Exploring the Remarkably High Photocatalytic Efficiency of Ultra-Thin Porous Graphitic Carbon Nitride Nanosheets.

Graphitic carbon nitride (g-C3N4) is a metal-free photocatalyst used for visible-driven hydrogen production, CO2 reduction, and organic pollutant degradation. In addition to the most attractive feature of visible photoactivity, its other benefits include thermal and photochemical stability, cost-effectiveness, and simple and easy-scale-up synthesis. However, its performance is still limited due to its low absorption at longer wavelengths in the visible range, and high charge recombination. In addition, the exfoliated nanosheets easily aggregate, causing the reduction in specific surface area, and thus its photoactivity. Herein, we propose the use of ultra-thin porous g-C3N4 nanosheets to overcome these limitations and improve its photocatalytic performance. Through the optimization of a novel multi-step synthetic protocol, based on an initial thermal treatment, the use of nitric acid (HNO3), and an ultrasonication step, we were able to obtain very thin and well-tuned material that yielded exceptional photodegradation performance of methyl orange (MO) under visible light irradiation, without the need for any co-catalyst. About 96% of MO was degraded in as short as 30 min, achieving a normalized apparent reaction rate constant (k) of 1.1 × 10-2 min-1mg-1. This represents the highest k value ever reported using C3N4-based photocatalysts for MO degradation, based on our thorough literature search. Ultrasonication in acid not only prevents agglomeration of g-C3N4 nanosheets but also tunes pore size distribution and plays a key role in this achievement. We also studied their performance in a photocatalytic hydrogen evolution reaction (HER), achieving a production of 1842 µmol h-1 g-1. Through a profound analysis of all the samples' structure, morphology, and optical properties, we provide physical insight into the improved performance of our optimized porous g-C3N4 sample for both photocatalytic reactions. This research may serve as a guide for improving the photocatalytic activity of porous two-dimensional (2D) semiconductors under visible light irradiation.

Surface engineering of two-dimensional hexagonal boron-nitride for optoelectronic devices.

Two-dimensional hexagonal boron nitride (2D h-BN) is being extensively studied in optoelectronic devices due to its electronic and photonic properties. However, the controlled optimization of h-BN's insulating properties is necessary to fully explore its potential in energy conversion and storage devices. In this work, we engineered the surface of h-BN nanoflakes via one-step in situ chemical functionalization using a liquid-phase exfoliation approach. The functionalized h-BN (F-h-BN) nanoflakes were subsequently dispersed on the surface of TiO2 to tune the TiO2/QDs interface of the optoelectronic device. The photoelectrochemical (PEC) devices based on TiO2/F-h-BN/QDs with optimized addition of carbon nanotubes (CNTs) and scattering layers showed 46% improvement compared to the control device (TiO2/QDs). This significant improvement is attributed to the reduced trap/carrier recombination and enhanced carrier injection rate of the TiO2-CNTs/F-h-BN/QDs photoanode. Furthermore, by employing an optimized TiO2-CNTs/F-h-BN/QDs photoanode, QDs-sensitized solar cells (QDSCs) yield an 18% improvement in photoconversion efficiency. This represents a potential and adaptability of our approach, and pathway to explore surface-engineered 2D materials to optimize the interface of solar energy conversion and other emerging optoelectronic devices.

Imaging Photon-Induced Near-Field Distributions of a Plasmonic, Self-Assembled Vesicle by a Laser-Integrated Electron Microscope.

Plasmonic polymeric nanoassemblies offer valuable opportunities in photoconversion applications. Localized surface plasmon mechanisms behind such nanoassemblies govern their functionalities under light illumination. However, an in-depth investigation at the single nanoparticle (NP) level is still challenging, especially when the buried interface is involved, due to the availability of suitable techniques. Here, we synthesized an anisotropic heterodimer composed of a self-assembled polymer vesicle (THPG) capped with a single gold NP, enabling an 8-fold enhancement in hydrogen generation compared to the nonplasmonic THPG vesicle. We explored the anisotropic heterodimer at the single particle level by employing advanced transmission electron microscopes, including one equipped with a femtosecond pulsed laser, which allows us to visualize the polarization- and frequency-dependent distribution of the enhanced electric near fields at the vicinity of Au cap and Au-polymer interface. These elaborated fundamental findings may guide designing new hybrid nanostructures tailored for plasmon-related applications.

Single-shot ultrafast terahertz photography.

Multidimensional imaging of transient events has proven pivotal in unveiling many fundamental mechanisms in physics, chemistry, and biology. In particular, real-time imaging modalities with ultrahigh temporal resolutions are required for capturing ultrashort events on picosecond timescales. Despite recent approaches witnessing a dramatic boost in high-speed photography, current single-shot ultrafast imaging schemes operate only at conventional optical wavelengths, being suitable solely within an optically-transparent framework. Here, leveraging on the unique penetration capability of terahertz radiation, we demonstrate a single-shot ultrafast terahertz photography system that can capture multiple frames of a complex ultrafast scene in non-transparent media with sub-picosecond temporal resolution. By multiplexing an optical probe beam in both the time and spatial-frequency domains, we encode the terahertz-captured three-dimensional dynamics into distinct spatial-frequency regions of a superimposed optical image, which is then computationally decoded and reconstructed. Our approach opens up the investigation of non-repeatable or destructive events that occur in optically-opaque scenarios.

Enhancing Efficiency of Nonfullerene Organic Solar Cells via Using Polyelectrolyte-Coated Plasmonic Gold Nanorods as Rear Interfacial Modifiers.

Sufficient sunlight absorption and exciton generation are critical for developing efficient nonfullerene organic solar cells (OSCs). In this work, polyelectrolyte polystyrenesulfonate (PSS)-coated plasmonic gold nanorods (GNRs@PSS) were incorporated, for the first time, into the inverted nonfullerene OSCs as rear interfacial modifiers to improve sunlight absorption and charge generation via the near-field plasmonic and backscattering effects. The plasmonic GNRs effectively improved the sunlight absorption and enhanced the charge generation. Meanwhile, the negatively charged PSS shell ensured the uniform dispersion of the GNRs on the surface of the photoactive layer, optimized the interfacial contact, and further promoted the hole transport to the electrode. These concerted synergistic effects augmented the efficiency (10.11%) by nearly 20% relative to the control device (8.47%). Remarkably, the ultrathin (∼2.2 nm) organic layer on the surface of GNRs was closely examined by acquiring the carbon contrast image through energy-filtered transmission electron microscopy (EF-TEM), which clearly confirmed the coating uniformity from the side to end-cap of GNRs. The surface plasmon resonance (SPR) effect of the GNRs@PSS on the surface of the photoactive layer was unprecedentedly mapped by photoinduced force microscopy (PiFM) under the illumination of a tunable wavelength supercontinuum laser mimicking sunlight. Furthermore, investigations into the effect of size, surface coverage, and incorporation location of GNRs@PSS on the performance of OSCs revealed that the appropriate design and incorporation of the plasmonic nanostructures are crucial, otherwise the performance can be decreased, as evidenced in the case of front interface integration.

Versatile metal-wire waveguides for broadband terahertz signal processing and multiplexing.

Waveguides play a pivotal role in the full deployment of terahertz communication systems. Besides signal transporting, innovative terahertz waveguides are required to provide versatile signal-processing functionalities. Despite fundamental components, such as Bragg gratings, have been recently realized, they typically rely on complex hybridization, in turn making it extremely challenging to go beyond the most elementary functions. Here, we propose a universal approach, in which multiscale-structured Bragg gratings can be directly etched on metal-wires. Such an approach, in combination with diverse waveguide designs, allows for the realization of a unique platform with remarkable structural simplicity, yet featuring unprecedented signal-processing capabilities. As an example, we introduce a four-wire waveguide geometry, amenable to support the low-loss and low-dispersion propagation of polarization-division multiplexed terahertz signals. Furthermore, by engraving on the wires judiciously designed Bragg gratings based on multiscale structures, it is possible to independently manipulate two polarization-division multiplexed terahertz signals. This platform opens up new exciting perspectives for exploiting the polarization degree of freedom and ultimately boosting the capacity and spectral efficiency of future terahertz networks.

3D Nanoscale Morphology Characterization of Ternary Organic Solar Cells.

It is highly desired to develop advanced characterization techniques to explore the 3D nanoscale morphology of the complicated blend film of ternary organic solar cells (OSCs). Here, ternary OSCs are constructed by incorporating the nonfullerene acceptor perylenediimide (PDI)-diketopyrrolopyrrole (DPP)-PDI and their morphology is characterized in depth to understand the performance variation. In particular, photoinduced force microscopy (PiFM) coupled with infrared laser spectroscopy is conducted to qualitatively study the distribution of donor and acceptors in the blend film by chemical identification and to quantitatively probe the segmentation of domains and the domain size distribution after PDI-DPP-PDI acceptor incorporation by PiFM imaging and data processing. In addition, the energy-filtered transmission electron microscopy with energy loss spectra is utilized to visualize the nanoscale morphology of ultrathin cross-sections in the configuration of the real ternary device for the first time in the field of photovoltaics. These measurements allow to "view" the surface and cross-sectional morphology and provide strong evidence that the PDI-DPP-PDI acceptor can suppress the aggregation of the fullerene molecules and generate the homogenous morphology with a higher-level of the molecularly mixed phase, which can prevent the charge recombination and stabilize the morphology of photoactive layer.

Phase-enabled metal-organic framework homojunction for highly selective CO2 photoreduction.

Conversion of clean solar energy to chemical fuels is one of the promising and up-and-coming applications of metal-organic frameworks. However, fast recombination of photogenerated charge carriers in these frameworks remains the most significant limitation for their photocatalytic application. Although the construction of homojunctions is a promising solution, it remains very challenging to synthesize them. Herein, we report a well-defined hierarchical homojunction based on metal-organic frameworks via a facile one-pot synthesis route directed by hollow transition metal nanoparticles. The homojunction is enabled by two concentric stacked nanoplates with slightly different crystal phases. The enhanced charge separation in the homojunction was visualized by in-situ surface photovoltage microscopy. Moreover, the as-prepared nanostacks displayed a visible-light-driven carbon dioxide reduction with very high carbon monooxide selectivity, and excellent stability. Our work provides a powerful platform to synthesize capable metal-organic framework complexes and sheds light on the hierarchical structure-function relationships of metal-organic frameworks.

Homodyne Solid-State Biased Coherent Detection of Ultra-Broadband Terahertz Pulses with Static Electric Fields.

We present an innovative implementation of the solid-state-biased coherent detection (SSBCD) technique, which we have recently introduced for the reconstruction of both amplitude and phase of ultra-broadband terahertz pulses. In our previous works, the SSBCD method has been operated via a heterodyne scheme, which involves demanding square-wave voltage amplifiers, phase-locked to the THz pulse train, as well as an electronic circuit for the demodulation of the readout signal. Here, we demonstrate that the SSBCD technique can be operated via a very simple homodyne scheme, exploiting plain static bias voltages. We show that the homodyne SSBCD signal turns into a bipolar transient when the static field overcomes the THz field strength, without the requirement of an additional demodulating circuit. Moreover, we introduce a differential configuration, which extends the applicability of the homodyne scheme to higher THz field strengths, also leading a two-fold improvement of the dynamic range compared to the heterodyne counterpart. Finally, we demonstrate that, by reversing the sign of the static voltage, it is possible to directly retrieve the absolute THz pulse polarity. The homodyne configuration makes the SSBCD technique of much easier access, leading to a vast range of field-resolved applications.

Optical resonances of hollow nanocubes controlled with sub-particle structural morphologies.

The structural details of nanoparticles at the sub-particle level are critical for our understanding of their functionalities and the basic mechanisms involved in their formation. In particular, the geometries of such features determine the particle's overall optical response. Hollow metallic nanoparticles (hollow-MNPs) that have cubic geometries, with varying morphologies on their walls and voids in their body, offer a platform to study the effects of such structural features on the properties of single nanoparticles and their ensemble. Here, we report the control over sub-particle pinholes and voids by modifying the dynamics of the galvanic reaction, and we connect these structures to the optical response of the hollow nanocubes. We observe that symmetry breakage in individual particles, caused by pinholes and voids, has a drastic effect on the plasmon-resonance peak positions in their UV-Vis-NIR spectra. Via electron microscopy imaging, statistical analyses, and electromagnetic simulations, we observe that enlargement in a pinhole's diameter and an increase in their number produce a redshift in the resonance absorption peak of the ensemble. Our results outline nanoparticle design avenues via sub-particle morphologies for several applications, including those operating in the biological window and those carrying chemical payloads in organisms.

Single-shot real-time sub-nanosecond electron imaging aided by compressed sensing: Analytical modeling and simulation.

Bringing ultrafast (nanosecond and below) temporal resolution to transmission electron microscopy (TEM) has historically been challenging. Despite significant recent progress in this direction, it remains difficult to achieve sub-nanosecond temporal resolution with a single electron pulse, in real-time (i.e., duration in which the event occurs) imaging. To address this limitation, here, we propose a methodology that combines laser-assisted TEM with computational imaging methodologies based on compressed sensing (CS). In this technique, a two-dimensional (2D) transient event [i.e. (x,y) frames that vary in time] is recorded through a CS paradigm, which consists of spatial encoding, temporal shearing via streaking, and spatiotemporal integration of an electron pulse. The 2D image generated on a camera is used to reconstruct the datacube of the ultrafast event, with two spatial and one temporal dimensions, via a CS-based image reconstruction algorithm. Using numerical simulation, we find that the reconstructed results are in good agreement with the ground truth, which demonstrates the applicability of CS-based computational imaging methodologies to laser-assisted TEM. Our proposed method, complementing the existing ultrafast stroboscopic and nanosecond single-shot techniques, opens up the possibility for single-shot, real-time, spatiotemporal imaging of irreversible structural phenomena with sub-nanosecond temporal resolution.

Thickness measurements using photonic modes in monochromated electron energy-loss spectroscopy.

Characteristic energies of photonic modes are a sensitive function of a nanostructures' geometrical parameters. In the case of translationally invariant planar waveguides, the eigen-energies reside in the infrared to ultraviolet parts of the optical spectrum and they sensitively depend on the thickness of the waveguide. Using swift electrons and the inherent Cherenkov radiation in dielectrics, the energies of such photonic states can be effectively probed via monochromated electron energy-loss spectroscopy (EELS). Here, by exploiting the strong photonic signals in EELS with 200 keV electrons, we correlate the energies of waveguide peaks in the 0.5-3.5 eV range with planar thicknesses of the samples. This procedure enables us to measure the thicknesses of cross-sectional transmission electron microscopy samples over a 1-500 nm range and with best-case accuracies below ± 2%. The measurements are absolute with the only requirement being the optical dielectric function of the material. Furthermore, we provide empirical formulation for rapid and direct thickness estimations for a 50-500 nm range. We demonstrate the methodology for two semiconducting materials, silicon and gallium arsenide, and discuss how it can be applied to other dielectrics that produce strong optical fingerprints in EELS. The asymptotic form of the loss function for two-dimensional materials is also discussed.

Graphene-layered steps and their fields visualized by 4D electron microscopy.

Enhanced image contrast has been seen at graphene-layered steps a few nanometers in height by means of photon-induced near-field electron microscopy (PINEM) using synchronous femtosecond pulses of light and electrons. The observed steps are formed by the edges of graphene strips lying on the surface of a graphene substrate, where the strips are hundreds of nanometers in width and many micrometers in length. PINEM measurements reflect the interaction of imaging electrons and induced (near) electric fields at the steps, and this leads to a much higher contrast than that achieved in bright-field transmission electron microscopy imaging of the same strips. Theory and numerical simulations support the experimental PINEM findings and elucidate the nature of the electric field at the steps formed by the graphene layers. These results extend the range of applications of the experimental PINEM methodology, which has previously been demonstrated for spherical, cylindrical, and triangular nanostructures, to shapes of high aspect ratio (rectangular strips), as well as into the regime of atomic layer thicknesses.

Entangled nanoparticles: discovery by visualization in 4D electron microscopy.

Particle interactions are fundamental to our understanding of nanomaterials and biological assemblies. Here, we report on the visualization of entangled particles, separated by as large as 70 nm, and the discovery of channels in their near-fields. For silver nanoparticles, the induced field of each particle extends to 50-100 nm, but when particles are brought close in separation we observe channels as narrow as 6 nm, a width that is 2 orders of magnitude smaller than the incident field wavelength. The channels' directions can be controlled by the polarization of the incident field, particle size, and separation. For this direct visualization of these nanoscopic near-fields, the high spatial, temporal, and energy resolutions needed were hitherto not possible without the methodology given here. This methodology, we anticipate, paves the way for further fundamental studies of particle entanglement and for possible applications spanning materials and macromolecular assemblies.

Ultrafast Kikuchi diffraction: nanoscale stress-strain dynamics of wave-guiding structures.

Complex structural dynamics at the nanoscale requires sufficiently small probes to be visualized. In conventional imaging using electron microscopy, the dimension of the probe is large enough to cause averaging over the structures present. However, by converging ultrafast electron bunches, it is possible to select a single nanoscale structure and study the dynamics, either in the image or using electron diffraction. Moreover, the span of incident wave vectors in a convergent beam enables sensitivity levels and information contents beyond those of parallel-beam illumination with a single wave vector Bragg diffraction. Here, we report the observation of propagating strain waves using ultrafast Kikuchi diffraction from nanoscale volumes within a wedge-shaped silicon single crystal. It is found that the heterogeneity of the strain in the lateral direction is only 100 nm. The transient elastic wave gives rise to a coherent oscillation with a period of 30 ps and with an envelope that has a width of 140 ps. The origin of this elastic deformation is theoretically examined using finite element analysis; it is identified as propagating shear waves. The wedge-shaped structure, unlike parallel-plate structure, is the key behind the traveling nature of the waves as its angle permits "transverse" propagation; the parallel-plate structure only exhibits the "longitudinal" motion. The studies reported suggest extension to a range of applications for nanostructures of different shapes and for exploring their ultrafast eigen-modes of stress-strain profiles.

Direct visualization of near-fields in nanoplasmonics and nanophotonics.

Electric fields of nanoscale particles are fundamental to our understanding of nanoplasmonics and nanophotonics. Success has been made in developing methods to probe the effect of their presence, but it remains difficult to directly image optically induced electric fields at the nanoscale and especially when ensembles of particles are involved. Here, using ultrafast electron microscopy, we report the space-time visualization of photon-induced electric fields for ensembles of silver nanoparticles having different sizes, shapes, and separations. The high-field-of-view measurements enable parallel processing of many particles in the ensemble with high throughput of information. Directly in the image, the evanescent fields are observed and visualized when the particles are polarized with the optical excitation. Because the particle size is smaller than the wavelength of light, the near-fields are those of nanoplasmonics and are precursors of far-field nanophotonics. The reported results pave the way for quantitative studies of fields in ensembles of complex morphologies with the nanoparticles being embedded or interfacial.

Subparticle ultrafast spectrum imaging in 4D electron microscopy.

Single-particle imaging of structures has become a powerful methodology in nanoscience and molecular and cell biology. We report the development of subparticle imaging with space, time, and energy resolutions of nanometers, femtoseconds, and millielectron volts, respectively. By using scanning electron probes across optically excited nanoparticles and interfaces, we simultaneously constructed energy-time and space-time maps. Spectrum images were then obtained for the nanoscale dielectric fields, with the energy resolution set by the photon rather than the electron, as demonstrated here with two examples (silver nanoparticles and the metallic copper-vacuum interface). This development thus combines the high spatial resolution of electron microscopy with the high energy resolution of optical techniques and ultrafast temporal response, opening the door to various applications in elemental analysis as well as mapping of interfaces and plasmonics.

Kikuchi ultrafast nanodiffraction in four-dimensional electron microscopy.

Coherent atomic motions in materials can be revealed using time-resolved X-ray and electron Bragg diffraction. Because of the size of the beam used, typically on the micron scale, the detection of nanoscale propagating waves in extended structures hitherto has not been reported. For elastic waves of complex motions, Bragg intensities contain all polarizations and they are not straightforward to disentangle. Here, we introduce Kikuchi diffraction dynamics, using convergent-beam geometry in an ultrafast electron microscope, to selectively probe propagating transverse elastic waves with nanoscale resolution. It is shown that Kikuchi band shifts, which are sensitive only to the tilting of atomic planes, reveal the resonance oscillations, unit cell angular amplitudes, and the polarization directions. For silicon, the observed wave packet temporal envelope (resonance frequency of 33 GHz), the out-of-phase temporal behavior of Kikuchi's edges, and the magnitude of angular amplitude (0.3 mrad) and polarization elucidate the nature of the motion: one that preserves the mass density (i.e., no compression or expansion) but leads to sliding of planes in the antisymmetric shear eigenmode of the elastic waveguide. As such, the method of Kikuchi diffraction dynamics, which is unique to electron imaging, can be used to characterize the atomic motions of propagating waves and their interactions with interfaces, defects, and grain boundaries at the nanoscale.

4D nanoscale diffraction observed by convergent-beam ultrafast electron microscopy.

Diffraction with focused electron probes is among the most powerful tools for the study of time-averaged nanoscale structures in condensed matter. Here, we report four-dimensional (4D) nanoscale diffraction, probing specific site dynamics with 10 orders of magnitude improvement in time resolution, in convergent-beam ultrafast electron microscopy (CB-UEM). As an application, we measured the change of diffraction intensities in laser-heated crystalline silicon as a function of time and fluence. The structural dynamics (change in 7.3 +/- 3.5 picoseconds), the temperatures (up to 366 kelvin), and the amplitudes of atomic vibrations (up to 0.084 angstroms) are determined for atoms strictly localized within the confined probe area (10 to 300 nanometers in diameter). We anticipate a broad range of applications for CB-UEM and its variants, especially in the studies of single particles and heterogeneous structures.

Nanomechanical motions of cantilevers: direct imaging in real space and time with 4D electron microscopy.

The function of many nano- and microscale systems is revealed when they are visualized in both space and time. Here, we report our first observation, using four-dimensional (4D) electron microscopy, of the nanomechanical motions of cantilevers. From the observed oscillations of nanometer displacements as a function of time, for free-standing beams, we are able to measure the frequency of modes of motion and determine Young's elastic modulus and the force and energy stored during the optomechanical expansions. The motion of the cantilever is triggered by molecular charge redistribution as the material, single-crystal organic semiconductor, switches from the equilibrium to the expanded structure. For these material structures, the expansion is colossal, typically reaching the micrometer scale, the modulus is 2 GPa, the force is 600 microN, and the energy is 200 pJ. These values translate to a large optomechanical efficiency (minimum of 1% and up to 10% or more) and a pressure of nearly 1,500 atm. We note that the observables here are real material changes in time, in contrast to those based on changes of optical/contrast intensity or diffraction.