Pulsed-beam transmission electron microscopy and radiation damage.

We review the use of pulsed electron-beams in transmission electron microscopes (TEMs) for the purpose of mitigating specimen damage. We begin by placing the importance of TEMs with respect to materials characterization into proper context, and we provide a brief overview of established methods for reducing or eliminating the deleterious effects of beam-induced damage. We then introduce the concept of pulsed-beam TEM, and we briefly describe the basic methods and instrument configurations used to create so-called temporally structured electron beams. Following a brief overview of the use of high-dose-rate pulsed-electron beams in cancer radiation therapy, we review historical speculations and more recent compelling but mostly anecdotal findings of a pulsed-beam TEM damage effect. This is followed by an in-depth technical review of recent works seeking to establish cause-and-effect relationships, to conclusively uncover the presence of an effect, and to explore the practicality of the approach. These studies, in particular, provide the most compelling evidence to date that using a pulsed electron beam in the TEM is indeed a viable way to mitigate damage. Throughout, we point out current gaps in understanding, and we conclude with a brief perspective of current needs and future directions.

Low repetition-rate, high-resolution femtosecond transmission electron microscopy.

The spatial and energy resolutions of state-of-the-art transmission electron microscopes (TEMs) have surpassed 50 pm and 5 meV. However, with respect to the time domain, even the fastest detectors combined with the brightest sources may only be able to reach the microsecond timescale. Thus, conventional methods are incapable of resolving the myriad fundamental ultrafast (i.e., attosecond to picosecond) atomic-scale dynamics. The successful demonstration of femtosecond (fs) laser-based (LB) ultrafast electron microscopy (UEM) nearly 20 years ago provided a means to span this nearly 10-order-of-magnitude temporal gap. While nanometer-picosecond UEM studies of dynamics are now well established, ultrafast Å-scale imaging has gone largely unrealized. Further, while instrument development has rightly been an emphasis, and while new modalities and uses of pulsed-beam TEM continue to emerge, the overall chemical and materials application space has been only modestly explored to date. In this Perspective, we argue that these apparent shortfalls can be attributed to a simple lack of data and detail. We speculate that present work and continued growth of the field will ultimately lead to the realization that Å-scale fs dynamics can indeed be imaged with minimally modified UEM instrumentation and with repetition rates (frep) below-and perhaps even well below-1 MHz. We further argue that the use of low frep, whether for LB UEM or for chopped/bunched beams, significantly expands the accessible application space. This calls for systematically establishing modality-specific limits so that especially promising technologies can be pursued, thus, ultimately facilitating broader adoption as individual instrument capabilities expand.

Single-photoelectron collection efficiency in 4D ultrafast electron microscopy.

In femtosecond (fs) 4D ultrafast electron microscopy (UEM), a tradeoff is made between photoelectrons per packet and time resolution. One consequence of this can be longer-than-desirable acquisition times for low-density packets, and particularly for low repetition rates when complete photothermal dissipation is required. Thus, gaining an understanding of photoelectron trajectories in the gun region is important for identifying factors that limit collection efficiency (CE; fraction of photoelectrons that enter the illumination system). Here, we continue our work on the systematic study of photoelectron trajectories in the gun region of a Thermo Fisher/FEI Tecnai Femto UEM, focusing specifically on CE in the single-electron regime. Using General Particle Tracer, calculated field maps, and the exact architecture of the Tecnai Femto UEM, we simulated the effects of fs laser parameters and key gun elements on CE. The results indicate CE strongly depends upon the laser spot size on the source, the (unbiased) Wehnelt aperture diameter, and the incident photon energy. The CE dispersion with laser spot size is found to be strongly dependent on aperture diameter, being nearly dispersionless for the largest apertures. A gun crossover is also observed, with the beam-waist position being dependent on the aperture diameter, further illustrating that the Wehnelt aperture acts as a simple, fixed electrostatic lens in UEM mode. This work provides further insights into the operational aspects of fs 4D UEM.

A quantitative method for in situ pump-beam metrology in 4D ultrafast electron microscopy.

We report a method for measuring spot size and focusing conditions of the femtosecond (fs) excitation laser in situ at the specimen location in 4D ultrafast electron microscopy (UEM). The method makes use of threshold laser ablation behaviors of thin amorphous carbon membranes. For Gaussian beam profiles and for ablation threshold fluence values, we analytically derive expressions describing the relationship between ablated hole size and the actual laser spot size. Using these expressions, we developed experimental procedures for characterizing the shape and spot size of the pump beam at the specimen. We demonstrate the viability of the approach for incident excitation wavelengths of 343 nm and 515 nm, thus illustrating the applicability of the method to a range of optical wavelengths without modification. Further, we show that by measuring ablated hole size as a function of focusing condition, a full metrological characterization of the Gaussian beam propagation properties can be performed. Finally, we find good agreement for spot sizes determined with this method and with those determined by extrapolation from measurements taken outside the microscope column. Overall, this method is a simple, cost-effective means for accurate and precise determination of key pump-beam parameters in situ at the specimen location in UEM experiments.

Holey Substrate-Directed Strain Patterning in Bilayer MoS2.

Key properties of two-dimensional (2D) layered materials are highly strain tunable, arising from bond modulation and associated reconfiguration of the energy bands around the Fermi level. Approaches to locally controlling and patterning strain have included both active and passive elastic deformation via sustained loading and templating with nanostructures. Here, by float-capturing ultrathin flakes of single-crystal 2H-MoS2 on amorphous holey silicon nitride substrates, we find that highly symmetric, high-fidelity strain patterns are formed. The hexagonally arranged holes and surface topography combine to generate highly conformal flake-substrate coverage creating patterns that match optimal centroidal Voronoi tessellation in 2D Euclidean space. Using TEM imaging and diffraction, as well as AFM topographic mapping, we determine that the substrate-driven 3D geometry of the flakes over the holes consists of symmetric, out-of-plane bowl-like deformation of up to 35 nm, with in-plane, isotropic tensile strains of up to 1.8% (measured with both selected-area diffraction and AFM). Atomistic and image simulations accurately predict spontaneous formation of the strain patterns, with van der Waals forces and substrate topography as the input parameters. These results show that predictable patterns and 3D topography can be spontaneously induced in 2D materials captured on bare, holey substrates. The method also enables electron scattering studies of precisely aligned, substrate-free strained regions in transmission mode.

Toward Å-fs-meV resolution in electron microscopy: systematic simulation of the temporal spread of single-electron packets.

Though efforts to improve the temporal resolution of transmission electron microscopes (TEMs) have waxed and waned for decades, with relatively recent advances routinely reaching sub-picosecond scales, fundamental and practical challenges have hindered the advance of combined Å-fs-meV resolutions, particularly for core-loss spectroscopy and real-space imaging. This is due in no small part to the complexity of the approach required to access timescales upon which electrons, atoms, molecules, and materials first begin to respond and transform - attoseconds to picoseconds. Here we present part of a larger effort devoted to systematically mapping the instrument parameter space of a TEM modified to reach ultrafast timescales. With General Particle Tracer, we studied the statistical temporal distributions of single-electron packets as a function of various fs pulsed-laser parameters and electron-gun configurations and fields for the exact architecture and dimensions of a Thermo Fisher Tecnai Femto ultrafast electron microscope. We focused on easily-adjustable parameters, such as laser pulse duration, laser spot size, photon energy, Wehnelt aperture diameter, and photocathode size. In addition to establishing trends and dispersion behaviors, we identify regimes within which packet duration can be 100s of fs and approach the 300 fs laser limit employed here. Overall, the results provide a detailed picture of the temporal behavior of single-electron packets in the Tecnai Femto gun region, forming the initial contribution of a larger effort.

Imaging Nanometer Phonon Softening at Crystal Surface Steps with 4D Ultrafast Electron Microscopy.

Step edges are an important and prevalent topological feature that influence catalytic, electronic, vibrational, and structural properties arising from modulation of atomic-scale force fields due to edge-atom relaxation. Direct probing of ultrafast atomic-to-nanoscale lattice dynamics at individual steps poses a particularly significant challenge owing to demanding spatiotemporal resolution requirements. Here, we achieve such resolutions with femtosecond 4D ultrafast electron microscopy and directly image nanometer-variant softening of photoexcited phonons at individual surface steps. We find large degrees of softening precisely at the step position, with a thickness-dependent, strain-induced frequency modulation extending tens of nanometers laterally from the atomic-scale discontinuity. The effect originates from anisotropic bond dilation and photoinduced incoherent atomic displacements delineated by abrupt molecular-layer cessation. The magnitude and spatiotemporal extent of softening is quantitatively described with a finite-element transient-deformation model. The high spatiotemporal resolutions demonstrated here enable uncovering of new insights into atomic-scale structure-function relationships of highly defect-sensitive, functional materials.

Coherent Phonon Disruption and Lock-In during a Photoinduced Charge-Density-Wave Phase Transition.

Ultrafast manipulation of phase domains in quantum materials is a promising approach to unraveling and harnessing interwoven charge and lattice degrees of freedom. Here we find evidence for coupling of displacively excited coherent acoustic phonons (CAPs) and periodic lattice distortions (PLDs) in the intensely studied charge-density-wave material, 1T-TaS2, using 4D ultrafast electron microscopy (UEM). Initial photoinduced Bragg-peak dynamics reveal partial CAP coherence and localized c-axis dilations. Weak, partially coherent dynamics give way to higher-amplitude, increasingly coherent oscillations, the transition period of which matches that of photoinduced incommensurate domain growth and stabilization from the nearly-commensurate phase. With UEM imaging, it is found that phonon wave trains emerge from linear defects 100 ps after photoexcitation. The CAPs consist of coupled longitudinal and transverse character and propagate at anomalously high velocities along wave vectors independent from PLDs, instead being dictated by defect orientation. Such behaviors illustrate a means to control phases in quantum materials using defect-engineered coherent-phonon seeding.

UEMtomaton: A Source-Available Platform to Aid in Start-up of Ultrafast Electron Microscopy Labs.

The steady rise in the number of ultrafast electron microscopy (UEM) labs, in addition to the opacity and lack of detailed descriptions of current approaches that would enable point-by-point construction, has created an opportunity for sharing common methods and instrumentation for (for example) automating data acquisition to assist in efficient lab start-up and to learn about common and robust protocols. In the spirit of open sharing of methods, we provide here a description of an entry-level method and user interface (UI) for automating UEM experiments, and we provide access to the source code and scripts (source-available) for ease of implementation or as a starting reference point for those entering or seeking to enter the field (https://github.com/CEMSFlannigan/UEMtomaton/releases/tag/v1.0). Core instrumentation and physical connections in the UEM lab at Minnesota are described. Interface communication schemes consisting of duo server-client pairs between critical components - the optical delay stage and the UEM digital camera - are presented, with emphasis placed on describing the logic and communications sequence designed to conduct automated series acquisitions. An application designed and programmed with C++/CLI as Windows Forms in Microsoft Visual Studio - dubbed UEMtomaton - is also presented. Key to the UI layout is centralization of the automation tasks and establishment of communication within the software rather than by interfacing with each individual workstation. It is our hope that this note provides useful insight for current and future UEM researchers, particularly with respect to generalizability and portability of the approach to emerging labs. We note that while this basic, entry-level approach is certainly not the most sophisticated or comprehensive of those currently in use, we feel there is nevertheless value in clearly communicating a proven straightforward method to hopefully lower the barrier to entry into the field.

Mitigating Damage to Hybrid Perovskites Using Pulsed-Beam TEM.

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI3) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å-2·s-1, we find up to a 17% reduction in damage at a total dose of 10 e·Å-2. We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI3 is less than that observed for other materials (e.g., C36H74), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI3 is in fact less susceptible to irradiation than C36H74, which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology.

High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope.

Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

Imaging phonon dynamics with ultrafast electron microscopy: Kinematical and dynamical simulations.

Ultrafast x-ray and electron scattering techniques have proven to be useful for probing the transient elastic lattice deformations associated with photoexcited coherent acoustic phonons. Indeed, femtosecond electron imaging using an ultrafast electron microscope (UEM) has been used to directly image the influence of nanoscale structural and morphological discontinuities on the emergence, propagation, dispersion, and decay behaviors in a variety of materials. Here, we describe our progress toward the development of methods ultimately aimed at quantifying acoustic-phonon properties from real-space UEM images via conventional image simulation methods extended to the associated strain-wave lattice deformation symmetries and extents. Using a model system consisting of pristine single-crystal Ge and a single, symmetric Lamb-type guided-wave mode, we calculate the transient strain profiles excited in a wedge specimen and then apply both kinematical- and dynamical-scattering methods to simulate the resulting UEM bright-field images. While measurable contrast strengths arising from the phonon wavetrains are found for optimally oriented specimens using both approaches, incorporation of dynamical scattering effects via a multi-slice method returns better qualitative agreement with experimental observations. Contrast strengths arising solely from phonon-induced local lattice deformations are increased by nearly an order of magnitude when incorporating multiple electron scattering effects. We also explicitly demonstrate the effects of changes in global specimen orientation on the observed contrast strength, and we discuss the implications for increasing the sophistication of the model with respect to quantification of phonon properties from UEM images.

Influence of Discrete Defects on Observed Acoustic-Phonon Dynamics in Layered Materials Probed with Ultrafast Electron Microscopy.

The structural anisotropy of layered materials leads to disparate lattice responses along different crystallographic directions following femtosecond photoexcitation. Ultrafast scattering methods are well-suited to resolving such responses, though probe size and specimen structure and morphology must be considered when interpreting results. Here we use ultrafast electron microscopy (UEM) imaging and diffraction to study the influence of individual multilayer terraces and few-layer step-edges on acoustic-phonon dynamics in 1T-TaS2 and 2H-MoS2. In TaS2, we find that a multilayer terrace produces distinct, localized responses arising from thickness-dependent c-axis phonon dynamics. Convolution of the responses is demonstrated with ultrafast selected-area diffraction by limiting the probe size and training it on the region of interest. This results in a reciprocal-space frequency response that is a convolution of the spatially separated behaviors. Sensitivity of phonon dynamics to few-layer step-edges in MoS2 and the capability of UEM imaging to resolve the influence of such defects are also demonstrated. Spatial frequency maps from the UEM image series reveal regions separated by a four-layer step-edge having 60.0 GHz and 63.3 GHz oscillation frequencies, again linked to c-axis phonon propagation. As with ultrafast diffraction, signal convolution is demonstrated by continuous increase of the size of the selected region of interest used in the analysis.

Observation of Anisotropic Strain-Wave Dynamics and Few-Layer Dephasing in MoS2 with Ultrafast Electron Microscopy.

The large elastic strains that can be sustained by transition metal dichalcogenides (TMDs), and the sensitivity of electronic properties to that strain, make these materials attractive targets for tunable optoelectronic devices. Defects have also been shown to influence the optical and electronic properties, characteristics that are especially important to understand for applications requiring high precision and sensitivity. Importantly, photoexcitation of TMDs is known to generate transient strain effects but the associated intralayer and interlayer low-frequency (tens of GHz) acoustic-phonon modes are largely unexplored, especially in relation to defects common to such materials. Here, with femtosecond electron imaging in an ultrafast electron microscope (UEM), we directly observe distinct photoexcited strain-wave dynamics specific to both the ab basal planes and the principal c-axis crystallographic stacking direction in multilayer 2H-MoS2, and we elucidate the microscopic interconnectedness of these modes to one another and to discrete defects, such as few-layer crystal step edges. By probing 3D structural information within a nanometer-picosecond 2D projected UEM image series, we were able to observe the excitation and evolution of both modes simultaneously. In this way, we found evidence of a delay between mode excitations; initiation of the interlayer (c-axis) strain-wave mode precedes the intralayer (ab plane) mode by 2.4 ps. Further, the intralayer mode is preferentially excited at free basal-plane edges, thus suggesting the initial impulsive structural changes along the c-axis direction and the increased freedom of motion of the MoS2 layer edges at terraces and step edges combine to launch in-plane strain waves at the longitudinal speed of sound (here observed to be 7.8 nm/ps). Sensitivity of the c-axis mode to layer number is observed through direct imaging of a picosecond spatiotemporal dephasing of the lattice oscillation in discrete crystal regions separated by a step edge consisting of four MoS2 layers. These results uncover new insights into the fundamental nanoscale structural responses of layered materials to ultrafast photoexcitation and illustrate the influence defects common to these materials have on behaviors that may impact the emergent optoelectronic properties.

Reducing Radiation Damage in Soft Matter with Femtosecond-Timed Single-Electron Packets.

Despite the development of a myriad of mitigation methods, radiation damage continues to be a major limiting factor in transmission electron microscopy. Intriguing results have been reported using pulsed-laser driven and chopped electron beams for modulated dose delivery, but the underlying relationships and effects remain unclear. Indeed, delivering precisely timed single-electron packets to the specimen has yet to be systematically explored, and no direct comparisons to conventional methods within a common parameter space have been made. Here, using a model linear saturated hydrocarbon (n-hexatriacontane, C36H74), we show that precisely timed delivery of each electron to the specimen, with a well-defined and uniform time between arrival, leads to a repeatable reduction in damage compared to conventional ultralow-dose methods for the same dose rate and the same accumulated dose. Using a femtosecond pulsed laser to confine the probability of electron emission to a 300 fs temporal window, we find damage to be sensitively dependent on the time between electron arrival (controlled with the laser repetition rate) and on the number of electrons per packet (controlled with the laser-pulse energy). Relative arrival times of 5, 20, and 100 µs were tested for electron packets comprised of, on average, 1, 5, and 20 electrons. In general, damage increased with decreasing time between electrons and, more substantially, with increasing electron number. Further, we find that improvements relative to conventional methods vanish once a threshold number of electrons per packet is reached. The results indicate that precise electron-by-electron dose delivery leads to a repeatable reduction in irreversible structural damage, and the systematic studies indicate this arises from control of the time between sequential electrons arriving within the same damage radius, all else being equal.

Sources of error in Debye-Waller-effect measurements relevant to studies of photoinduced structural dynamics.

We identify and quantify several practical effects likely to be present in both static and ultrafast electron-scattering experiments that may interfere with the Debye-Waller (DW) effect. Using 120-nm thick, small-grained, polycrystalline aluminum foils as a test system, we illustrate the impact of specimen tilting, in-plane translation, and changes in z height on Debye-Scherrer-ring intensities. We find that tilting by less than one degree can result in statistically-significant changes in diffracted-beam intensities for large specimen regions containing > 105 nanocrystalline grains. We demonstrate that, in addition to effective changes in the field of view with tilting, slight texturing of the film can result in deviations from expected DW-effect behavior. Further, we find that in-plane translations of as little as 20 nm also produce statistically-significant intensity changes, while normalization to total image counts eliminates such effects arising from changes in z height. The results indicate that the use of polycrystalline films in ultrafast electron-scattering experiments can greatly reduce the negative impacts of these effects as compared to single-crystal specimens, though it does not entirely eliminate them. Thus, it is important to account for such effects when studying thin-foil specimens having relatively short reciprocal-lattice rods.

The Chemical History of a Bubble.

Acoustic cavitation (the growth, oscillation, and rapid collapse of bubbles in a liquid) occurs in all liquids irradiated with sufficient intensity of sound or ultrasound. The collapse of such bubbles creates local heating and provides a unique source of energy for driving chemical reactions. In addition to sonochemical bond scission and formation, cavitation also induces light emission in many liquids. This phenomenon of sonoluminescence (SL) has captured the imagination of many researchers since it was first observed 85 years ago. SL provides a direct probe of cavitation events and has provided most of our understanding of the conditions created inside collapsing bubbles. Spectroscopic analyses of SL from single acoustically levitated bubbles as well as from clouds of bubbles have revealed molecular, atomic, and ionic line and band emission riding atop an underlying continuum arising from radiative plasma processes. Application of spectrometric methods of pyrometry and plasma diagnostics to these spectra has permitted quantitative measurement of the intracavity conditions: relative peak intensities for temperature measurements, peak shifts and broadening for pressures, and peak asymmetries for plasma electron densities. The studies discussed herein have revealed that extraordinary conditions are generated inside the collapsing bubbles in ordinary room-temperature liquids: observable temperatures exceeding 15 000 K (i.e., three times the surface temperature of our sun), pressures of well over 1000 bar (more than the pressure at the bottom of the Mariana Trench), and heating and cooling rates in excess of 1012 K·s-1. Scientists from many disciplines, and even nonscientists, have been and continue to be intrigued by the consequences of dynamic bubbles in liquids. As chemists, we are fascinated by the high energy reactions and processes that occur during acoustic cavitation and by the use of SL as a spectroscopic probe of the events during cavitation. Within the chemical realm of SL and cavitation there are many interesting questions that are now answered but also many that remain to be explored, so we hope that this Account reveals to the reader some of the most fascinating of those curiosities as we explore the chemical history of a bubble. The high energy species produced inside collapsing bubbles also lead to secondary reactions from the high energy species created within the collapsing bubble diffusing into the bulk liquid and expanding the range of sonochemical reactions observed, especially in redox reactions relevant to nanomaterials synthesis. Bubbles near solid surfaces deform upon collapse, which lessens the internal heating within the bubble, as shown by SL studies, but introduces important mechanical consequences in terms of surface damage and increased surface reactivity. Our understanding of the conditions created during cavitation has informed the applications of ultrasound to a wide range of chemical applications, from nanomaterials to synthetically useful organic reactions to biomedical and pharmaceutical uses. Indeed, we echo Michael Faraday's observation concerning a candle flame, "There is not a law under which any part of this universe is governed which does not come into play and is touched upon in these phenomena." ( Faraday , M. The Chemical History of a Candle ; Harper & Brothers : New York , 1861 ).

Defect-mediated phonon dynamics in TaS2 and WSe2.

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.

Spatiotemporal Evolution of Coherent Elastic Strain Waves in a Single MoS2 Flake.

We use bright-field imaging in an ultrafast electron microscope to spatiotemporally map the evolution of photoexcited coherent strain waves in a single, micrometer-size flake of MoS2. Following in situ femtosecond photoexcitation, we observe individual wave trains emerge from discrete nanoscale morphological features and propagate in-plane along specific wave vectors at approximately the speed of sound (7 nm/ps). Over the span of several hundred picoseconds, the 50 GHz wave trains (20 ps periods) are observed to undergo phonon-phonon scattering and wave-train interference, resulting in a transition to larger-scale, incoherent structural dynamics. This incoherent motion further evolves into coherent nanomechanical oscillations over a few nanoseconds, ultimately leading to megahertz, whole-flake multimode resonances having microsecond lifetimes. These results provide insight into the low-frequency structural response of MoS2 to relatively coherent optical photoexcitation by elucidating the origin and the evolution of high-velocity, gigahertz strain waves.