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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.

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.

We report the design and fabrication of a heterojunction photoanode consisting of two-dimensional (2D) functionalized hexagonal boron nitride (F-h-BN) nanoflakes, introduced at the interface between SnO2 and quantum dots (QDs) (e.g. CdS and CdS–CdSe), used as a photoanode in a photoelectrochemical cell (PEC) for hydrogen (H2) generation. We highlight the effect of 2D F-h-BN nanoflakes on the carrier recombination and performance of the PEC system. In addition, the tailoring of SnO2 film thickness and incorporation of multi-walled carbon nanotubes (MWCNTs) were investigated for their effect on carrier dynamics and overall device performance. Our results show that a PEC device based on SnO2/F-h-BN/CdS QDs exhibits a 60% improvement in the saturated photocurrent density (at 1.0 V vs. RHE) compared to the control device, due to improved electron injection and reduced carrier recombination at the metal oxide/QDs/electrolyte interface. The highest saturated photocurrent density value reached 6.35 mA cm−2 (at 1.0 V vs. RHE), after thickness optimization of the SnO2 film, incorporation (0.015 wt%) of MWCNTs, and cascade CdS–CdSe QDs. In addition, the PEC system maintains 98% of the initial value of photocurrent density after four hours of continuous one sun illumination (AM 1.5G, 100 mW cm−2). Our results offer a simple yet cost-effective and efficient strategy to enhance the performance of QD based PEC H2 generation and potentially other optoelectronic devices.

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.

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.

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.

Saving energy and designing an environmentally friendly atmosphere in modern buildings will require smart windows that can adapt to a variety of conditions and requirements, such as weather, human load and personal desire. The key element of such windows is the material system that transmits light in and out of the building in a controlled manner. To address the need for such a system, here we report the fabrication of novel, flexible, large-area devices that are based on suspended organometallic nanorods. As a result of the detailed characterization and extensive optimization of nanorod synthesis and device fabrication, our fabricated devices achieve superior optical and stability performances, with optical modulation as high as 73.7% (the highest value reported to date) and bending capability up to ∼180 degrees without any structural damage. This performance is further reinforced by repeated switching testing between high (“on”) and low (“off”) optical transmittance states over 500 cycles. Finally, we are able to scale up the fabrication of such devices to large areas (24 cm by 9 cm, size limited by our laboratory-scale doctor blade), underlining the possibility of adopting the results reported herein for future flexible smart windows and electronics. An interesting finding that the eventual SPD performance is indeed largely dependent on the diameter of the nanorods instead of their aspect ratios provides useful guidelines for future development.

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.

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.

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.

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.

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.