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.

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.

Optimization and performance of nitrogen-doped carbon dots as a color conversion layer for white-LED applications.

In this study, green-emitting nitrogen-doped carbon dots (N-CDots) were synthesized and incorporated into drop-cast composite films for use as color conversion layers in a white-LED configuration to generate white light. In order to resolve the red deficiency of this configuration, a commercial red phosphor was integrated into the system. Moreover, the N-CDots were also processed into polymer/N-CDot composite fibers, for which we determined the amount of N-CDots that yielded adequate white-light properties. Finally, we showed that white light with excellent properties could be generated by employing both of the fabricated N-CDot composites either as drop-cast films or composite fibers. Hence, N-CDots provide a promising alternative to inorganic phosphors that are commonly employed in white-LED configurations.

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.

Green fabrication of lanthanide-doped hydroxide-based phosphors: Y(OH)3:Eu3+ nanoparticles for white light generation.

Phosphors can serve as color conversion layers to generate white light with varying optical features, including color rendering index (CRI), high correlated color temperature (CCT), and luminous efficacy. However, they are typically produced under harsh synthesis conditions such as high temperature, high pressure, and/or by employing a large amount of solvent. In this work, a facile, water-based, rapid method has been proposed to fabricate lanthanide-doped hydroxide-based phosphors. In this sense, sub-micrometer-sized Y(OH)3:Eu3+ particles (as red phosphor) were synthesized in water at ambient conditions in ≤60 min reaction time. The doping ratio was controlled from 2.5-20 mol %. Additionally, first principle calculations were performed on Y(OH)3:Eu3+ to understand the preferable doping scenario and its optoelectronic properties. As an application, these fabricated red phosphors were integrated into a PDMS/YAG:Ce3+ composite and used to generate white light. The resulting white light showed a remarkable improvement (≈24%) in terms of luminous efficiency, a slight reduction of CCT (from 3900 to 3600 K), and an unchanged CRI (≈60) as the amount of Y(OH)3:Eu3+ was increased.

Phosphor-based white LED by various glassy particles: control over luminous efficiency.

Generating white light through a mainstream remote phosphor design suffers from phosphor conversion efficiency loss due to a backscattering of light. Such a loss also reduces luminous efficiency of the resulting white light. To overcome this issue, various glassy scatterers with different morphologies such as glass bubbles, glass beads, and nanosized silica particles were employed as scatterers, together with a fixed amount of yellow phosphor (YAG:Ce3+) and a poly(dimethylsiloxane) (PDMS) matrix. In addition, the simulation of the system validates the rigorous multiple scattering of the incoming light most probably due to refractive index mismatch between the glass bubbles and surrounding PDMS matrix along with the internal reflections.

Polarized emission from CsPbBr3 nanowire embedded-electrospun PU fibers.

Interest in all-inorganic halide perovskites has been increasing dramatically due to their high quantum yield, band gap tunability, and ease of fabrication in compositional and geometric diversity. In this study, we synthesized several hundreds of nanometer long and ∼4 nm thick CsPbBr 3 nanowires (NWs). They were then integrated into electrospun polyurethane (PU) fibers to examine the polarization behavior of the composite fiber assembly. Aligned electrospun fibers containing CsPbBr 3 NWs showed a remarkable increase in the degree of polarization from 0.17-0.30. This combination of NWs and PU fibers provides a promising composite material for various applications such as optoelectronic devices and solar cells.

A BODIPY-Based Fluorescent Probe to Visually Detect Phosgene: Toward the Development of a Handheld Phosgene Detector.

A boron-dipyrromethene (BODIPY)-based fluorescent probe with a phosgene-specific reactive motif shows remarkable selectivity toward phosgene, in the presence of which the nonfluorescent dye rapidly transforms into a new structure and induces a fluorescent response clearly observable to the naked eye under ultraviolet light. Given that dynamic, a prototypical handheld phosgene detector with a promising sensing capability that expedites the detection of gaseous phosgene without sophisticated instrumentation was developed. The proposed method using the handheld detector involves a rapid response period suitable for issuing early warnings during emergency situations.

Null Extinction of Ceria@silica Hybrid Particles: Transparent Polystyrene Composites.

Scattering of light in optical materials, particularly in composites based on transparent polymer and inorganic pigment nanoparticles, is a chronic problem. It might originate mainly from light scattering because of a refractive index mismatch between the particles and transparent polymer matrix. Thus, the intensity of light is rapidly diminished and optical transparency is reduced. Refractive index matching between the pigment core and the surrounding transparent matrix using a secondary component at the interface (shell) has recently appeared as a promising approach to alter light scattering. Here, CeO2 (ceria) nanoparticles with a diameter of 25 nm are coated with a SiO2 (silica) shell with various thicknesses in a range of 6.5-67.5 nm using the Stöber method. When the hybrid core-shell particles are dispersed into transparent polystyrene (PS), the transmission of the freestanding PS composite films increases over both the ultraviolet (UV) and visible region as the shell thickness increases particularly at 37.5 nm. The increase of transmission can be attributed to the reduction in the scattering coefficient of the hybrid particles. On the other hand, the particles in tetrahydrofuran (THF) absorb over UV and the intensity of absorption shows a systematic decrease as the shell thickness increases. Thus, the silica shell suppresses not only the scattering coefficient but also the molar absorptivity of the core ceria particles. The experimental results regarding the target shell thickness to develop low extinction (scattering + absorption) composites show a qualitative agreement with the predictions of Effective Medium Theory.