Ding-Shyue Yang

Interfaces play a crucial role in energy transport at the nanoscale. However, direct experimental observations of interfacial thermal conductance across molecular junctions have remained challenging due to the high spatiotemporal resolution required for probing. Here, we report dynamic energy transport processes across multi-component molecular junctions observed at the atomic level by employing reflection ultrafast electron diffraction. A clear temporal sequence of energy transfer is revealed at early times following photoexcitation of Au(111) surfaces chemically bonded with self-assembled monolayers (SAMs) of alkanethiols: from the gold surface layer (SL) to the head groups of a SAM and then to the CH2-CH2 methylene lattice. Remarkably, the structural dynamics of the gold SL differ significantly from those of clean gold. Furthermore, the methylene lattice dynamics exhibit chain-length insensitivity but with a length-dependent retention time to reach full thermalization. Quantitatively, we find an agreement in the increased out-of-plane atomic motions between the surface gold atoms and the SAM methylene units, signifying the nature of motion-based coupling for interfacial energy transport. High interfacial thermal conductance (~300 MW/m^2/K) and high thermal conductivity for the methylene lattice (~60 W/m/K) are obtained under the condition of impulsive heating, which provide strong support for previous room-temperature theoretical predictions and also the ballistic nature of intrachain heat transfer. This time- and spatially-resolved experimental approach will enable future quantitative assessment of interfacial energy transport across solid-molecule junctions.

Cryo-electron tomography (cryo-ET) is a powerful modality for resolving cellular structures in their native state. While single-particle cryo-electron microscopy excels in determining protein structures purified from recombinant or endogenous sources due to an abundance of particles, weak contrast issues are accentuated in cryo-ET by low copy numbers in crowded cellular milieux. Continuous laser phase plates offer improved contrast in cryo-ET; however, their implementation demands exceptionally high-peak optical intensities. Instead, a novel experimental approach to enhance contrast in cryo-ET is to manipulate the phase of scattered pulsed electrons using ultrafast pulsed photons. Here, we outline the experimental design of a proof-of-concept electron microscope and demonstrate synchronization between electron packets and laser pulses. Furthermore, we show ultrabright photoemission of electrons from an alloy field emission tip using femtosecond ultraviolet pulses. These experiments pave the way toward exploring the utility of the ponderomotive effect using pulsed radiation to increase phase contrast in cryo-ET of subcellular protein complexes in situ, thus advancing the field of cell biology.

Rubrene is one of the leading organic semiconductors in scientific and industrial research, showing good conductivities and utilities in devices such as organic field-effect transistors. In these applications, the rubrene crystals often contact ionic liquids and other materials. Consequently, their surface properties and interfacial interactions influence the device’s performance. Although rubrene has been extensively studied with multiple structure characterization techniques, a complete description of the structure of rubrene single-crystal surfaces at the molecular level remains elusive. This study elucidates the molecular orientation and arrangement on the surface of rubrene single crystals with sum frequency generation (SFG) spectroscopy and reflection high-energy electron diffraction, respectively. The results confirm the near-surface unit cells with in-plane lattice parameters of a = 7.24 Å and b = 14.3 Å and an out-of-plane constant of c = 26.9 Å. Furthermore, the SFG analysis yields the tilt and rotation angles of θ = 15° and φ = 43° with respect to the crystalline c and a axes, respectively, and an in-plane twist of ψ = 3° for the surface phenyl rings.

Clathrate hydrates (CHs) are believed to exist in cold regions of space, such as comets and icy moons. While spectroscopic studies have explored their formation under similar laboratory conditions, direct structural characterization using diffraction techniques has remained elusive. We present the first electron diffraction study of tetrahydrofuran (THF) and 1,3-dioxolane (DIOX) CHs in the form of nanometer-thin ice films under an ultrahigh vacuum at cryogenic temperatures. Using reflection high-energy electron diffraction, we show that THF CH grows readily on various substrates during thermal annealing of an amorphous ice mixture of THF and water, and the formation is independent of the nature of the substrate. The growth of DIOX CHs on a Au(111) substrate is similar. A comparison of electron diffraction patterns with calculated X-ray diffraction patterns indicates that THF and DIOX form structure II CH (5¹²6⁴) with a lattice constant of ∼17.2 Å (cubic Fd3̅m). Both CHs were also grown on Ru(0001) and were examined by reflection absorption infrared spectroscopy. A direct comparison of diffraction data to infrared spectra as a function of the temperature further demonstrates the strength of multiple probes in examining complex systems possessing diverse molecular interactions.

Metals exhibit nonequilibrium electron and lattice subsystems at transient times following femtosecond laser excitation. In the past four decades, various optical spectroscopy and time-resolved diffraction methods have been used to study electron–phonon coupling and the effects of underlying dynamical processes. Here, we take advantage of the surface specificity of reflection ultrafast electron diffraction (UED) to examine the structural dynamics of photoexcited metal surfaces, which are apparently slower in recovery than predicted by thermal diffusion from the profile of absorbed energy. Fast diffusion of hot electrons is found to critically reduce surface excitation and affect the temporal dependence of the increased atomic motions on not only the ultrashort but also sub-nanosecond times. Whereas the two-temperature model with the accepted physical constants of platinum can reproduce the observed surface lattice dynamics, gold is found to exhibit appreciably larger-than-expected dynamic vibrational amplitudes of surface atoms while keeping the commonly used electron–phonon coupling constant. Such surface behavioral difference at transient times can be understood in the context of the different strengths of binding to surface atoms for the two metals. In addition, with the quantitative agreements between diffraction and theoretical results, we provide convincing evidence that surface structural dynamics can be reliably obtained by reflection UED even in the presence of laser-induced transient electric fields.

Metals exhibit nonequilibrium electron and lattice subsystems at transient times following femtosecond laser excitation. In the past four decades, various optical spectroscopy and time-resolved diffraction methods have been used to study electron-phonon coupling and the effects of underlying dynamical processes. Here, we take advantage of the surface specificity of reflection ultrafast electron diffraction (UED) to examine the structural dynamics of photoexcited metal surfaces, which are apparently slower in recovery than predicted by thermal diffusion from the profile of absorbed energy. Fast diffusion of hot electrons is found to critically reduce surface excitation and affect the temporal dependence of the increased atomic motions on not only the ultrashort but sub-nanosecond times. Whereas the two-temperature model with the accepted physical constants of platinum can reproduce the observed surface lattice dynamics, gold is found to exhibit appreciably larger-than-expected dynamic vibrational amplitudes of surface atoms while keeping the commonly used electron-phonon coupling constant. Such surface behavioral difference at transient times can be understood in the context of the different strengths of binding to surface atoms for the two metals. In addition, with the quantitative agreements between diffraction and theoretical results, we provide convincing evidence that surface structural dynamics can be reliably obtained by reflection UED even in the presence of laser-induced transient electric fields.

Revived attention in black phosphorus (bP) has been tremendous in the past decade. While many photoinitiated experiments have been conducted, a cross-examination of bP’s photocarrier and structural dynamics is still lacking. In this article, we provide such analysis by examining time-resolved data acquired using optical transient reflectivity and reflection ultrafast electron diffraction, two complementary methods under the same experimental conditions. At elevated excitation fluences, we find that more than 90% of the photoinjected carriers are annihilated within the first picosecond (ps) and transfer their energy to phonons in a nonthermal, anisotropic fashion. Electronically, the remaining carrier density around the band edges induces a significant interaction that leads to an interlayer lattice contraction in a few ps but soon diminishes as a result of the continuing loss of carriers. Structurally, phonon–phonon scattering redistributes the energy in the lattice and results in the generation of out-of-plane coherent acoustic phonons and thermal lattice expansion. Their onset times at ∼6 ps are found to be in good agreement. Later, a thermalized quasi-equilibrium state is reached following a period of about 40–50 ps. Hence, we propose a picture with five temporal regimes for bP’s photodynamics.

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.

Revived attention in black phosphorus (bP) has been tremendous in the past decade. While many photoinitiated experiments have been conducted, a cross-examination of bP's photocarrier and structural dynamics is still lacking. In this report, we provide such analysis by examining time-resolved data acquired using optical transient reflectivity and reflection ultrafast electron diffraction, two complementary methods under the same experimental conditions. At elevated excitation fluences, we find that more than 90% of the photoinjected carriers are annihilated within the first picosecond (ps) and transfer their energy to phonons in a nonthermal, anisotropic fashion. Electronically, the remaining carrier density around the band edges induces a significant interaction that leads to an interlayer lattice contraction in a few ps but soon diminishes as a result of the continuing loss of carriers. Structurally, phonon-phonon scattering redistributes the energy in the lattice and results in the generation of out-of-plane coherent acoustic phonons and thermal lattice expansion. Their onset times at ~6 ps are found to be in good agreement. Later, a thermalized quasi-equilibrium state is reached following a period of about 40-50 ps. Hence, we propose a picture with five temporal regimes for bP's photodynamics.