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Ultrafast first-order phase transitions exhibit distinct transition pathways and dynamical properties that are not accessible during quasi-equilibrium transitions. Phenomena arising at the ultrafast timescale are important for understanding the transition mechanisms and in applications using the fast switching of electronic properties or magnetism. These transitions are accompanied by nanoscale structural dynamics that have been challenging to explore by optical or electronic transport probes. Here, X-ray nanodiffraction imaging shows that the nanoscale structural dynamics arising in ultrafast phase transitions differ dramatically from the transitions under slowly varying parameters. The solid-solid phase transitions in a FeRh thin film involve concurrent structural and magnetic changes and can be sensitively probed by monitoring their diffraction signatures following femtosecond optical excitation. Time-dependent nanodiffraction maps with 100-ps temporal and 25-nm spatial resolutions reveal that the preexisting nanoscale variation in phase composition results in spatially inhomogeneous changes of phase fraction after ultrafast optical excitation. The spatial inhomogeneity leads to nanoscale temperature variations and subsequent in-plane heat transport, which are responsible for spatially distinct relaxation pathways on nanometer length scales. The spatial gradients of the phase composition and elastic strain increase upon excitation rather than exhibiting the decrease previously reported in quasi-equilibrium transformations. Long-range elastic interactions thus do not play significant roles in the ultrafast phase transition. These microscopic insights into first-order phase transitions provide routes to manipulate nanoscopic phases in functional materials on ultrafast time scales by engineering initial nanoscale phase distributions.

Time-resolved electron microscopy is based on the excitation of a sample by pulsed laser radiation and its probing by synchronized photoelectron bunches in the electron microscope column. With femtosecond lasers, if probing pulses with a small number of electrons—in the limit, single-electron wave packets—are used, the stroboscopic regime enables ultrahigh spatiotemporal resolution to be obtained, which is not restricted by the Coulomb repulsion of electrons. This review article presents the current state of the ultrafast electron microscopy (UEM) method for detecting the structural dynamics of matter in the time range from picoseconds to attoseconds. Moreover, in the imaging mode, the spatial resolution lies, at best, in the subnanometer range, which limits the range of observation of structural changes in the sample. The ultrafast electron diffraction (UED), which created the methodological basis for the development of UEM, has opened the possibility of creating molecular movies that show the behavior of the investigated quantum system in the space-time continuum with details of sub-Å spatial resolution. Therefore, this review on the development of UEM begins with a description of the main achievements of UED, which formed the basis for the creation and further development of the UEM method. A number of recent experiments are presented to illustrate the potential of the UEM method.

Mix-and-inject serial crystallography (MISC) is a technique designed to image enzyme catalyzed reactions in which small protein crystals are mixed with a substrate just prior to being probed by an X-ray pulse. This approach offers several advantages over flow cell studies. It provides (i) room temperature structures at near atomic resolution, (ii) time resolution ranging from microseconds to seconds, and (iii) convenient reaction initiation. It outruns radiation damage by using femtosecond X-ray pulses allowing damage and chemistry to be separated. Here, we demonstrate that MISC is feasible at an X-ray free electron laser by studying the reaction of M. tuberculosis ß-lactamase microcrystals with ceftriaxone antibiotic solution. Electron density maps of the apo-ß-lactamase and of the ceftriaxone bound form were obtained at 2.8 Å and 2.4 Å resolution, respectively. These results pave the way to study cyclic and non-cyclic reactions and represent a new field of time-resolved structural dynamics for numerous substrate-triggered biological reactions.

The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface.

We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge, and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes is observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. This first, time-resolved element-specific study of perovskites helps understand the rather modest charge carrier mobilities in these materials.

Toward the end of his career, Zewail developed strong interest in fast electron spectroscopy and imaging, a field to which he made important contributions toward his aim of making molecular movies free of radiation damage. We therefore compare here the atomistic mechanisms leading to destruction of protein samples in diffract-and-destroy experiments for the cases of high-energy electron beam irradiation and X-ray laser pulses. The damage processes and their time-scales are compared and relevant elastic, inelastic, and photoelectron cross sections are given. Inelastic mean-free paths for ejected electrons at very low energies in insulators are compared with the bioparticle size. The dose rate and structural damage rate for electrons are found to be much lower, allowing longer pulses, reduced beam current, and Coulomb interactions for the formation of smaller probes. High-angle electron scattering from the nucleus, which has no parallel in the X-ray case, tracks the slowly moving nuclei during the explosion, just as the gain of the XFEL (X-ray free-electron laser) has no parallel in the electron case. Despite reduced damage and much larger elastic scattering cross sections in the electron case, leading to not dissimilar elastic scattering rates (when account is taken of the greatly increased incident XFEL fluence), progress for single-particle electron diffraction is seen to depend on the effort to reduce emittance growth due to Coulomb interactions, and so allow formation of intense sub-micron beams no larger than a virus.

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si0.25Ge0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M4,5-edge (∼30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons across the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct ( Δ E gap , Ge , direct = 0.8   eV ) and Si0.25Ge0.75 indirect gaps ( Δ E gap , Si 0.25 Ge 0.75 , indirect = 0.95   eV ) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si0.25Ge0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution.

In the past decade, we have witnessed the rapid growth of the field of ultrafast electron microscopy (UEM), which provides intuitive means to watch atomic and molecular motions of matter. Yet, because of the limited current of the pulsed electron beam resulting from space-charge effects, observations have been mainly made to periodic motions of the crystalline structure of hundreds of nanometers or higher by stroboscopic imaging at high repetition rates. Here, we develop an advanced UEM with robust capabilities for circumventing the present limitations by integrating a direct electron detection camera for the first time which allows for imaging at low repetition rates. This approach is expected to promote UEM to a more powerful platform to visualize molecular and collective motions and dissect fundamental physical, chemical, and materials phenomena in space and time.

We report correlative crystallographic and morphological studies of defect-dependent phonon dynamics in single flakes of 1T-TaS2 and 2H-WSe2 using selected-area diffraction and bright-field imaging in an ultrafast electron microscope. In both materials, we observe in-plane speed-of-sound acoustic-phonon wave trains, the dynamics of which (i.e., emergence, propagation, and interference) are strongly dependent upon discrete interfacial features (e.g., vacuum/crystal and crystal/crystal interfaces). In TaS2, we observe cross-propagating in-plane acoustic-phonon wave trains of differing frequencies that undergo coherent interference approximately 200 ps after initial emergence from distinct interfacial regions. With ultrafast bright-field imaging, the properties of the interfering wave trains are observed to correspond to the beat frequency of the individual oscillations, while intensity oscillations of Bragg spots generated from selected areas within the region of interest match well with the real-space dynamics. In WSe2, distinct acoustic-phonon dynamics are observed emanating and propagating away from structurally dissimilar morphological discontinuities (vacuum/crystal interface and crystal terrace), and results of ultrafast selected-area diffraction reveal thickness-dependent phonon frequencies. The overall observed dynamics are well-described using finite element analysis and time-dependent linear-elastic continuum mechanics.

A review that summarizes the most recent technological developments in the field of ultrafast structural dynamics with focus on the use of ultrashort X-ray and electron pulses follows. Atomistic views of chemical processes and phase transformations have long been the exclusive domain of computer simulators. The advent of femtosecond (fs) hard X-ray and fs-electron diffraction techniques made it possible to bring such a level of scrutiny to the experimental area. The following review article provides a summary of the main ultrafast techniques that enabled the generation of atomically resolved movies utilizing ultrashort X-ray and electron pulses. Recent advances are discussed with emphasis on synchrotron-based methods, tabletop fs-X-ray plasma sources, ultrabright fs-electron diffractometers, and timing techniques developed to further improve the temporal resolution and fully exploit the use of intense and ultrashort X-ray free electron laser (XFEL) pulses.