resolution, unraveling the dynamics of their micro-structure. However, harnessing these capabilities requires a bespoke high-pressure and high-temperature sample system that is optimized to maximize signal intensity and address instrument-specific challenges, such as drift in beamline components, x-ray scattering background, and multi-x-ray-beam overlap. We present a pressure cell compatible with a wide range of SCFs with built-in optical access for XPCS and XPXP and discuss critical aspects of the pressure cell design, with a particular focus on the design optimization for XPCS.

In situ aggregation and early states of gelation of gold nanoparticle dispersions.

The aggregation and onset of gelation of PEGylated gold nanoparticles dispersed in a glycerol-water mixture is studied by small-angle X-ray scattering and X-ray photon correlation spectroscopy. Tracking structural dynamics with sub-ms time resolution over a total experimental time of 8 hours corresponding to a time windows larger than 108 Brownian times and varying the temperature between 298 K and 266 K we can identify three regimes. First, while cooling to 275 K the particles show Brownian motion that slows down due to the increasing viscosity. Second, upon further cooling the static structure changes significantly, indicated by a broad structure factor peak. We attribute this to the formation of aggregates while the dynamics are still dominated by single-particle diffusion. Finally, the relaxation functions become more and more stretched accompanied by an increased slow down of the dynamics. At the same time the structure changes continuously indicating the onset of gelation. Our observations further suggest that the colloidal aggregation and gelation is characterized first by structural changes with a subsequent slowing down of the systems dynamics. The analysis also reveals that the details of the gelation process and the gel structure strongly depend on the thickness of the PEG-coating of the gold nanoparticles.