Bradley J. Siwick

Ultrafast electron optics: Propagation dynamics of femtosecond electron packets

Time-resolved electron diffraction harbors great promise for resolving the fastest chemical processes with atomic level detail. The main obstacles to achieving this real-time view of a chemical reaction are associated with delivering short electron pulses with sufficient electron density to the sample. In this article, the propagation dynamics of femtosecond electron packets in the drift region of a photoelectron gun are investigated with an N-body numerical simulation and mean-field model. It is found that space-charge effects can broaden the electron pulse to many times its original length and generate many eV of kinetic energy bandwidth in only a few nanoseconds. There is excellent agreement between the N-body simulation and the mean-field model for both space-charge induced temporal and kinetic energy distribution broadening. The numerical simulation also shows that the redistribution of electrons inside the packet results in changes to the pulse envelope and the development of a spatially linear axia...

A photoinduced metal-like phase of monoclinic VO2 revealed by ultrafast electron diffraction

How to make vanadium dioxide metallic At about 70°C, the material vanadium dioxide (VO2) switches from being a semiconductor to a metal. The switch happens so fast that it may be useful in electronic devices, but it is not clear whether the switch is primarily caused by enhanced interactions between electrons or by a change in the crystal structure. Morrison et al. shone laser light on a sample of VO2, initially in a semiconducting state. They used electron diffraction to monitor the changes in the materials crystal structure and simultaneously measured its optical properties to monitor the electronic state. For certain laser powers, VO2 switched to a long-lived metallic state even though it preserved its initial crystal structure. Science, this issue p. 445 Simultaneous measurements of structural and optical properties are used to study optically excited vanadium dioxide. The complex interplay among several active degrees of freedom (charge, lattice, orbital, and spin) is thought to determine the electronic properties of many oxides. We report on combined ultrafast electron diffraction and infrared transmissivity experiments in which we directly monitored and separated the lattice and charge density reorganizations that are associated with the optically induced semiconductor-metal transition in vanadium dioxide (VO2). By photoexciting the monoclinic semiconducting phase, we were able to induce a transition to a metastable state that retained the periodic lattice distortion characteristic of the semiconductor but also acquired metal-like mid-infrared optical properties. Our results demonstrate that ultrafast electron diffraction is capable of following details of both lattice and electronic structural dynamics on the ultrafast time scale.

Electron source concept for single-shot sub-100 fs electron diffraction in the 100 keV range

We present a method for producing sub-100 fs electron bunches that are suitable for single-shot ultrafast electron diffraction experiments in the 100 keV energy range. A combination of analytical estimates and state-of-the-art particle tracking simulations show that it is possible to create 100 keV, 0.1 pC, 30 fs electron bunches with a spot size smaller than 500 μm and a transverse coherence length of 3 nm, using established technologies in a table-top setup. The system operates in the space-charge dominated regime to produce energy-correlated bunches that are recompressed by radio-frequency techniques. With this approach we overcome the Coulomb expansion of the bunch, providing a single-shot, ultrafast electron diffraction source concept.

Ultrafast electron diffraction with radio-frequency compressed electron pulses

We report on the complete characterization of time resolution in an ultrafast electron diffraction (UED) instrument based on radio-frequency electron pulse compression. The temporal impulse response function of the instrument was determined directly in pump-probe geometry by performing electron-laser pulse cross-correlation measurements using the ponderomotive interaction. With optimal settings, a stable impulse response of 334±10 fs was measured at a bunch charge of 0.1 pC (6.24 × 105 electrons/pulse); a dramatic improvement compared to performance without pulse compression. Phase stability currently limits the impulse response of the UED diffractometer to the range of 334–500 fs, for bunch charges ranging between 0.1 and 0.6 pC.

Polymeric nanostructured material for high-density three-dimensional optical memory storage

The unique properties of a polymer photonic crystal are examined with respect to applications as a medium for high-density three-dimensional optical data storage media. The nanocomposite material was produced from core-shell latex particles, in which the latex cores contained dye-labeled polymer. Nonfluorescent latex shells were attached to the core particles. Upon annealing, the close-packed core-shell particles formed a nanostructured material with the fluorescent particles periodically embedded into the optically inert matrix in a hexagonal close-packed structure. A two-photon laser scanning microscope was used to write bits of information into the material by photobleaching the optically sensitive particles and, under much lower fluence, read out the resulting image. Relative to conventional homogeneous storage media, the nanostructured periodic material is shown to increase the effective optical storage density by at least a factor of 2 by spatially localizing the optically active region and imposing...

Characterization of ultrashort electron pulses by electron-laser pulse cross correlation.

An all-optical method to determine the duration of ultrashort electron pulses is presented. This technique makes use of the laser pulse ponderomotive potential to effectively sample the temporal envelope of the electron pulse by sequentially scattering different sections of the pulse out of the main beam. Using laser pulse parameters that are easily accessible with modern tabletop chirped-pulse amplification laser sources, it is possible to measure the instantaneous duration of electron pulses shorter than 100 fs in the energy range that is most useful for electron diffraction studies, 10-300 keV.

Nanocrystallization of amorphous germanium films observed with nanosecond temporal resolution

Using dynamic transmission electron microscopy we measure nucleation and growth rates during laser driven crystallization of amorphous germanium (a-Ge) films supported by silicon monoxide membranes. The films were crystallized using single 532 nm laser pulses at a fluence of ∼128 mJ cm−2. Devitrification processes initiate less than 20 ns after excitation and are complete within ∼55 ns. The nucleation rate was estimated by tracking crystallite density as a function of time and reached a maximum of ∼1.6×1022 nuclei/cm3 s. This study provides information on nanocrystallization phenomena in a-Ge, which is important for the implementation of nanostructured group IV semiconductors in optoelectronics devices.

Influence of Ions on Aqueous Acid–Base Reactions

We study the effects of bromide salts on the rate and mechanism of the aqueous proton/deuteron-transfer reaction between the photoacid 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS) and the base acetate. The proton/deuteron release is triggered by exciting HPTS with 400 nm femtosecond laser pulses. Probing the electronic and vibrational resonances of the photoacid, the conjugate photobase, the hydrated proton/deuteron and the accepting base with femtosecond visible and mid-infrared pulses monitors the proton transfer. Two reaction channels are identified: 1) direct long-range proton transfer over hydrogen-bonded water bridges that connect the acid and base and 2) acid dissociation to produce fully solvated protons followed by proton scavenging from solution by acetate. We observe that the addition of salt affects the long-range reaction pathway, and reduces both the rate at which protons are released to solution by HPTS and the rate at which solvated protons are scavenged from solution by acetate. We study the dependence of these effects on the nature and concentration of the dissolved salt.

In situ laser crystallization of amorphous silicon: Controlled nanosecond studies in the dynamic transmission electron microscope

We describe an in situ method for studying the influence of deposited laser energy on microstructural evolution during nanosecond laser driven crystallization of amorphous Si. By monitoring microstructural evolution as a function of deposited energy in a dynamic transmission electron microscope (DTEM), information on grain size and defect concentration can be correlated directly with processing conditions. This work demonstrates that DTEM studies are a promising approach for obtaining fundamental information on nucleation and growth processes that have technological importance for the development of thin film transistors.

In situ investigation of explosive crystallization in a-Ge: Experimental determination of the interface response function using dynamic transmission electron microscopy

The crystallization of amorphous semiconductors is a strongly exothermic process. Once initiated the release of latent heat can be sufficient to drive a self-sustaining crystallization front through the material in a manner that has been described as explosive. Here, we perform a quantitative in situ study of explosive crystallization in amorphous germanium using dynamic transmission electron microscopy. Direct observations of the speed of the explosive crystallization front as it evolves along a laser-imprinted temperature gradient are used to experimentally determine the complete interface response function (i.e., the temperature-dependent front propagation speed) for this process, which reaches a peak of 16 m/s. Fitting to the Frenkel-Wilson kinetic law demonstrates that the diffusivity of the material locally/immediately in advance of the explosive crystallization front is inconsistent with those of a liquid phase. This result suggests a modification to the liquid-mediated mechanism commonly used to describe this process that replaces the phase change at the leading amorphous-liquid interface with a change in bonding character (from covalent to metallic) occurring in the hot amorphous material.