Ultrafast all-optical second harmonic wavefront shaping.

Optical communication can be revolutionized by encoding data into the orbital angular momentum of light beams. However, state-of-the-art approaches for dynamic control of complex optical wavefronts are mainly based on liquid crystal spatial light modulators or miniaturized mirrors, which suffer from intrinsically slow (µs-ms) response times. Here, we experimentally realize a hybrid meta-optical system that enables complex control of the wavefront of light with pulse-duration limited dynamics. Specifically, by combining ultrafast polarization switching in a WSe2 monolayer with a dielectric metasurface, we demonstrate second harmonic beam deflection and structuring of orbital angular momentum on the femtosecond timescale. Our results pave the way to robust encoding of information for free space optical links, while reaching response times compatible with real-world telecom applications.

Colloidal Plasmonic TiN Nanoparticles for Efficient Solar Seawater Desalination.

Transferring traditional plasmonic noble metal nanomaterials from the laboratory to industrial production has remained challenging due to the high price of noble metals. The development of cost-effective non-noble-metal alternatives with outstanding plasmonic properties has therefore become essential. Herein, we report on the gram-scale production of differently shaped TiN nanoparticles with strong plasmon-enabled broadband light absorption, including differently sized TiN nanospheres, nanobipyramids, and nanorod arrays. The TiN nanospheres and nanobipyramids are further coembedded in highly porous poly(vinyl alcohol) films to function as a photothermal material for solar seawater desalination. A seawater evaporation rate of 3.8 kg m-2 h-1 is achieved, which marks the record performance among all plasmonic solar seawater desalination systems reported so far. The removal percentage of phenol reaches 98.3%, which is attributed to the joint action of the excellent photocatalytic ability and the superhydrophilicity of the porous TiN-based composite film.

All-State Switching of the Mie Resonance of Conductive Polyaniline Nanospheres.

Polyaniline (PANI), a conductive polymer, is a promising active material for optical switching. In most studies, active switching has so far been realized only between two states, whereas PANI has a total of six states. The optical properties of nanoscale PANI in all six states have remained unclear. Herein we report on all-state switching of the Mie resonance on PANI nanospheres (NSs) and active plasmon switching on PANI-coated Au nanodisks (NDs). All-state switching of differently sized PANI NSs is achieved by proton doping/dedoping and electrochemical methods. Theoretical studies show that the scattering peaks of the individual PANI NSs originate from Mie resonances. All-state switching is further demonstrated on PANI-coated circular Au NDs, where an unprecedentedly large plasmon peak shift of ∼200 nm is realized. Our study not only provides a fundamental understanding of the optical properties of PANI but also opens the probability for developing high-performance dynamic media for active plasmonics.

A Schottky-Barrier-Free Plasmonic Semiconductor Photocatalyst for Nitrogen Fixation in a "One-Stone-Two-Birds" Manner.

Plasmonic photocatalysis has received much attention owing to attractive plasmonic enhancement effects in improving the solar-to-chemical conversion efficiency. However, the photocatalytic efficiencies have remained low mainly due to the short carrier lifetime caused by the rapid recombination of plasmon-generated hot charge carriers. Although plasmonic metal-semiconductor heterostructures can improve the separation of hot charge carriers, a large portion of the hot charge carriers are lost when they cross the Schottky barrier. Herein, a Schottky-barrier-free plasmonic semiconductor photocatalyst, MoO3- x , which allows for efficient N2 photofixation in a "one-stone-two-birds" manner, is demonstrated. The oxygen vacancies in MoO3- x serve as the "stone." They "kill two birds" by functioning as the active sites for the chemisorption of N2 molecules and inducing localized surface plasmon resonance for the generation of hot charge carriers. Benefiting from this unique strategy, plasmonic MoO3- x exhibits a remarkable photoreactivity for NH3 production up to the wavelength of 1064 nm with apparent quantum efficiencies over 1%, and a solar-to-ammonia conversion efficiency of 0.057% without any hole scavenger. This work shows the great potential of plasmonic semiconductors to be directly used for photocatalysis. The concept of the Schottky-barrier-free design will pave a new path for the rational design of efficient photocatalysts.

Site-Selective Deposition of Metal-Organic Frameworks on Gold Nanobipyramids for Surface-Enhanced Raman Scattering.

Site-selective deposition of metal-organic frameworks (MOFs) on metal nanocrystals has remained challenging because of the difficult control of the nucleation and growth of MOFs. Herein we report on a facile wet-chemistry approach for the selective deposition of zeolitic imidazolate framework-8 (ZIF-8) on anisotropic Au nanobipyramids (NBPs) and nanorods. ZIF-8 is selectively deposited at the ends and waist and around the entire surface of the elongated Au nanocrystals. The NBP-based nanostructures with end-deposited ZIF-8 exhibit the best surface-enhanced Raman scattering (SERS) performance, implying that molecules can be concentrated by ZIF-8 at the hot spots. In addition, the SERS signal exhibits good selectivity for small molecules because of the molecular sieving effect of ZIF-8. This study opens up a promising route for constructing plasmonic nanostructures with site selectively deposited ZIF-8, which hold enormous potential for molecular sensing, optical switching, and plasmonic catalysis.

Selective Deposition of Catalytic Metals on Plasmonic Au Nanocups for Room-Light-Active Photooxidation of o-Phenylenediamine.

Plasmonic hotspots can enhance hot charge carrier generation, offering new opportunities for improving the photocatalytic activity. In this work, eight types of heteronanostructures are synthesized by selectively depositing catalytic metals at the different sites of highly asymmetric Au nanocups for the photocatalytic oxidation of o-phenylenediamine. The oxidation of this molecule has so far mainly relied on the use of H2O2 as an oxidizing agent in the presence of an appropriate catalyst. The photocatalytic oxidation under visible light has not been reported before. The Au nanocups with AgPt nanoparticles grown at the opening edge and bottom exhibit the highest photocatalytic activity. The generated hot electrons and holes both participate in the reaction. The hot carriers from the interband and intraband transitions are both utilized. The optimal catalyst shows a favorable activity even under room light. Simulations reveal that the profound electric field enhancement at the hotspots boosts the hot-carrier density in the catalytic nanoparticles, explaining the overwhelming photocatalytic activity of the optimal catalyst.

(Gold nanorod core)/(poly(3,4-ethylene-dioxythiophene) shell) nanostructures and their monolayer arrays for plasmonic switching.

(Gold nanorod core)/(poly(3,4-ethylene-dioxythiophene) (PEDOT) shell) nanostructures are prepared by the surfactant-assisted oxidative polymerization of 3,4-ethylene-dioxythiophene on the surface of gold nanorods (NRs). The PEDOT shell exhibits distinct dielectric properties at doped and undoped states, which allows the manipulation of plasmonic responses of the Au nanorod core. The shift in plasmon resonance induced by the dedoping of PEDOT is found to be associated with the overlap between the plasmon resonance band of the core/shell nanostructure and the spectral region where the largest refractive index variation of PEDOT occurs, as well as with the type of the dedopant. Macroscopic two-dimensional (2D) monolayer arrays of core/shell nanostructures with controlled particle number densities are fabricated on indium tin oxide (ITO)-coated glass substrates by electrophoretic deposition. A reversible plasmonic shift of about 70 nm is obtained on the core/shell nanostructure monolayer array with a number density of around 18 particles per µm2. Our design of colloidal (Au nanorod core)/(PEDOT shell) nanostructures and their 2D monolayer arrays paves the way for the fabrication of high-performance plasmonic switches in large-scale practical usages as well as for the preparation of advanced, programmable chromic materials for a broad range of applications, such as smart windows, anti-counterfeiting tags, and medical and environmental sensors.