arXiv subjects

Donald A. Walko

Publications and source records attributed to Donald A. Walko.

At least 19 recordsLinked to original sources

arXiv2026

Structural Phase Separation Couples to Charge-Density-Wave Formation in Kagome Metal FeGe

The intertwining of charge, spin, and lattice degrees of freedom underlies the emergent properties of correlated materials. A recent prominent example is the kagome metal FeGe, which hosts coexisting charge density wave (CDW) and antiferromagnetic orders, accompanied by a lattice distortion associated with partial Ge-Ge dimerization. Using temperature-dependent high-resolution X-ray diffraction measurements, we observed a robust splitting of the lattice reflection into two coexisting peaks with distinct lattice constants at the CDW transition temperature TCDW, providing direct evidence for a first-order structural phase transition that is absent in samples with suppressed CDW order. Furthermore, the long-range CDW order was found to be only commensurate with lattice structures with the compressed out-of-plane lattice constant. The Landau free energy analysis shows that strong lattice-charge coupling is a key factor in stabilizing long-range CDW order. Our work clarifies the critical role of structural transformation in the CDW formation and opens opportunities for strain control of electronic phases in FeGe.

cond-mat.mtrl-sci↗

arXiv2026

Persistent structural distortions and absent superconductivity in trilayer nickelate thin films

A new family of high-temperature superconductors was recently discovered in the $n=2,3$ Ruddlesden-Popper nickelates, where superconductivity emerges concomitant with suppression of parent density waves and structural octahedral rotations under hydrostatic pressure. Intriguingly, compressive strain mimics the structural effects of pressure in the $n=2$ phase, yielding ambient-pressure superconductivity. However, analogous strain-stabilized superconductivity has not been realized in the $n=3$. Here, we use atomically-precise synthesis, transport, picoscale electron microscopy, and synchrotron X-ray diffraction to probe $n=3$ La$_4$Ni$_3$O$_{10}$ thin films. Although compressive strain suppresses density wave order, we do not observe superconductivity even under the largest strain state. Importantly, we identify a structural distortion unique to strained $n=3$ thin films that may inhibit superconductivity: persistent, layer-inequivalent octahedral rotations around the $c$-axis. Our results highlight key differences between the $n=3$ and $n=2$ systems, suggesting that ambient-pressure superconductivity in the $n=3$ may require new methods beyond epitaxial strain engineering.

cond-mat.mtrl-sci↗

arXiv2026

Room-temperature multistage metastability in a moiré superstructure

Metastability is fundamental not only to phase ordering and transitions, but also to a broad range of modern technologies, from memory devices to metallic glasses. In condensed-matter physics, charge density waves (CDWs) offer versatile platforms for accessing metastable states due to their sensitivity to external stimuli. However, most metastable CDW states are stabilized only at low temperatures, limiting their practical utility. In this study, we report the observation of electrically driven, room-temperature, nonvolatile metastable states in the bulk form of EuTe$_4$, a recently discovered compound that hosts an innate moiré superlattice characterized by the stacking of incommensurate monolayer and bilayer CDWs. Systematic transport measurements reveal discrete resistivity plateaus and strong electric-field sensitivity, with a large number of metastable states readily induced across a wide temperature window within a giant hysteresis loop, making them well-suited for high-temperature, multi-bit memory applications. By integrating photoemission spectroscopy, diffraction, and in-situ transport measurements, we uncover that these metastable states do not stem from conventional mechanisms such as the emergence of new ordered phases or changes in incommensurate periodicity. Instead, they are characterized by a suppression of the original CDW amplitude and a reduction in correlation length, pointing to a unique electric-field-induced switching of out-of-plane CDW phases in the moiré superstructure. Our findings not only provide critical insights into metastable phenomena in moiré systems with stacked electronic orders but also establish EuTe$_4$ as a promising platform for developing room-temperature, multi-bit memory devices.

cond-mat.str-el↗

arXiv2026

The Evolution of Magnetism in a Thin Film Pyrochlore Ferromagnetic Insulator

The pyrochlore vanadates are compelling candidates for next-generation dissipationless devices. Lu2V2O7 and Y2V2O7 are ferromagnetic insulators (Tc ~ 70 K) that are believed to exhibit the magnon Hall effect and are expected to host topological magnons. Their completely dissipationless magnon edge states could be harnessed to realize low-power information transport in spintronic or magnonic devices. As a crucial step in the realization of devices, we synthesize the first thin films of pyrochlore Y2V2O7 on isostructural Y2Ti2O7 substrates and explore the evolution of their magnetic properties down to the ultrathin limit. All films are insulating ferromagnets with transition temperatures of up to the bulk value (Tc ~ 68 K) that decrease with thickness according to finite-size effects. Our films also exhibit a change in anisotropy from in-plane to out-of-plane easy axis coincident with the development of partial strain relaxation and nonzero magnetic hysteresis in an applied field. This evolution demonstrates the impact of strain on magnetic anisotropy and paves the way to tunable magnon topology.

cond-mat.mtrl-sci↗

arXiv2026

Photoinduced metastable cation disorder in metal halide double perovskites

Lead-free perovskites have emerged as environmentally benign alternatives to lead-halide counterparts for optoelectronics. Among them, the double perovskite Cs2AgInCl6 family exhibits remarkable white-light emission with proper composition engineering, enabled by strong electron-phonon coupling and the formation of self-trapped excitons (STEs). Despite these advantages, the fundamental photo- and structural dynamics governing their excited-state behavior remain poorly understood. Here, we report a long-lived metastable phase in the Cs2AgInCl6 double perovskite family and unravel this process and the concomitant electronic and structural evolution using a suite of tools including transient optical spectroscopy, time-resolved X-ray diffraction (TR-XRD) and X-ray absorption (TR-XAS). We show that the photoinduced, transient metastable phase is associated with B-site (Ag-In) disorder, which induces a dramatically reduced optical bandgap. Supported by TR-XRD and first-principles calculations, the Ag-In disorder drives the formation of Ag-rich and In-rich domains with millisecond lifetimes, with lifetimes increasing at lower temperatures. TR-XAS further reveals that photogenerated STEs oxidize Ag+ to Ag2+, facilitating this highly temporally asymmetric order-disorder transition. Our findings demonstrate a new mechanism, mediated by hole-localized STE formation, that enables prolongation of transient light-induced states to the multi-millisecond regime in double perovskites, opening possibilities to harvesting the functional properties of metastable phases of these materials.

cond-mat.mtrl-sci↗

arXiv2025

Emergent Atomic Scale Polarisation Vortices in BaTiS3

Topological defects, such as vortices and skyrmions in magnetic and dipolar systems, can give rise to properties that are not observed in typical magnets and dielectrics. Here, we report the discovery of long-range ordered periodic dipole arrays of atomic-scale vortices and antivortices in the unconventional charge-density-wave (CDW) phase of BaTiS3, a quasi-1D chalcogenide. Synchrotron X-ray diffraction (XRD) reveals the presence of a multi-q ordering in BaTiS3 that confines vortex-vortex-antivortex polarisation triplets to the a-b plane with alternating handedness along the c-axis. The multi-q displacive distortions are characterised by three distinctive off-centre TiS6 configurations, whose ratios are independently confirmed by 47/49Ti solid-state nuclear magnetic resonance (SSNMR). Using first-principles calculations and phenomenological modelling, we show that the dipolar vortex unit cell in BaTiS3 arises from the coupling between multiple lattice instabilities arising from flat, soft phonon bands. This mechanism contrasts with classical dipolar textures in ferroelectric heterostructures that emerge from the competition between electrostatic and strain energies. The observation of dipolar vortices in BaTiS3 brings the ultimate scaling limit for real-space dipolar topological structures down to about a nanometre and unveils the intimate connection between crystal symmetry and real-space topology. Our work sets up zero-filling semiconducting materials with competing structural instabilities as a playground for realising and understanding quantum polarisation topologies.

cond-mat.mtrl-sci↗

arXiv2025

Spatiotemporal Mapping of Anisotropic Thermal Transport in GaN Thin Films via Ultrafast X-ray Diffraction

Efficient thermal management is essential for the reliability of modern power electronics, where increasing device density leads to severe heat dissipation challenges. However, in thin-film systems, thermal transport is often compromised by interfacial resistance and microscale defects introduced during synthesis or transfer, which are difficult to characterize using conventional techniques. Here we present a non-contact, spatiotemporal-resolved ultrafast x-ray diffraction method to extract in-plane thermal conductivity and thermal boundary conductance, using GaN thin films on silicon as a model system. By tracking the pump-induced lattice strain, we reconstruct the lateral heat flow dynamics and quantitatively probe thermal transport near a wrinkle defect. We uncover pronounced asymmetric heat dissipation across the wrinkle, with a four-fold reduction in the local thermal conductivity near the wrinkle and a 25% drop in interfacial conductance. Our work demonstrates that ultrafast x-ray diffraction can serve as a precise thermal metrology tool for characterizing heat transport in multilayered thin-film structures for next-generation microelectronic devices.

cond-mat.mtrl-sci↗

arXiv2025

Topotactic oxidation of Ruddlesden-Popper nickelates reveals new structural family: oxygen-intercalated layered perovskites

Layered perovskites such as the Dion-Jacobson, Ruddlesden-Popper, and Aurivillius families host a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here we report a new family of layered perovskites, realized through topotactic oxygen intercalation of La_{n+1}Ni_{n}O_{3n+1} (n=1-4) Ruddlesden-Popper nickelate thin films grown by ozone-assisted molecular-beam epitaxy. Post-growth ozone annealing induces a large c-axis expansion - 17.8% for La_{2}NiO_{4} (n=1) - that monotonically decreases with increasing n. Surface X-ray diffraction coupled with Coherent Bragg Rod Analysis reveals that this structural expansion arises from the intercalation of approximately 0.7 oxygen atoms per formula unit into interstitial sites within the rock salt spacer layers. The resulting structures exhibit a spacer layer composition intermediate between that of the Ruddlesden-Popper and Aurivillius phases, defining a new class of layered perovskites. Oxygen-intercalated nickelates exhibit metallicity and significantly enhanced nickel-oxygen hybridization, a feature linked to high-temperature superconductivity. Our work establishes topotactic oxidation as a powerful synthetic approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to tune properties via spacer-layer chemistry.

cond-mat.mtrl-sci↗

arXiv2024

Dual mechanisms for transient capacitance anomaly in improper ferroelectrics

The recent discovery of transient negative capacitance has sparked an intense debate on the role of homogeneous and inhomogeneous mechanisms in polarizations switching. In this work, we report observation of transient negative capacitance in improper ferroelectric h-YbFeO3 films in a resistor-capacitor circuit, and a concaved shape of anomaly in the voltage wave form, in the early and late stage of the polarizations switching respectively. Using a phenomenological model, we show that the early-stage negative capacitance is likely due to the inhomogeneous switching involving nucleation and domain wall motion, while the anomaly at the late stage, which appears to be a reminiscent negative capacitance is the manifestation of the thermodynamically unstable part of the free-energy landscape in the homogeneous switching. The complex free-energy landscape in hexagonal ferrites may be the key to cause the abrupt change in polarization switching speed and the corresponding anomaly. These results reconcile the two seemingly conflicting mechanisms in the polarization switching and highlight their different roles at different stages. The unique energy-landscape in hexagonal ferrites that reveals the dual switching mechanism suggests the promising application potential in terms of negative capacitance.

cond-mat.mtrl-sci↗

arXiv2024

Hidden correlations in stochastic photoinduced dynamics of a solid-state electrolyte

Photoexcitation by ultrashort laser pulses plays a crucial role in controlling reaction pathways, creating nonequilibrium material properties, and offering a microscopic view of complex dynamics at the molecular level. The photo response following a laser pulse is, in general, non-identical between multiple exposures due to spatiotemporal fluctuations in a material or the stochastic nature of dynamical pathways. However, most ultrafast experiments using a stroboscopic pump-probe scheme struggle to distinguish intrinsic sample fluctuations from extrinsic apparatus noise, often missing seemingly random deviations from the averaged shot-to-shot response. Leveraging the stability and high photon-flux of time-resolved X-ray micro-diffraction at a synchrotron, we developed a method to quantitatively characterize the shot-to-shot variation of the photoinduced dynamics in a solid-state electrolyte. By analyzing temporal evolutions of the lattice parameter of a single grain in a powder ensemble, we found that the sample responses after different shots contain random fluctuations that are, however, not independent. Instead, there is a correlation between the nonequilibrium lattice trajectories following adjacent laser shots with a characteristic "correlation length" of approximately 1,500 shots, which represents an energy barrier of 0.38~eV for switching the photoinduced pathway, a value interestingly commensurate with the activation energy of lithium ion diffusion. Not only does our nonequilibrium noise correlation spectroscopy provide a new strategy for studying fluctuations that are central to phase transitions in both condensed matter and molecular systems, it also paves the way for discovering hidden correlations and novel metastable states buried in oft-presumed random, uncorrelated fluctuating dynamics.

cond-mat.mtrl-sci↗

arXiv2024

Non-equilibrium pathways to emergent polar supertextures

Ultrafast stimuli can stabilize metastable states of matter inaccessible by equilibrium means. Establishing the spatiotemporal link between ultrafast excitation and metastability is crucial to understanding these phenomena. Here, we use single-shot optical-pump, X-ray-probe measurements to provide snapshots of the emergence of a persistent polar vortex supercrystal in a heterostructure that hosts a fine balance between built-in electrostatic and elastic frustrations by design. By perturbing this balance with photoinduced charges, a starting heterogenous mixture of polar phases disorders within a few picoseconds, resulting in a soup state composed of disordered ferroelectric and suppressed vortex orders. On the pico-to-nanosecond timescales, transient labyrinthine fluctuations form in this soup along with a recovering vortex order. On longer timescales, these fluctuations are progressively quenched by dynamical strain modulations, which drive the collective emergence of a single supercrystal phase. Our results, corroborated by dynamical phase-field modeling, reveal how ultrafast excitation of designer systems generates pathways for persistent metastability.

cond-mat.mtrl-sci↗

arXiv2023

X-ray induced electron and ion fragmentation dynamics in IBr

Characterization of the inner-shell decay processes in molecules containing heavy elements is key to understanding x-ray damage of molecules and materials and for medical applications with Auger-electron-emitting radionuclides. The 1s hole states of heavy atoms can be produced by absorption of tunable x-rays and the resulting vacancy decays characterized by recording emitted photons, electrons, and ions. The 1s hole states in heavy elements have large x-ray fluorescence yields that transfer the hole to intermediate electron shells that then decay by sequential Auger-electron transitions that increase the ion's charge state until the final state is reached. In molecules the charge is spread across the atomic sites, resulting in dissociation to energetic atomic ions. We have used x-ray/ion coincidence spectroscopy to measure charge states and energies of I$^{q+}$ and Br$^{q'+}$ atomic ions following 1s ionization at the I and Br \textit{K}-edges of IBr. We present the charge states and kinetic energies of the two correlated fragment ions associated with core-excited states produced during the various steps of the cascades. To understand the dynamics leading to the ion data, we develop a computational model that combines Monte-Carlo/Molecular Dynamics simulations with a classical over-the-barrier model to track inner-shell cascades and redistribution of electrons in valence orbitals and nuclear motion of fragments.

physics.atom-ph↗

arXiv2022

On-chip picosecond synchrotron pulse shaper

Synchrotrons are powerful and productive in revealing the spatiotemporal complexities in matter. However, X-ray pulses produced by the synchrotrons are predetermined in specific patterns and widths, limiting their operational flexibility and temporal resolution. Here, we introduce the on-chip picosecond synchrotron pulse shaper that shapes the sub-nm-wavelength hard X-ray pulses at individual beamlines, flexibly and efficiently beyond the synchrotron pulse limit. The pulse shaper is developed using the widely available silicon-on-insulator technology, oscillates in torsional motion at the same frequency or at harmonics of the storage ring, and manipulates X-ray pulses through the narrow Bragg peak of the crystalline silicon. Stable pulse manipulation is achieved by synchronizing the shaper timing to the X-ray timing using electrostatic closed-loop control. Tunable shaping windows down to 40 $ps$ are demonstrated, allowing X-ray pulse picking, streaking, and slicing in the majority of worldwide synchrotrons. The compact, on-chip shaper offers a simple but versatile approach to boost synchrotron operating flexibility and to investigate structural dynamics from condensed matter to biological systems beyond the current synchrotron-source limit.

physics.acc-ph↗

arXiv2021

Unconventional hysteretic transition in a charge density wave

Hysteresis underlies a large number of phase transitions in solids, giving rise to exotic metastable states that are otherwise inaccessible. Here, we report an unconventional hysteretic transition in a quasi-2D material, EuTe4. By combining transport, photoemission, diffraction, and x-ray absorption measurements, we observed that the hysteresis loop has a temperature width of more than 400 K, setting a record among crystalline solids. The transition has an origin distinct from known mechanisms, lying entirely within the incommensurate charge-density-wave (CDW) phase of EuTe4 with no change in the CDW modulation periodicity. We interpret the hysteresis as an unusual switching of the relative CDW phases in different layers, a phenomenon unique to quasi-2D compounds that is not present in either purely 2D or strongly-coupled 3D systems. Our findings challenge the established theories on metastable states in density wave systems, pushing the boundary of understanding hysteretic transitions in a broken-symmetry state.

cond-mat.mtrl-sci↗

arXiv2021

Subterahertz collective dynamics of polar vortices

The collective dynamics of topological structures have been of great interest from both fundamental and applied perspectives. For example, the studies of dynamical properties of magnetic vortices and skyrmions not only deepened the understanding of many-body physics but also led to potential applications in data processing and storage. Topological structures constructed from electrical polarization rather than spin have recently been realized in ferroelectric superlattices, promising for ultrafast electric-field control of topological orders. However, little is known about the dynamics of such complex extended nanostructures which in turn underlies their functionalities. Using terahertz-field excitation and femtosecond x-ray diffraction measurements, we observe ultrafast collective polarization dynamics that are unique to polar vortices, with orders of magnitude higher frequencies and smaller lateral size than those of experimentally realized magnetic vortices. A previously unseen soft mode, hereafter referred to as a vortexon, emerges as transient arrays of nanoscale circular patterns of atomic displacements, which reverse their vorticity on picosecond time scales. Its frequency is significantly reduced at a critical strain, indicating a condensation of structural dynamics. First-principles-based atomistic calculations and phase-field modeling reveal the microscopic atomic arrangements and frequencies of the vortex modes. The discovery of subterahertz collective dynamics in polar vortices opens up opportunities for applications of electric-field driven data processing in topological structures with ultrahigh speed and density.

cond-mat.mes-hall↗

arXiv2020

Stern Layers on Surfaces of RuO2(100), RuO2(110), and Pt(111): Surface X-ray Scattering Studies

Surface X-ray scattering studies of electrochemical Stern layer are reported. The Stern layers formed at the interfaces of RuO2 (110) and (100) in 0.1 M CsF electrolyte are compared to the previously reported Stern layer on Pt(111) [Liu et al., J. Phys. Chem. Lett., 9 (2018) 1265]. While the Cs+ density profiles at the potentials close to hydrogen evolution reaction are similar, the hydration layers intervening the surface and the Cs+ layer on RuO2 surfaces are significantly denser than the hydration layer on Pt(111) surface possibly due to the oxygen termination of RuO2 surfaces. We also discuss in-plane ordering in the Stern layer on Pt(111) surface.

cond-mat.mtrl-sci↗

arXiv2017

Unconventional slowing down of electronic recovery in photoexcited charge-ordered La$_{1/3}$Sr$_{2/3}$FeO$_3$

Ordered electronic phases are intimately related to emerging phenomena such as high Tc superconductivity and colossal magnetoresistance. The coupling of electronic charge with other degrees of freedom such as lattice and spin are of central interest in correlated systems. Their correlations have been intensively studied from femtosecond to picosecond time scales, while the dynamics of ordered electronic phases beyond nanoseconds are usually assumed to follow a trivia thermally driven recovery. Here, we report an unusual slowing down of the recovery of an electronic phase across a first-order phase transition, far beyond thermal relaxation time. Following optical excitation, the recovery time of both transient optical reflectivity and x-ray diffraction intensity from a charge-ordered superstructure in a La$_{1/3}$Sr$_{2/3}$FeO$_3$ thin film increases by orders of magnitude longer than the independently measured lattice cooling time when the sample temperature approaches the phase transition temperature. The combined experimental and theoretical investigations show that the slowing down of electronic recovery corresponds to the pseudo-critical dynamics that originates from magnetic interactions close to a weakly first-order phase transition. This extraordinary long electronic recovery time exemplifies an interplay of ordered electronic phases with magnetism beyond thermal processes in correlated systems.

cond-mat.str-el↗

arXiv2016

Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

cond-mat.mes-hall↗