Switching of electrochemical selectivity due to plasmonic field-induced dissociation.

Electrochemical reactivity is known to be dictated by the structure and composition of the electrocatalyst-electrolyte interface. Here, we show that optically generated electric fields at this interface can influence electrochemical reactivity insofar as to completely switch reaction selectivity. We study an electrocatalyst composed of gold-copper alloy nanoparticles known to be active toward the reduction of CO2 to CO. However, under the action of highly localized electric fields generated by plasmonic excitation of the gold-copper alloy nanoparticles, water splitting becomes favored at the expense of CO2 reduction. Real-time time-dependent density functional tight binding calculations indicate that optically generated electric fields promote transient-hole-transfer-driven dissociation of the O─H bond of water preferentially over transient-electron-driven dissociation of the C─O bond of CO2. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.

Picosecond carrier dynamics in InAs and GaAs revealed by ultrafast electron microscopy.

Understanding the limits of spatiotemporal carrier dynamics, especially in III-V semiconductors, is key to designing ultrafast and ultrasmall optoelectronic components. However, identifying such limits and the properties controlling them has been elusive. Here, using scanning ultrafast electron microscopy, in bulk n-GaAs and p-InAs, we simultaneously measure picosecond carrier dynamics along with three related quantities: subsurface band bending, above-surface vacuum potentials, and surface trap densities. We make two unexpected observations. First, we uncover a negative-time contrast in secondary electrons resulting from an interplay among these quantities. Second, despite dopant concentrations and surface state densities differing by many orders of magnitude between the two materials, their carrier dynamics, measured by photoexcited band bending and filling of surface states, occur at a seemingly common timescale of about 100 ps. This observation may indicate fundamental kinetic limits tied to a multitude of material and surface properties of optoelectronic III-V semiconductors and highlights the need for techniques that simultaneously measure electro-optical kinetic properties.

In Situ Electron Microscopy of Transformations of Copper Nanoparticles under Plasmonic Excitation.

Metal nanoparticles are attracting interest for their light-absorption properties, but such materials are known to dynamically evolve under the action of chemical and physical perturbations, resulting in changes in their structure and composition. Using a transmission electron microscope equipped for optical excitation of the specimen, the structural evolution of Cu-based nanoparticles under simultaneous electron beam irradiation and plasmonic excitation was investigated with high spatiotemporal resolution. These nanoparticles initially have a Cu core-Cu2O oxide shell structure, but over the course of imaging, they undergo hollowing via the nanoscale Kirkendall effect. We captured the nucleation of a void within the core, which then rapidly grows along specific crystallographic directions until the core is hollowed out. Hollowing is triggered by electron-beam irradiation; plasmonic excitation enhances the kinetics of the transformation likely by the effect of photothermal heating.

Time-resolved transmission electron microscopy for nanoscale chemical dynamics.

The ability of transmission electron microscopy (TEM) to image a structure ranging from millimetres to Ångströms has made it an indispensable component of the toolkit of modern chemists. TEM has enabled unprecedented understanding of the atomic structures of materials and how structure relates to properties and functions. Recent developments in TEM have advanced the technique beyond static material characterization to probing structural evolution on the nanoscale in real time. Accompanying advances in data collection have pushed the temporal resolution into the microsecond regime with the use of direct-electron detectors and down to the femtosecond regime with pump-probe microscopy. Consequently, studies have deftly applied TEM for understanding nanoscale dynamics, often in operando. In this Review, time-resolved in situ TEM techniques and their applications for probing chemical and physical processes are discussed, along with emerging directions in the TEM field.

Plasmon-Assisted Ammonia Electrosynthesis.

Ammonia is a promising liquid-phase carrier for the storage, transport, and deployment of carbon-free energy. However, the realization of an ammonia economy is predicated on the availability of green methods for the production of ammonia powered by electricity from renewable sources or by solar energy. Here, we demonstrate the synthesis of ammonium from nitrate powered by a synergistic combination of electricity and light. We use an electrocatalyst composed of gold nanoparticles, which have dual attributes of electrochemical nitrate reduction activity and visible-light-harvesting ability due to their localized surface plasmon resonances. Plasmonic excitation of the electrocatalyst induces ammonium synthesis with up to a 15× boost in activity relative to conventional electrocatalysis. We devise a strategy to account for the effect of photothermal heating of the electrode surface, which allows the observed enhancement to be attributed to non-thermal effects such as energetic carriers and charged interfaces induced by plasmonic excitation. The synergy between electrochemical activation and plasmonic activation is the most optimal at a potential close to the onset of nitrate reduction. Plasmon-assisted electrochemistry presents an opportunity for conventional limits of electrocatalytic conversion to be surpassed due to non-equilibrium conditions generated by plasmonic excitation.

Transient lensing from a photoemitted electron gas imaged by ultrafast electron microscopy.

Understanding and controlling ultrafast charge carrier dynamics is of fundamental importance in diverse fields of (quantum) science and technology. Here, we create a three-dimensional hot electron gas through two-photon photoemission from a copper surface in vacuum. We employ an ultrafast electron microscope to record movies of the subsequent electron dynamics on the picosecond-nanosecond time scale. After a prompt Coulomb explosion, the subsequent dynamics is characterized by a rapid oblate-to-prolate shape transformation of the electron gas, and periodic and long-lived electron cyclotron oscillations inside the magnetic field of the objective lens. In this regime, the collective behavior of the oscillating electrons causes a transient, mean-field lensing effect and pronounced distortions in the images. We derive an analytical expression for the time-dependent focal length of the electron-gas lens, and perform numerical electron dynamics and probe image simulations to determine the role of Coulomb self-fields and image charges. This work inspires the visualization of cyclotron dynamics inside two-dimensional electron-gas materials and enables the elucidation of electron/plasma dynamics and properties that could benefit the development of high-brightness electron and X-ray sources.

Experimental Demonstration of an Electride as a 2D Material.

Because of their loosely bound electrons, electrides offer physical properties useful in chemical synthesis and electronics. For these applications and others, nanosized electrides offer advantages, but to-date no electride has been synthesized as a nanomaterial. We demonstrate experimentally that Ca2N, a layered electride in which layers of atoms are separated by layers of a 2D electron gas (2DEG), can be exfoliated into two-dimensional (2D) nanosheets using liquid exfoliation. The 2D flakes are stable in a nitrogen atmosphere or in select organic solvents for at least one month. Electron microscopy and elemental analysis reveal that the 2D flakes retain the crystal structure and stoichiometry of the parent 3D Ca2N. In addition, the 2D flakes exhibit metallic character and an optical response that agrees with DFT calculations. Together these findings suggest that the 2DEG is preserved in the 2D material. With this work, we bring electrides into the nanoregime and experimentally demonstrate a 2D electride, Ca2N.