Ultrafast Time-resolved Electron Diffraction Research Articles

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.

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.

Generation of sub-100fs electron pulses for time-resolved electron diffraction using a direct synchronization method.

To investigate photoinduced phenomena in various materials and molecules, ultrashort pulsed x-ray and electron sources with high brightness and high repetition rates are required. The x-ray and electron's typical and de Broglie wavelengths are shorter than lattice constants of materials and molecules. Therefore, photoinduced structural dynamics on the femtosecond to picosecond timescales can be directly observed in a diffraction manner by using these pulses. This research created a tabletop ultrashort pulsed electron diffraction setup that used a femtosecond laser and electron pulse compression cavity that was directly synchronized to the microwave master oscillator (∼3GHz). A compressed electron pulse with a 1kHz repetition rate contained 228 000 electrons. The electron pulse duration was estimated to be less than 100fs at the sample position by using photoinduced immediate lattice changes in an ultrathin silicon film (50nm). The newly developed time-resolved electron diffraction setup has a pulse duration that is comparable to femtosecond laser pulse widths (35-100fs). The pulse duration, in particular, fits within the timescale of photoinduced phenomena in quantum materials. Our developed ultrafast time-resolved electron diffraction setup with a sub-100fs temporal resolution would be a powerful tool in material science with a combination of optical pump-probe, time-resolved photoemission spectroscopic, and pulsed x-ray measurements.

Photoinduced oxygen transport in cobalt double-perovskite crystal EuBaCo2O5.39

Understanding and controlling atomic motions in solid are essential in ionic materials, such as ion conductors, electrolyte and electrodes of batteries, and gas separators. Although photoinduced proton transport in solid materials has been demonstrated, photoinduced transport of heavier ions, such as the oxide ion, in solid materials remains entirely elusive. Herein, we apply ultrafast time-resolved electron diffraction to observe the large displacement of oxide ions in a strongly correlated material, EuBaCo2O5.39, under near-ultraviolet photoexcitation at room temperature. The mechanism of the photoinduced transport of oxide ions is revealed via the combination of ultrafast optical spectroscopy and density functional theory calculations. Our findings show that photoexcitation induces ionic motions in a ceramic crystal at room temperature through the charge transfer that strongly couples with large ionic displacement under the nonequilibrium condition.

Phonon transport probed at carbon nanotube yarn/sheet boundaries by ultrafast structural dynamics

Modern integrated devices and electrical circuits have often been designed with carbon nanostructures, such as carbon nanotubes (CNTs) and graphene due to their high thermal and electrical transport properties. These transport properties are strongly correlated to their acoustic phonon and carrier dynamics. Thus, understanding the phonon and carrier dynamics of carbon nanostructures in extremely small regions will lead to their further practical applications. Here, we demonstrate ultrafast time-resolved electron diffraction and ultrafast transient spectroscopy to characterize the phonon and carrier dynamics at the boundary of quasi-one-dimensional CNTs before and after Joule annealing. The results from ultrafast time-resolved electron diffraction show that the CNTs after Joule annealing reach the phonon equilibrium state extremely fast with a timescale of 10 ps, which indicates that thermal transport in CNTs improves following Joule annealing. The methodology described in this study connects conventional macroscopic thermo- and electrodynamics to those at the nanometer scale. Realistic timescale kinetic simulations were performed to further elaborate on the phenomena that occur in CNTs during Joule annealing. The insights obtained in this study are expected to pave the way to parameterize the unexplored thermal and electrical properties of carbon materials at the nanometer scale.

Ultrafast isomerization-induced cooperative motions to higher molecular orientation in smectic liquid-crystalline azobenzene molecules

The photoisomerization of molecules is widely used to control the structure of soft matter in both natural and synthetic systems. However, the structural dynamics of the molecules during isomerization and their subsequent response are difficult to elucidate due to their complex and ultrafast nature. Herein, we describe the ultrafast formation of higher-orientation of liquid-crystalline (LC) azobenzene molecules via linearly polarized ultraviolet light (UV) using ultrafast time-resolved electron diffraction. The ultrafast orientation is caused by the trans-to-cis isomerization of the azobenzene molecules. Our observations are consistent with simplified molecular dynamics calculations that revealed that the molecules are aligned with the laser polarization axis by their cooperative motion after photoisomerization. This insight advances the fundamental chemistry of photoresponsive molecules in soft matter as well as their ultrafast photomechanical applications.

Selective Reduction Mechanism of Graphene Oxide Driven by the Photon Mode versus the Thermal Mode.

A two-dimensional nanocarbon, graphene, has attracted substantial interest due to its excellent properties. The reduction of graphene oxide (GO) has been investigated for the mass production of graphene used in practical applications. Different reduction processes produce different properties in graphene, affecting the performance of the final materials or devices. Therefore, an understanding of the mechanisms of GO reduction is important for controlling the properties of functional two-dimensional systems. Here, we determined the average structure of reduced GO prepared via heating and photoexcitation and clearly distinguished their reduction mechanisms using ultrafast time-resolved electron diffraction, time-resolved infrared vibrational spectroscopy, and time-dependent density functional theory calculations. The oxygen atoms of epoxy groups are selectively removed from the basal plane of GO by photoexcitation (photon mode), in stark contrast to the behavior observed for the thermal reduction of hydroxyl and epoxy groups (thermal mode). The difference originates from the selective excitation of epoxy bonds via an electronic transition due to their antibonding character. This work will enable the preparation of the optimum GO for the intended applications and expands the application scope of two-dimensional systems.

Bond Dissociation Triggering Molecular Disorder in Amorphous H2O.

We developed a system to deposit H2O molecules onto ultrathin silicon nitride substrates in situ using time-resolved transmission electron diffraction apparatus and performed ultrafast time-resolved electron diffraction measurements in the noncrystalline (amorphous) H2O under near-ultraviolet photoexcitation. The observed dynamics directly represent O-H bond dissociation via multiphoton absorption and charge transfer, which trigger ionization and intermolecular disorder in the amorphous H2O. Our results illustrate the intriguing nature of light-matter and matter-matter interactions in H2O molecules.

Ultrafast time-resolved electron diffraction revealing the nonthermal dynamics of near-UV photoexcitation-induced amorphization in Ge2Sb2Te5.

Because of their robust switching capability, chalcogenide glass materials have been used for a wide range of applications, including optical storages devices. These phase transitions are achieved by laser irradiation via thermal processes. Recent studies have suggested the potential of nonthermal phase transitions in the chalcogenide glass material Ge2Sb2Te5 triggered by ultrashort optical pulses; however, a detailed understanding of the amorphization and damage mechanisms governed by nonthermal processes is still lacking. Here we performed ultrafast time-resolved electron diffraction and single-shot optical pump-probe measurements followed by femtosecond near-ultraviolet pulse irradiation to study the structural dynamics of polycrystalline Ge2Sb2Te5. The experimental results present a nonthermal crystal-to-amorphous phase transition of Ge2Sb2Te5 initiated by the displacements of Ge atoms. Above the fluence threshold, we found that the permanent amorphization caused by multi-displacement effects is accompanied by a partial hexagonal crystallization.

Coherent phonons in bismuth film observed by ultrafast electron diffraction

The generation of coherent phonons in polycrystalline bismuth film excited with femtosecond laser pulse is observed by ultrafast time-resolved electron diffraction. The dynamics of the diffracted intensities from the (110), (202), and (024) lattice planes show pronounced oscillations at 130–150 GHz. The origin of these coherent acoustic phonons is discussed in view of optical phonon decay into two acoustic phonons. Different drop times in the intensity of the diffraction orders are observed and interpreted as anisotropy in the energy transfer rate of coherent optical phonons.

Ultrafast Time-Resolved Electron Diffraction based on Photocathode RF Gun Generating MeV Electron Pulses

Ultrafast Time-Resolved Electron Diffraction based on Photocathode RF Gun Generating MeV Electron Pulses

100-femtosecond MeV electron source for ultrafast electron diffraction

A near-relativistic 100-fs MeV electron beam is developed by using a photocathode rf gun for revealing the hidden ultrafast dynamics of intricate molecular and atomic processes in materials through experimentation of ultrafast time-resolved electron diffraction (UED). The transverse and longitudinal dynamics of femtosecond electron beam in the rf gun were studied theoretically by particle simulation. The growths of the emittance, bunch length and energy spread due to the rf and space charge effects were investigated by changing the laser parameters, field gradient and electron charge. The theoretical studies indicate that a 100-fs MeV electron beam with the transverse emittance of 0.1 mm mrad and the relative energy spread of 10 −3–10 −4 at bunch charge of 0.1–2 pC (10 6–10 7 electrons per pulse) is achievable for UED, in which the intensity is three orders of magnitude higher than that produced by the conventional dc or pulsed guns.

Ultra-fast Time-Resolved Electron Diffraction of Strongly Driven Phase Transitions on Silicon Surfaces

AbstractThe dynamics of strongly driven phase transitions at surfaces are studied by ultra-fast time-resolved reflection high energy electron diffraction. The surfaces are excited by an intense fs-laser pulse (pump) and probed by an ultra-short electron pulse with variable time delay. The order-disorder phase transition from a c(4×2) to a (2×1) of the bare Si(001) surface shows a transient decrease of the intensity of the c(4×2) spots which recovers on a time scale of a few hundred picoseconds indicating the excitation of the phase transition. On Si(111) a monolayer of Indium induces a (4×1) reconstruction which undergoes a Peierls like phase transition to a (8ד2”) reconstruction below 100 K. Upon laser excitation at a temperature of 40 K the phase transition was strongly driven. The (8ד2”)-diffraction spots instantaneously disappears, while the intensity of the (4×1)-spots increases. This increase of the (4×1) spot intensity excludes an explanation by the Debye-Waller-Effect and is evidence for a true structural phase transition at a surface.

Ultrafast time-resolved electron diffraction with megavolt electron beams

A rf photocathode electron gun is used as an electron source for ultrafast time-resolved pump-probe electron diffraction. The authors observed single-shot diffraction patterns from a 160nm Al foil using the 5.4MeV electron beam from the Gun Test Facility at the Stanford Linear Accelerator. Excellent agreement with simulations suggests that single-shot diffraction experiments with a time resolution approaching 100fs are possible.

Band structure of bismuth telluride, bismuth selenide and their respective alloys

Understanding and controlling atomic motions in solid are essential in ionic materials, such as ion conductors, electrolyte and electrodes of batteries, and gas separators. Although photoinduced proton transport in solid materials has been demonstrated, photoinduced transport of heavier ions, such as the oxide ion, in solid materials remains entirely elusive. Herein, we apply ultrafast time-resolved electron diffraction to observe the large displacement of oxide ions in a strongly correlated material, EuBaCo2O5.39, under near-ultraviolet photoexcitation at room temperature. The mechanism of the photoinduced transport of oxide ions is revealed via the combination of ultrafast optical spectroscopy and density functional theory calculations. Our findings show that photoexcitation induces ionic motions in a ceramic crystal at room temperature through the charge transfer that strongly couples with large ionic displacement under the nonequilibrium condition.