Unveiling Spatial and Temporal Dynamics of Plasmon-Enhanced Localized Fields in Metallic Nanoframes through Ultrafast Electron Microscopy.

Plasmonic nanomaterials, particularly noble metal nanoframes (NFs), are important for applications such as catalysis, biosensing, and energy harvesting due to their ability to enhance localized electric fields and atomic efficiency via localized surface plasmon resonance (LSPR). Yet the fundamental structure-function relationships and plasmonic dynamics of the NFS are difficult to study experimentally and thus far rely predominately on computational methodologies, limiting their utilization. This study leverages the capabilities of ultrafast electron microscopy (UEM), specifically photon-induced near-field electron microscopy (PINEM), to probe the light-matter interactions within plasmonic NF structures. The effects of shape, size, and plasmonic coupling of Pt@Au core-shell NFs on spatial and temporal characteristics of plasmon-enhanced localized electric fields are explored. Importantly, time-resolved PINEM analysis reveals that the plasmonic fields around hexagonal NF prisms exhibit a spatially dependent excitation and decay rate, indicating a nuanced interplay between the spatial geometry of the NF and the temporal evolution of the localized electric field. These results and observations uncover nanophotonic energy transfer dynamics in NFs and highlight their potential for applications in biosensing and photocatalysis.

Imaging hot photocarrier transfer across a semiconductor heterojunction with ultrafast electron microscopy.

Semiconductor heterojunctions have gained significant attention for efficient optoelectronic devices owing to their unique interfaces and synergistic effects. Interaction between charge carriers with the heterojunction plays a crucial role in determining device performance, while its spatial-temporal mapping remains lacking. In this study, we employ scanning ultrafast electron microscopy (SUEM), an emerging technique that combines high spatial-temporal resolution and surface sensitivity, to investigate photocarrier dynamics across a Si/Ge heterojunction. Charge dynamics are selectively examined across the junction and compared to far bulk areas, through which the impact of the built-in potential, band offsets, and surface effects is directly visualized. In particular, we find that the heterojunction drastically modifies the hot photocarrier diffusivities in both Si and Ge regions due to charge trapping. These findings are further elucidated with insights from the band structure and surface potential measured by complementary techniques. This work demonstrates the tremendous effect of heterointerfaces on hot photocarrier dynamics and showcases the potential of SUEM in characterizing realistic optoelectronic devices.

Laser-Induced Stress-Driven Nanoplate Jumping Visualized by Ultrafast Electron Microscopy.

Understanding laser-induced jumping has attracted great interest in nanomaterial launching and transfer but requires a high spatiotemporal resolution visualization. Here, we report a jumping dynamics of nanoplate driven by ultrafast laser-induced stress using time-resolved transmission electron microscopy. Single-shot imaging reveals a nondestructive launching of gold nanoplates in several nanoseconds after the pulsed femtosecond laser excitation. The temperature rise and acoustic vibration, derived from ultrafast electron crystallography with a picosecond time resolution, confirm the existence of a laser-induced elastic stress wave. The generation, propagation, and reflection of thermal stress waves are further clarified by atomic simulation. The nonequilibrium ultrafast laser heating produces a compressive stress wave within several picoseconds, constrained by the supporting substrate under nanoplate to provide thrust force. This compressive stress is subsequently reflected into tensile stress by the substrate, promoting the nanoplate to jump off the substrate. Furthermore, the uneven interface adhesion results in the jumping flip of nanoplates, as well as, diminished their jumping speed. This study unveils the jumping regime driven by impulsive laser-excited stress and offers understanding of light-matter interaction.

Direct Nanosecond Multiframe Imaging of Irreversible Dynamics in 4D Electron Microscopy.

Irreversible ultrafast events are prevalent in nature, yet their capture in real time poses significant challenges. Traditional single-shot imaging technologies, which utilize a single optical pump and single delayed electron probe, offer high spatiotemporal resolution but fail to capture the entire dynamic evolutions. Here, we introduce a novel imaging method employing a single optical pump and delayed multiple electron probes. This approach, facilitated by an innovative deflector in ultrafast electron microscopy, enables the acquisition of nine frames per exposure, paving the way for statistical and quantitative analyses. We have developed an algorithm that corrects frame-by-frame distortions, realizing a cross-correlation enhancement of ∼26%. Achieving ∼12 nm and 20 ns resolution, our method allows for the comprehensive visualization of laser-induced behaviors in Au nanoparticles, including merging, jumping, and collision processes. Our results demonstrate the capability of this multiframe imaging technique to document irreversible processes across materials science and biology with unprecedented nanometer-nanosecond precision.

A Femtosecond Electron-Based Versatile Microscopy for Visualizing Carrier Dynamics in Semiconductors Across Spatiotemporal and Energetic Domains.

Carrier dynamics detection in different dimensions (space, time, and energy) with high resolutions plays a pivotal role in the development of modern semiconductor devices, especially in low-dimensional, high-speed, and ultrasensitive devices. Here, a femtosecond electron-based versatile microscopy is reported that combines scanning ultrafast electron microscopy (SUEM) imaging and time-resolved cathodoluminescence (TRCL) detection, which allows for visualizing and decoupling different dynamic processes of carriers involved in surface and bulk in semiconductors with unprecedented spatiotemporal and energetic resolutions. The achieved spatial resolution is better than 10 nm, and the temporal resolutions for SUEM imaging and TRCL detection are ≈500 fs and ≈4.5 ps, respectively, representing state-of-the-art performance. To demonstrate its unique capability, the surface and bulk carrier dynamics involved in n-type gallium arsenide (GaAs) are directly tracked and distinguished. It is revealed, in real time and space, that hot carrier cooling, defect trapping, and interband-/defect-assisted radiative recombination in the energy domain result in ordinal super-diffusion, localization, and sub-diffusion of carriers at the surface, elucidating the crucial role of surface states on carrier dynamics. The study not only gives a comprehensive physical picture of carrier dynamics in GaAs, but also provides a powerful platform for exploring complex carrier dynamics in semiconductors for promoting their device performance.

Ultrafast Nanoimaging of Spin-Mediated Shear Waves in an Acoustic Cavity.

Strong spin-lattice coupling in van der Waals (vdW) magnets shows potential for innovative magneto-mechanical applications. Here, nanoscale and picosecond imaging by ultrafast electron microscopy reveal heterogeneous spin-mediated coherent acoustic phonon dynamics in a thin-film cavity of the vdW antiferromagnet FePS3. The harmonics of the interlayer shear acoustic modes are observed, in which the even and odd harmonics exhibit distinct nanoscopic dynamics. Corroborated by acoustic wave simulation, the role of defects in forming even harmonics is elucidated. Above the Néel temperature (TN), the interlayer shear acoustic harmonics are suppressed, while the in-plane traveling wave is predominantly excited. The dominant acoustic dynamics shifts from the out-of-plane shear to the in-plane traveling wave across TN, demonstrating that magnetic properties can influence phonon scattering pathways. The spatiotemporally resolved structural characterization provides valuable nanoscopic insights for interlayer-shear-mode-based acoustic cavities, opening up possibilities for magneto-mechanical applications of vdW magnets.

Ultrafast Coupling of Optical Near Fields to Low-Energy Electrons Probed in a Point-Projection Microscope.

We report the first observation of the coupling of strong optical near fields to wavepackets of free, 100 eV electrons with <50 fs temporal resolution in an ultrafast point-projection microscope. Optical near fields are created by excitation of a thin, nanometer-sized Yagi-Uda antenna, with 20 fs near-infrared laser pulses. Phase matching between electrons and near fields is achieved due to strong spatial confinement of the antenna near field. Energy-resolved projection images of the antenna are recorded in an optical pump-electron probe scheme. We show that the phase modulation of the electron by transverse-field components results in a transient electron deflection while longitudinal near-field components broaden the kinetic energy distribution. This low-energy electron near-field coupling is used here to characterize the chirp of the ultrafast electron wavepackets, acquired upon propagation from the electron emitter to the sample. Our results bring direct mapping of different vectorial components of highly localized optical near fields into reach.

Direct mapping of bending and torsional dynamics in individual nanostructures.

Investigating coherent acoustic vibrations in nanostructured materials provides fundamental insights into optomechanical responses and microscopic energy flow. Extensive measurements of vibrational dynamics have been performed for a wide variety of nanoparticles and nanoparticle assemblies. However, virtually all of them show that only the dilation modes are launched after laser excitations, and the acoustic bending and torsional motions, which are commonly observed in photoexcited chemical bonds, are absent. Unambiguous identification and refined characterization of these "missing" modes have been a long-standing issue. In this report, we investigated the acoustic vibrational dynamics of individual Au nanoprisms on free-standing graphene substrates using an ultrafast high-sensitivity dark-field imaging approach in four-dimensional transmission electron microscopy. Following optical excitations, we observed low-frequency multiple-mode oscillations and higher superposition amplitudes at nanoprism corners and edges on the subnanoparticle level. In combination with finite-element simulations, we determined that these vibrational modes correspond to out-of-plane bending and torsional motions, superimposed by an overall tilting effect of the nanoprisms. The launch and relaxation processes of these modes are highly pertinent to substrate effects and nanoparticle geometries. These findings contribute to the fundamental understanding about acoustic dynamics of individual nanostructures and their interaction with substrates.

Characterization of transverse electron pulse trains using RF powered traveling wave metallic comb striplines.

Advancements in ultrafast electron microscopy have allowed elucidation of spatially selective structural dynamics. However, as the spatial resolution and imaging capabilities have made progress, quantitative characterization of the electron pulse trains has not been reported at the same rate. In fact, inexperienced users have difficulty replicating the technique because only a few dedicated microscopes have been characterized thoroughly. Systems replacing laser driven photoexcitation with electrically driven deflectors especially suffer from a lack of quantified characterization because of the limited quantity. The primary advantages to electrically driven systems are broader frequency ranges, ease of use and simple synchronization to electrical pumping. Here, we characterize the technical parameters for electrically driven UEM including the shape, size and duration of the electron pulses using low and high frequency chopping methods. At high frequencies, pulses are generated by sweeping the electron beam across a chopping aperture. For low frequencies, the beam is continuously forced off the optic axis by a DC potential, then momentarily aligned by a countering pulse. Using both methods, we present examples that measure probe durations of 2 ns and 10 ps for the low and high frequency techniques, respectively. We also discuss how the implementation of a pulsed probe affects STEM imaging conditions by adjusting the first condenser lens.

Ultrafast Electron Microscopy of Nanoscale Charge Dynamics in Semiconductors.

The ultrafast dynamics of charge carriers in solids plays a pivotal role in emerging optoelectronics, photonics, energy harvesting, and quantum technology applications. However, the investigation and direct visualization of such nonequilibrium phenomena remains as a long-standing challenge, owing to the nanometer-femtosecond spatiotemporal scales at which the charge carriers evolve. Here, we propose and demonstrate an interaction mechanism enabling nanoscale imaging of the femtosecond dynamics of charge carriers in solids. This imaging modality, which we name charge dynamics electron microscopy (CDEM), exploits the strong interaction of free-electron pulses with terahertz (THz) near fields produced by the moving charges in an ultrafast scanning transmission electron microscope. The measured free-electron energy at different spatiotemporal coordinates allows us to directly retrieve the THz near-field amplitude and phase, from which we reconstruct movies of the generated charges by comparison to microscopic theory. The CDEM technique thus allows us to investigate previously inaccessible spatiotemporal regimes of charge dynamics in solids, providing insight into the photo-Dember effect and showing oscillations of photogenerated electron-hole distributions inside a semiconductor. Our work facilitates the exploration of a wide range of previously inaccessible charge-transport phenomena in condensed matter using ultrafast electron microscopy.

Design of an ultrafast pulsed ponderomotive phase plate for cryo-electron tomography.

Ponderomotive phase plates have shown that temporally consistent phase contrast is possible within electron microscopes via high-fluence static laser modes resonating in Fabry-Perot cavities. Here, we explore using pulsed laser beams as an alternative method of generating high fluences. We find through forward-stepping finite element models that picosecond or shorter interactions are required for meaningful fluences and phase shifts, with higher pulse energies and smaller beam waists leading to predicted higher fluences. An additional model based on quasi-classical assumptions is used to discover the shape of the phase plate by incorporating the oscillatory nature of the electric field. From these results, we find the transient nature of the laser pulses removes the influence of Kapitza-Dirac diffraction patterns that appear in the static resonator cases. We conclude by predicting that a total laser pulse energy of 8.7 µJ is enough to induce the required π/2 phase shift for Zernike-like phase microscopy.

Attosecond electron-beam technology: a review of recent progress.

Electron microscopy and diffraction with ultrashort pulsed electron beams are capable of imaging transient phenomena with the combined ultrafast temporal and atomic-scale spatial resolutions. The emerging field of optical electron beam control allowed the manipulation of relativistic and sub-relativistic electron beams at the level of optical cycles. Specifically, it enabled the generation of electron beams in the form of attosecond pulse trains and individual attosecond pulses. In this review, we describe the basics of the attosecond electron beam control and overview the recent experimental progress. High-energy electron pulses of attosecond sub-optical cycle duration open up novel opportunities for space-time-resolved imaging of ultrafast chemical and physical processes, coherent photon generation, free electron quantum optics, electron-atom scattering with shaped wave packets and laser-driven particle acceleration. Graphical Abstract.

Stroboscopic ultrafast imaging using RF strip-lines in a commercial transmission electron microscope.

The development of ultrafast electron microscopy (UEM), specifically stroboscopic imaging, has brought the study of structural dynamics to a new level by overcoming the spatial limitations of ultrafast spectroscopy and the temporal restrictions of traditional TEM simultaneously. Combining the concepts governing both techniques has enabled direct visualization of dynamics with spatiotemporal resolutions in the picosecond-nanometer regime. Here, we push the limits of imaging using a pulsed electron beam via RF induced transverse deflection based on the newly developed 200 keV frequency-tunable strip-line pulser. We demonstrate a 0.2 nm spatial resolution and elucidation of magnetic spin induction maps using the phase-microscopy method. We also present beam coherence measurements and expand our study using the breathing modes of a silicon interdigitated comb under RF excitation which achieves improved temporal synchronization between the electron pulse-train and electric field. A new RF holder has also been developed with impedance matching to the RF signal to minimize transmission power loss to samples and its performance is compared with a conventional sample holder.

Cathodoluminescence in Ultrafast Electron Microscopy.

Implementing the modern technologies of light-emitting devices, light harvesting, and quantum information processing requires the understanding of the structure-function relations at spatial scales below the optical diffraction limit and time scales of energy and information flows. Here, we distinctively combine cathodoluminescence (CL) with ultrafast electron microscopy (UEM), termed CL-UEM, because CL and UEM synergetically afford the required spectral and spatiotemporal sensitivities, respectively. For color centers in nanodiamonds, we demonstrate the measurement of CL lifetime with a local sensitivity of 50 nm and a time resolution of 100 ps. It is revealed that the emitting states of the color centers can be populated through charge transfer among the color centers across diamond lattices upon high-energy electron beam excitation. The technical advance achieved in this study will facilitate the specific control over energy conversion at nanoscales, relevant to quantum dots and single-photon sources.

Transient Strain-Induced Electronic Structure Modulation in a Semiconducting Polymer Imaged by Scanning Ultrafast Electron Microscopy.

Understanding the optoelectronic properties of semiconducting polymers under external strain is essential for their applications in flexible devices. Although prior studies have highlighted the impact of static and macroscopic strains, assessing the effect of a local transient deformation before structural relaxation occurs remains challenging. Here, we employ scanning ultrafast electron microscopy (SUEM) to image the dynamics of a photoinduced transient strain in the semiconducting polymer poly(3-hexylthiophene) (P3HT). We observe that the photoinduced SUEM contrast, corresponding to the local change of secondary electron emission, exhibits an unusual ring-shaped profile. We attribute the observation to the electronic structure modulation of P3HT caused by a photoinduced strain field owing to its low modulus and strong electron-lattice coupling, supported by a finite-element analysis. Our work provides insights into tailoring optoelectronic properties using transient mechanical deformation in semiconducting polymers and demonstrates the versatility of SUEM to study photophysical processes in diverse materials.

Photo-Thermal Switching of Individual Plasmonically Activated Spin Crossover Nanoparticle Imaged by Ultrafast Transmission Electron Microscopy.

Spin crossover (SCO) is a promising switching phenomenon when implemented in electronic devices as molecules, thin films or nanoparticles. Among the properties modulated along this phenomenon, optically induced mechanical changes are of tremendous importance as they can work as fast light-induced mechanical switches or allow to investigate and control microstructural strains and fatigability. The development of characterization techniques probing nanoscopic behavior with high spatio-temporal resolution allows to trigger and visualize such mechanical changes of individual nanoscopic objects. Here, ultrafast transmission electron microscopy (UTEM) is used to precisely probe the length changes of individual switchable nanoparticles induced thermally by nanosecond laser pulses. This allows revealing of the mechanisms of spin switching, leading to the macroscopic expansion of SCO materials. This study is conducted on individual pure SCO nanoparticles and SCO nanoparticles encapsulating gold nanorods that serve for plasmonic heating under laser pulses. Length changes are compared with time-resolved optical measurements performed on an assembly of these particles.

Visualization of Plasmonic Couplings Using Ultrafast Electron Microscopy.

Hybrids of graphene and metal plasmonic nanostructures are promising building blocks for applications in optoelectronics, surface-enhanced scattering, biosensing, and quantum information. An understanding of the coupling mechanism in these hybrid systems is of vital importance to its applications. Previous efforts in this field mainly focused on spectroscopic studies of strong coupling within the hybrids with no spatial resolution. Here we report direct imaging of the local plasmonic coupling between single Au nanocapsules and graphene step edges at the nanometer scale by photon-induced near-field electron microscopy in an ultrafast electron microscope for the first time. The proximity of a step in the graphene to the nanocapsule causes asymmetric surface charge density at the ends of the nanocapsules. Computational electromagnetic simulations confirm the experimental observations. The results reported here indicate that this hybrid system could be used to manipulate the localized electromagnetic field on the nanoscale, enabling promising future plasmonic devices.

Modulation of Cathodoluminescence Emission by Interference with External Light.

Spontaneous processes triggered in a sample by free electrons, such as cathodoluminescence, are commonly regarded and detected as stochastic events. Here, we supplement this picture by showing through first-principles theory that light and free-electron pulses can interfere when interacting with a nanostructure, giving rise to a modulation in the spectral distribution of the cathodoluminescence light emission that is strongly dependent on the electron wave function. Specifically, for a temporally focused electron, cathodoluminescence can be canceled upon illumination with a spectrally modulated dimmed laser that is phase-locked relative to the electron density profile. We illustrate this idea with realistic simulations under attainable conditions in currently available ultrafast electron microscopes. We further argue that the interference between excitations produced by light and free electrons enables the manipulation of the ultrafast materials response by combining the spectral and temporal selectivity of the light with the atomic resolution of electron beams.

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'.

Light-Induced Anisotropic Morphological Dynamics of Black Phosphorus Membranes Visualized by Dark-Field Ultrafast Electron Microscopy.

Black phosphorus (BP) is an elemental layered material with a strong in-plane anisotropic structure. This structure is accompanied by anisotropic optical, electrical, thermal, and mechanical properties. Despite interest in BP from both fundamental and technical aspects, investigation into the structural dynamics of BP caused by strain fields, which are prevalent for two-dimensional (2D) materials and tune the material physical properties, has been overlooked. Here, we report the morphological dynamics of photoexcited BP membranes observed using time-resolved diffractograms and dark-field images obtained via ultrafast electron microscopy. Aided by 4D reconstruction, we visualize the nonequilibrium bulging of thin BP membranes and reveal that the buckling transition is driven by impulsive thermal stress upon photoexcitation in real time. The bulging, buckling, and flattening (on strain release) showed anisotropic spatiotemporal behavior. Our observations offer insights into the fleeting morphology of anisotropic 2D matter and provide a glimpse into the mapping of transient, modulated physical properties upon impulsive excitation, as well as strain engineering at the nanoscale.