Ultrafast Electron Diffraction Research Articles

Photo-induced structural dynamics of o-nitrophenol by ultrafast electron diffraction.

The photo-induced dynamics of o-nitrophenol, particularly its photolysis, has garnered significant scientific interest as a potential source of nitrous acid in the atmosphere. Although the photolysis products and preceding photo-induced electronic structure dynamics have been investigated extensively, the nuclear dynamics accompanying the non-radiative relaxation of o-nitrophenol on the ultrafast timescale, which include an intramolecular proton transfer step, have not been experimentally resolved. Herein, we present a direct observation of the ultrafast nuclear motions mediating photo-relaxation using ultrafast electron diffraction. This work spatiotemporally resolves the loss of planarity which enables access to a conical intersection between the first excited state and the ground state after the proton transfer step, on the femtosecond timescale and with sub-Angstrom resolution. Our observations, supported by ab initio multiple spawning simulations, provide new insights into the proton transfer mediated relaxation mechanism in o-nitrophenol.

Characterization of a LaB6 tip as a thermionically enhanced photoemitter

There is a widespread interest in time-resolved electron spectroscopies such as ultrafast electron diffraction, ultrafast electron microscopy, and ultrafast electron energy loss spectroscopy. These techniques require pulsed electron beams with both high current and brightness. LaB6 is commonly used as a thermionic emitter because of its low work function and high electron yield. However, its use as a pulsed photocathode has not been widely explored. Here, we present measurements of the electron yield from a LaB6 filament exposed to 392 nm UV ultrafast laser pulses under a wide range of filament temperatures. We find that sample heating strongly enhances photoelectron yield, an effect known as thermionically enhanced photoemission. However, it also creates potentially undesirable, continuous thermionic background. We conclude that the ideal optimal operating conditions strongly depend on the type of measurement and require defining and quantifying an appropriate figure of merit.

First demonstration of ultrafast-electron diffraction using a 3-GHz electro-optical comb generator as a UV photoinjector laser

We demonstrate ultrafast-electron diffraction using an electro-optic comb-generator, emitting a 3 GHz train of ps pulses at 257 nm. This new operation mode improves electron coherence and reduces space-charge effects.

Coherent acoustic phonons in a coupled hexagonal boron nitride-graphite heterostructure.

Femtosecond optically excited coherent acoustic phonon modes (CAPs) are investigated in a free-standing van der Waals heterostructure composed of a 20-nm transparent hexagonal boron nitride (hBN) and a 42-nm opaque graphite layer. Employing ultrafast electron diffraction, which allows for the independent evaluation of strain dynamics in the constituent material layers, three different CAP modes are identified within the bilayer stack after the optical excitation of the graphite layer. An analytical model is used to discuss the creation of individual CAP modes. Furthermore, their excitation mechanisms in the heterostructure are inferred from the relative phases of these modes by comparison with a numerical linear-chain model. The results support an ultrafast heat transfer mechanism from graphite to the hBN lattice system, which is important to consider when using this material combination in devices.

Nanoscale Energy Transport Dynamics across Nonbonded Solid-Molecule Interfaces and in Molecular Thin Films.

Thermal conductance across a solid-solid interface requires an atomic- or molecular-level understanding, especially when a system is in a non-equilibrium state and/or consists of nanosized materials with prominent differences in structures, properties, and vibrational behaviors. Here, we report the lattice dynamics of graphite-supported molecular thin films of ethanol, whose layers exhibit in-plane hydrogen-bonded chains and out-of-plane van der Waals stacking with clear structural anisotropy. The direct structure-probing method of ultrafast electron diffraction reveals a surprising temperature difference of more than 400 K at pico- to sub-nanosecond times across the graphite-ethanol interface, yet the temporal behavior signifies a reasonably large thermal boundary conductance. This apparent conflict in a non-equilibrium condition can be resolved by considering the coupling of out-of-plane motions, instead of the commonly used temperature-based model, at transient times for energy transport across the interface separated by van der Waals interactions with mismatched unit sizes and no strong bonds. The importance of spatiotemporally resolved structural dynamics at the atomic or molecular level is emphasized.

Analytical Scaling Laws for Radiofrequency-Based Pulse Compression in Ultrafast Electron Diffraction Beamlines

We present an envelope equation-based approach to obtain analytical scaling laws for the shortest pulse length achievable using radiofrequency (RF)-based bunch compression. The derived formulas elucidate the dependencies on the electron beam energy and beam charge and reveal how relativistic energies are strongly desirable to obtain bunches containing 1 million electrons with single-digit femtosecond pulse lengths. However, the non-linearities associated with the RF curvature and the beam propagation in drift spaces significantly limit the attainability of extreme compression ratios. Therefore, an additional higher frequency RF cavity is implemented, which linearizes the bunch compression, enabling the generation of ultrashort beams in the sub-femtosecond regime.

Towards a compact all-optical terahertz-driven electron source

In this study, we propose a physical design of a compact all-optical terahertz (THz)-driven electron source. The 300-mm accelerator beamline, powered by a Joule-level laser system, can be easily integrated into the tabletop scale. A THz-driven electron gun, a tapered dielectric-loaded cylindrical waveguide, THz-driven bunch compressors, and permanent magnetic solenoids (PMSs) have been designed and optimized. Dynamic simulations show that the electron source can deliver 19 fC electron beams at 3 MeV, with a normalized transverse emittance of 0.079 π.mm.mrad. A minimum relative energy spread of 0.04% or a minimum root-mean-square (RMS) bunch length of 6.1 fs can be achieved. Sensitivity analysis shows that the THz-driven electron source can effectively work with a laser power jitter within 1.5%. Simulation studies also reveal the potential of the designed THz-driven electron source for achieving high-quality ultrafast electron diffraction (UED). Prototype THz-driven electron guns have been fabricated and are currently under testing, and more comprehensive results will be reported in future works.

Relativistic ultrafast electron diffraction at high repetition rates.

The ability to resolve the dynamics of matter on its native temporal and spatial scales constitutes a key challenge and convergent theme across chemistry, biology, and materials science. The last couple of decades have witnessed ultrafast electron diffraction (UED) emerge as one of the forefront techniques with the sensitivity to resolve atomic motions. Increasingly sophisticated UED instruments are being developed that are aimed at increasing the beam brightness in order to observe structural signatures, but so far they have been limited to low average current beams. Here, we present the technical design and capabilities of the HiRES (High Repetition-rate Electron Scattering) instrument, which blends relativistic electrons and high repetition rates to achieve orders of magnitude improvement in average beam current compared to the existing state-of-the-art instruments. The setup utilizes a novel electron source to deliver femtosecond duration electron pulses at up to MHz repetition rates for UED experiments. Instrument response function of sub-500 fs is demonstrated with < 100 fs time resolution targeted in future. We provide example cases of diffraction measurements on solid-state and gas-phase samples, including both micro- and nanodiffraction (featuring 100 nm beam size) modes, which showcase the potential of the instrument for novel UED experiments.

Simulation of ultrafast electron diffraction intensity under coherent acoustic phonons.

Ultrafast electron diffraction has been proven to be a powerful tool for the study of coherent acoustic phonons owing to its high sensitivity to crystal structures. However, this sensitivity leads to complicated behavior of the diffraction intensity, which complicates the analysis process of phonons, especially higher harmonics. Here, we theoretically analyze the effects of photoinduced coherent transverse and longitudinal acoustic phonons on electron diffraction to provide a guide for the exploitation and modulation of coherent phonons. The simulation of the electron diffraction was performed in 30-nm films with different optical penetration depths based on the atomic displacements obtained by solving the wave equation. The simulation results exhibit a complex relationship between the frequencies of the phonons and diffraction signals, which highly depends on the laser penetration depth, sample thickness, and temporal stress distribution. In addition, an intensity decomposition method is proposed to account for the in-phase oscillation and high harmonics caused by inhomogeneous excitation. These results can provide new perspectives and insights for a comprehensive and accurate understanding of the lattice response under coherent phonons.

Electronic intraband scattering in a transition-metal dichalcogenide observed by double-excitation ultrafast electron diffraction

Electronic dynamics in the excited state of transition-metal dichalcogenides (TMDs) has attracted great interest. To understand the ultrafast intraband scattering process of excited electrons in the conduction band, we demonstrated ultrafast time-resolved electron diffraction measurements with double-optical-pulse excitation and ultrafast transient reflectivity measurements of a TMD material, 2H-MoTe2. Due to the saturable absorption (or Pauli blocking) effect present in 2H-MoTe2, the system does not absorb the second excitation pulse until the excited electrons generated by the first excitation pulse with a specific fluence are scattered in the conduction band. By exploiting the Pauli blocking effect in ultrafast time-resolved electron diffraction measurements with double-optical-pulse excitation, we found that the excited electrons were scattered within 100 fs comparable to the excitation optical pulse duration. Furthermore, the excited electrons were relaxed to the lowest energy level of the conduction band (K- or Σ-valley) within 1–2 ps.

Femtosecond Electronic and Hydrogen Structural Dynamics in Ammonia Imaged with Ultrafast Electron Diffraction.

Directly imaging structural dynamics involving hydrogen atoms by ultrafast diffraction methods is complicated by their low scattering cross sections. Here we demonstrate that megaelectronvolt ultrafast electron diffraction is sufficiently sensitive to follow hydrogen dynamics in isolated molecules. In a study of the photodissociation of gas phase ammonia, we simultaneously observe signatures of the nuclear and corresponding electronic structure changes resulting from the dissociation dynamics in the time-dependent diffraction. Both assignments are confirmed by abinitio simulations of the photochemical dynamics and the resulting diffraction observable. While the temporal resolution of the experiment is insufficient to resolve the dissociation in time, our results represent an important step towards the observation of proton dynamics in real space and time.

Atomically smooth films of CsSb: A chemically robust visible light photocathode

Alkali antimonide semiconductor photocathodes provide a promising platform for the generation of high-brightness electron beams, which are necessary for the development of cutting-edge probes, including x-ray free electron lasers and ultrafast electron diffraction. Nonetheless, to harness the intrinsic brightness limits in these compounds, extrinsic degrading factors, including surface roughness and contamination, must be overcome. By exploring the growth of CsxSb thin films monitored by in situ electron diffraction, the conditions to reproducibly synthesize atomically smooth films of CsSb on 3C–SiC (100) and graphene-coated TiO2 (110) substrates are identified, and detailed structural, morphological, and electronic characterization is presented. These films combine high quantum efficiency in the visible (up to 1.2% at 400 nm), an easily accessible photoemission threshold of 566 nm, low surface roughness (down to 600 pm on a 1 μm scale), and a robustness against oxidation up to 15 times greater than Cs3Sb. These properties lead us to suggest that CsSb has the potential to operate as an alternative to Cs3Sb in electron source applications where the demands of the vacuum environment might otherwise preclude the use of traditional alkali antimonides.

Electromagnetic-Thermal Coupling Study for RF Compression Cavity Applied to Ultrafast Electron Diffraction.

Ultrafast electron diffraction (UED) is a powerful tool for observing the evolution of transient structures at the atomic level. However, temporal resolution is a huge challenge for UEDs, mainly depending on the pulse duration. Unfortunately, the Coulomb force between electrons causes the pulse duration to increase continually when propagating, reducing the temporal resolution. In this paper, we theoretically design a radio frequency (RF) compression cavity using the finite-element method of electromagnetic-thermal coupling to overcome this limitation and obtain a high-brightness, short-pulse-duration, and stable electron beam. In addition, the cavity's size parameters are optimized, and a water-cooling system is designed to ensure stable operation. To the best of our knowledge, this is the first time that the electromagnetic-thermal coupling method has been used to study the RF cavity applied to UED. The results show that the RF cavity operates in TM010 mode with a resonant frequency of 2970 MHz and generates a resonant electric field. This mode of operation generates an electric field that varies periodically and transiently, compressing the electronic pulse duration. The electromagnetic-thermal coupling method proposed in this study effectively improves the temporal resolution of UED.

Localised surface plasmon resonance inducing cooperative Jahn–Teller effect for crystal phase-change in a nanocrystal

The Jahn–Teller effect, a phase transition phenomenon involving the spontaneous breakdown of symmetry in molecules and crystals, causes important physical and chemical changes that affect various fields of science. In this study, we discovered that localised surface plasmon resonance (LSPR) induced the cooperative Jahn–Teller effect in covellite CuS nanocrystals (NCs), causing metastable displacive ion movements. Electron diffraction measurements under photo illumination, ultrafast time-resolved electron diffraction analyses, and theoretical calculations of semiconductive plasmonic CuS NCs showed that metastable displacive ion movements due to the LSPR-induced cooperative Jahn–Teller effect delayed the relaxation of LSPR in the microsecond region. Furthermore, the displacive ion movements caused photo-switching of the conductivity in CuS NC films at room temperature (22 °C), such as in transparent variable resistance infrared sensors. This study pushes the limits of plasmonics from tentative control of collective oscillation to metastable crystal structure manipulation.

Novel applications of generative adversarial networks (GANs) in the analysis of ultrafast electron diffraction (UED) images.

Inferring transient molecular structural dynamics from diffraction data is an ambiguous task that often requires different approximation methods. In this paper, we present an attempt to tackle this problem using machine learning. Although most recent applications of machine learning for the analysis of diffraction images apply only a single neural network to an experimental dataset and train it on the task of prediction, our approach utilizes an additional generator network trained on both synthetic and experimental data. Our network converts experimental data into idealized diffraction patterns from which information is extracted via a convolutional neural network trained on synthetic data only. We validate this approach on ultrafast electron diffraction data of bismuth samples undergoing thermalization upon excitation via 800nm laser pulses. The network was able to predict transient temperatures with a deviation of less than 6% from analytically estimated values. Notably, this performance was achieved on a dataset of 408 images only. We believe that employing this network in experimental settings where high volumes of visual data are collected, such as beam lines, could provide insights into the structural dynamics of different samples.

The Design of Relativistic Ultrafast Electron Diffraction and Imaging (RUEDI) Facility for Materials in Extremes.

The Design of Relativistic Ultrafast Electron Diffraction and Imaging (RUEDI) Facility for Materials in Extremes.

Light-induced hexatic state in a layered quantum material

The tunability of materials properties by light promises a wealth of future applications in energy conversion and information technology. Strongly correlated materials such as transition metal dichalcogenides offer optical control of electronic phases, charge ordering and interlayer correlations by photodoping. Here, we find the emergence of a transient hexatic state during the laser-induced transformation between two charge-density wave phases in a thin-film transition metal dichalcogenide, 1T-type tantalum disulfide (1T-TaS2). Introducing tilt-series ultrafast nanobeam electron diffraction, we reconstruct charge-density wave rocking curves at high momentum resolution. An intermittent suppression of three-dimensional structural correlations promotes a loss of in-plane translational order caused by a high density of unbound topological defects, characteristic of a hexatic intermediate. Our results demonstrate the merit of tomographic ultrafast structural probing in tracing coupled order parameters, heralding universal nanoscale access to laser-induced dimensionality control in functional heterostructures and devices.

Multi-scale time-resolved electron diffraction: A case study in moiré materials

Ultrafast-optical-pump — structural-probe measurements, including ultrafast electron and x-ray scattering, provide direct experimental access to the fundamental timescales of atomic motion, and are thus foundational techniques for studying matter out of equilibrium. High-performance detectors are needed in scattering experiments to obtain maximum scientific value from every probe particle. We deploy a hybrid pixel array direct electron detector to perform ultrafast electron diffraction experiments on a WSe2/MoSe2 2D heterobilayer, resolving the weak features of diffuse scattering and moiré superlattice structure without saturating the zero order peak. Enabled by the detector’s high frame rate, we show that a chopping technique provides diffraction difference images with signal-to-noise at the shot noise limit. Finally, we demonstrate that a fast detector frame rate coupled with a high repetition rate probe can provide continuous time resolution from femtoseconds to seconds, enabling us to perform a scanning ultrafast electron diffraction experiment that maps thermal transport in WSe2/MoSe2 and resolves distinct diffusion mechanisms in space and time.

Strong Coupling of Self‐Trapped Excitons to Acoustic Phonons in Bismuth Perovskite Cs3Bi2I9

AbstractTo assess the potential optoelectronic applications of metal‐halide perovskites, it is critical to have a detailed understanding of the nature and dynamics of interactions between carriers and the polar lattices. Here, the electronic and structural dynamics of bismuth‐based perovskite Cs3Bi2I9 are revealed by transient reflectivity and ultrafast electron diffraction. A cross‐examination of these results combined with theoretical analyses allows the identification of the major carrier–phonon coupling mechanism and the associated time scales. It is found that carriers photoinjected into Cs3Bi2I9 form self‐trapped excitons on an ultrafast time scale. However, they retain most of their energy, and their coupling to Fröhlich‐type optical phonons is limited at early times. Instead, the long‐lived excitons exert an electronic stress via deformation potential and develop a prominent, sustaining strain field as coherent acoustic phonons in 10 ps. From sub‐ps to ns and beyond, a similar extent of the atomic displacements is found throughout the different stages of structural distortions, from limited local modulations to a coherent strain field to the Debye–Waller random atomic motions on longer times. The current results suggest the potential use of bismuth‐based perovskites for applications other than photovoltaics to take advantage of the carriers’ stronger self‐trapping and long lifetimes.

Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.