Subpicosecond Optical Stress Generation in Multiferroic BiFeO3.

Optical excitation leads to ultrafast stress generation in the prototypical multiferroic BiFeO3. The time scales of stress generation are set by the dynamics of the population of excited electronic states and the coupling of the electronic configuration to the structure. X-ray free-electron laser diffraction reveals high-wavevector subpicosecond-time scale stress generation following ultraviolet excitation of a BiFeO3 thin film. Stress generation includes a fast component with a 1/e rise time with an upper limit of 300 fs and longer-rise time components extending to 1.5 ps. The contributions of the fast and delayed components vary as a function of optical fluence, with a reduced a fast-component contribution at high fluence. The results provide insight into stress-generation mechanisms linked to the population of excited electrons and point to new directions in the application of nanoscale multiferroics and related ferroic complex oxides. The fast component of the stress indicates that structural parameters and properties of ferroelectric thin film materials can be optically modulated with 3 dB bandwidths of at least 0.5 THz.

Shock growth of ice crystal near equilibrium melting pressure under dynamic compression.

Crystal growth is governed by an interplay between macroscopic driving force and microscopic interface kinetics at the crystal-liquid interface. Unlike the local equilibrium growth condition, the interplay becomes blurred under local nonequilibrium, which raises many questions about the nature of diverse crystal growth and morphological transitions. Here, we systematically control the growth condition from local equilibrium to local nonequilibrium by using an advanced dynamic diamond anvil cell (dDAC) and generate anomalously fast growth of ice VI phase with a morphological transition from three- to two-dimension (3D to 2D), which is called a shock crystal growth. Unlike expected, the shock growth occurs from the edges of 3D crystal along the (112) crystal plane rather than its corners, which implies that the fast compression yields effectively large overpressure at the crystal-liquid interface, manifesting the local nonequilibrium condition. Molecular dynamics (MD) simulation reproduces the faster growth of the (112) plane than other planes upon applying large overpressure. Moreover, the MD study reveals that the 2D shock crystal growth originates from the similarity of the interface structure between water and the (112) crystal plane under the large overpressure. This study provides insight into crystal growth under dynamic compressions, which makes a bridge for the unknown behaviors of crystal growth between under static and dynamic pressure conditions.

Real-Time Monitoring of Colloidal Crystallization in Electrostatically-Levitated Drops.

Colloidal crystallization is analogous to the crystallization in bulk atomic systems in various aspects, which has been explored as a model system. However, a real-time probing of the phenomenon still remains challenging. Here, a levitation system for a study of colloidal crystallization is demonstrated. Colloidal particles in a levitated droplet are gradually concentrated by isotropic evaporation of water from the surface of the droplet, resulting in crystallization. The structural change of the colloidal array during crystallization is investigated by simultaneously measuring the volume and reflectance spectra of the droplet. The crystal nucleates from the surface of the droplet at which the volume fraction exceeds the threshold and then the growth proceeds. The crystal growth behavior depends on the initial concentrations of colloidal particles and salts which determine the overall direction of crystal growth and interparticle spacing, respectively. The results show that a levitating bulk droplet has a great potential as a tool for in situ investigation of colloidal crystallization.

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet.

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

The X-ray Correlation Spectroscopy instrument at the Linac Coherent Light Source.

The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4-25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. A description of the instrument capabilities and recent achievements is presented.

Resolving high-speed colloidal dynamics beyond detector response time via two pulse speckle contrast correlation.

We report an alternate light scattering approach to measure intermediate scattering function and structures of colloidal suspension by using two-pulse speckle contrast correlation analysis. By systematically controlling time-delays between two laser pulses incident on the sample, we are able to monitor transient evolution of coherent diffraction pattern, from which particle dynamics at different length and time scales are obtained simultaneously. Our result demonstrates the feasibility of utilizing a megapixel detector to achieve sufficient data statistics in a short amount of time while enabling microsecond time-resolution. Ultimately, this method provides means to measure high-speed dynamics well beyond the time response limit of a large area two-dimensional (2D) detector.

Controlling the Phase Distribution of Single Bromide Quasi-2-Dimensional Perovskite Crystals via Solvent Engineering for Pure-Blue Light-Emitting Diodes.

To achieve pure-blue emission (460-470 nm), we manipulate the crystallization process of the quasi-2D perovskite, (PBA)2Csn-1PbnBr3n+1, prepared by a solution process. The strategy involves controlling the distribution of "n" phases with different bandgaps, solely utilizing changes in the precursor's supersaturation to ensure that the desired emission aligns with the smallest bandgap. Adjustments in photoluminescence (PL) wavelength are made by changing the solute concentration and solvent polarity, as these factors heavily influence the diffusion of cations, a crucial determinant for the value of "n". Subsequently, we enhance the PL quantum yield from 31 to 51% at 461 nm using trioctylphosphine oxide (TOPO) as an additive of antisolvent, which passivates halide vacancy and promotes orderly crystal growth, leading to faster carrier transfer between phases. With these strategies, we successfully demonstrate pure-blue LEDs with a turn-on voltage of 3.3 V and an external quantum efficiency of 5.5% at an emission peak of 470 nm with a full-width at half-maximum of 31 nm.

Impact of molecular symmetry on crystallization pathways in highly supersaturated KH2PO4 solutions.

Solute structure and its evolution in supersaturated aqueous solutions are key clues to understand Ostwald's step rule. Here, we measure the structural evolution of solute molecules in highly supersaturated solutions of KH2PO4 (KDP) and NH4H2PO4 (ADP) using a combination of electrostatic levitation and synchrotron X-ray scattering. The measurement reveals the existence of a solution-solution transition in KDP solution, caused by changing molecular symmetries and structural evolution of the solution with supersaturation. Moreover, we find that the molecular symmetry of H2PO4- impacts on phase selection. These findings manifest that molecular symmetry and its structural evolution can govern the crystallization pathways in aqueous solutions, explaining the microscopic origin of Ostwald's step rule.

Single shot speckle and coherence analysis of the hard X-ray free electron laser LCLS.

The single shot based coherence properties of hard x-ray pulses from the Linac Coherent Light Source (LCLS) were measured by analyzing coherent diffraction patterns from nano-particles and gold nanopowder. The intensity histogram of the small angle x-ray scattering ring from nano-particles reveals the fully transversely coherent nature of the LCLS beam with a number of transverse mode 〈Ms〉 = 1.1. On the other hand, the speckle contrasts measured at a large wavevector yields information about the longitudinal coherence of the LCLS radiation after a silicon (111) monochromator. The quantitative agreement between our data and the simulation confirms a mean coherence time of 2.2 fs and a x-ray pulse duration of 29 fs. Finally the observed reduction of the speckle contrast generated by x-rays with pulse duration longer than 30 fs indicates ultrafast dynamics taking place at an atomic length scale prior to the permanent sample damage.

Exploring TEM Coherence Properties via Speckle Contrast Analysis in Coherent Electron Scattering of Amorphous Material.

We investigate the coherence properties of a transmission electron microscope by analyzing nano-diffraction speckles originating from bulk metallic glass. The spatial correlation function of the coherent diffraction patterns, obtained in the transmission geometry, reveals the highly coherent nature of the electron probe beam and its spatial dimension incident on the sample. Quantitative agreement between the measured speckle contrast and an analytical model yields estimates for the transverse and longitudinal coherence lengths of the source. We also demonstrate that the coherence can be controlled by changing the beam convergence angle. Our findings underscore the preservation of electron beam coherence throughout the electron optics, as evidenced by the high-contrast speckles observed in the scattering patterns of the amorphous system. This study paves the way for the application of advanced coherent diffraction methodologies to investigate local structures and dynamics occurring at atomic-length scales across a diverse range of materials.

Time-Resolved Structural Measurement of Thermal Resistance across a Buried Semiconductor Heterostructure Interface.

The precise control and understanding of heat flow in heterostructures is pivotal for advancements in thermoelectric energy conversion, thermal barrier coatings, and efficient heat management in electronic and optoelectronic devices. In this study, we employ high-angular-resolution time-resolved X-ray diffraction to structurally measure thermal resistance in a laser-excited AlGaAs/GaAs semiconductor heterostructure. Our methodology offers femtometer-scale spatial sensitivity and nanosecond time resolution, enabling us to directly observe heat transport across a buried interface. We corroborate established Thermal Boundary Resistance (TBR) values for AlGaAs/GaAs heterostructures and demonstrate that TBR arises from material property discrepancies on either side of a nearly flawless atomic interface. This work not only sheds light on the fundamental mechanisms governing heat flow across buried interfaces but also presents a robust experimental framework that can be extended to other heterostructure systems, paving the way for optimized thermal management in next-generation devices.

Simultaneous measurements of volume, pressure, optical images, and crystal structure with a dynamic diamond anvil cell: A real-time event monitoring system.

The dynamic diamond anvil cell (dDAC) technique has attracted great interest because it possibly provides a bridge between static and dynamic compression studies with fast, repeatable, and controllable compression rates. The dDAC can be a particularly useful tool to study the pathways and kinetics of phase transitions under dynamic pressurization if simultaneous measurements of physical quantities are possible as a function of time. We here report the development of a real-time event monitoring (RTEM) system with dDAC, which can simultaneously record the volume, pressure, optical image, and structure of materials during dynamic compression runs. In particular, the volume measurement using both Fabry-Pérot interferogram and optical images facilitates the construction of an equation of state (EoS) using the dDAC in a home-laboratory. We also developed an in-line ruby pressure measurement (IRPM) system to be deployed at a synchrotron x-ray facility. This system provides simultaneous measurements of pressure and x-ray diffraction in low and narrow pressure ranges. The EoSs of ice VI obtained from the RTEM and the x-ray diffraction data with the IRPM are consistent with each other. The complementarity of both RTEM and IRPM systems will provide a great opportunity to scrutinize the detailed kinetic pathways of phase transitions using dDAC.

High wavevector temporal speckle correlations at the Linac Coherent Light Source.

We report on the feasibility of high wavevector temporal speckle correlation measurements at the world's first hard x-ray free electron laser, the Linac Coherent Light Source (LCLS). Due to the chaotic nature of LCLS, the spectral profile of the x-ray radiation fluctuates on a pulse-to-pulse basis. Its impact on the determination of the single shot speckle contrast in a wide angle x-ray scattering geometry is investigated by analyzing FEL power spectra that are simulated based on the nominal operational parameters of LCLS. Ultimately, a potential scheme to deliver a single-mode hard x-ray pulse is proposed by using a narrow bandpass crystal monochromator.

Femtosecond single-shot imaging of nanoscale ferromagnetic order in Co/Pd multilayers using resonant x-ray holography.

We present the first single-shot images of ferromagnetic, nanoscale spin order taken with femtosecond x-ray pulses. X-ray-induced electron and spin dynamics can be outrun with pulses shorter than 80 fs in the investigated fluence regime, and no permanent aftereffects in the samples are observed below a fluence of 25 mJ/cm(2). Employing resonant spatially muliplexed x-ray holography results in a low imaging threshold of 5 mJ/cm(2). Our results open new ways to combine ultrafast laser spectroscopy with sequential snapshot imaging on a single sample, generating a movie of excited state dynamics.

Structural measurement of electron-phonon coupling and electronic thermal transport across a metal-semiconductor interface.

Scattering of energetic charge carriers and their coupling to lattice vibrations (phonons) in dielectric materials and semiconductors are crucial processes that determine the functional limits of optoelectronics, photovoltaics, and photocatalysts. The strength of these energy exchanges is often described by the electron-phonon coupling coefficient, which is difficult to measure due to the microscopic time- and length-scales involved. In the present study, we propose an alternate means to quantify the coupling parameter along with thermal boundary resistance and electron conductivity by performing a high angular-resolution time-resolved X-ray diffraction measurement of propagating lattice deformation following laser excitation of a nanoscale, polycrystalline metal film on a semiconductor substrate. Our data present direct experimental evidence for identifying the ballistic and diffusive transport components occurring at the interface, where only the latter participates in thermal diffusion. This approach provides a robust measurement that can be applied to investigate microscopic energy transport in various solid-state materials.

Development of a hard X-ray delay line for X-ray photon correlation spectroscopy and jitter-free pump-probe experiments at X-ray free-electron laser sources.

A hard X-ray delay line capable of splitting and delaying single X-ray pulses has been developed with the aim of performing X-ray photon correlation spectroscopy (XPCS) and X-ray pump-probe experiments at hard X-ray free-electron laser sources. The performance of the device was tested with 8.39 keV synchrotron radiation. Time delays up to 2.95 ns have been demonstrated. The feasibility of the device for performing XPCS studies was tested by recording static speckle patterns. The achieved speckle contrast of 56% indicates the possibility of performing ultra-fast XPCS studies with the delay line.

Hydration breaking and chemical ordering in a levitated NaCl solution droplet beyond the metastable zone width limit: evidence for the early stage of two-step nucleation.

For over two decades, NaCl nucleation from a supersaturated aqueous solution has been predicted to occur via a two-step nucleation (TSN) mechanism, i.e., two sequential events, the formation of locally dense liquid regions followed by structural ordering. However, the formation of dense liquid regions in the very early stage of TSN has never been experimentally observed. By using a state-of-the-art technique, a combination of electrostatic levitation (ESL) and in situ synchrotron X-ray and Raman scatterings, we find experimental evidence that indicates the formation of dense liquid regions in NaCl bulk solution at an unprecedentedly high level of supersaturation (S = 2.31). As supersaturation increases, evolution of ion clusters leads to chemical ordering, but no topological ordering, which is a precursor for forming the dense disordered regions of ion clusters at the early stage of TSN. Moreover, as the ion clusters proceed to evolve under highly supersaturated conditions, we observe the breakage of the water hydration structure indicating the stability limit of the dense liquid regions, and thus leading to nucleation. The evolution of solute clusters and breakage of hydration in highly supersaturated NaCl bulk solution will provide new insights into the detailed mechanism of TSN for many other aqueous solutions.

Double-pulse speckle contrast correlations with near Fourier transform limited free-electron laser light using hard X-ray split-and-delay.

The ability to deliver two coherent X-ray pulses with precise time-delays ranging from a few femtoseconds to nanoseconds enables critical capabilities of probing ultra-fast phenomena in condensed matter systems at X-ray free electron laser (FEL) sources. Recent progress made in the hard X-ray split-and-delay optics developments now brings a very promising prospect for resolving atomic-scale motions that were not accessible by previous time-resolved techniques. Here, we report on characterizing the spatial and temporal coherence properties of the hard X-ray FEL beam after propagating through split-and-delay optics. Speckle contrast analysis of small-angle scattering measurements from nanoparticles reveals well-preserved transverse coherence of the beam. Measuring intensity fluctuations from successive X-ray pulses also reveals that only single or double temporal modes remain in the transmitted beam, corresponding to nearly Fourier transform limited pulses.

Coherence and pulse duration characterization of the PAL-XFEL in the hard X-ray regime.

We characterize the spatial and temporal coherence properties of hard X-ray pulses from the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL, Pohang, Korea). The measurement of the single-shot speckle contrast, together with the introduction of corrections considering experimental conditions, allows obtaining an intrinsic degree of transverse coherence of 0.85 ± 0.06. In the Self-Amplified Spontaneous Emission regime, the analysis of the intensity distribution of X-ray pulses also provides an estimate for the number of longitudinal modes. For monochromatic and pink (i.e. natural bandwidth provided by the first harmonic of the undulator) beams, we observe that the number of temporal modes is 6.0 ± 0.4 and 90.0 ± 7.2, respectively. Assuming a coherence time of 2.06 fs and 0.14 fs for the monochromatic and pink beam respectively, we estimate an average X-ray pulse duration of 12.6 ± 1.0 fs.

Solution electrostatic levitator for measuring surface properties and bulk structures of an extremely supersaturated solution drop above metastable zone width limit.

We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH2PO4) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.