Manipulation of charge transfer and transport in plasmonic-ferroelectric hybrids for photoelectrochemical applications

Utilizing plasmonic nanostructures for efficient and flexible conversion of solar energy into electricity or fuel presents a new paradigm in photovoltaics and photoelectrochemistry research. In a conventional photoelectrochemical cell, consisting of a plasmonic structure in contact with a semiconductor, the type of photoelectrochemical reaction is determined by the band bending at the semiconductor/electrolyte interface. The nature of the reaction is thus hard to tune. Here instead of using a semiconductor, we employed a ferroelectric material, Pb(Zr,Ti)O3 (PZT). By depositing gold nanoparticle arrays and PZT films on ITO substrates, and studying the photocurrent as well as the femtosecond transient absorbance in different configurations, we demonstrate an effective charge transfer between the nanoparticle array and PZT. Most importantly, we show that the photocurrent can be tuned by nearly an order of magnitude when changing the ferroelectric polarization in PZT, demonstrating a versatile and tunable system for energy harvesting

Fully understanding the positive roles of plasmonic nanoparticles in ameliorating the efficiency of organic solar cells

Herein, we constructed inverted PBDTTT-CF:PC70BM bulk-heterojunction organic solar cells by introducing Au nanoparticles to a ZnO buffer layer and a great improvement in energy conversion efficiency has been realized. To discover the positive roles of such plasmonic nanoparticles in the process of solar energy conversion, photovoltaic devices with the same architecture but different sized Au nanoparticles were purposely fabricated and it has been observed that the overall efficiency can be remarkably improved from 6.67% to 7.86% by embedding 41 nm Au nanoparticles in the buffer layer. The devices with other sizes of Au nanoparticles show a relatively low performance. Subsequent investigations including finite difference time domain simulation and transient photoluminescence studies reveal that the existence of the plasmonic particles could not only improve the optical absorption and facilitate the exciton separation, but can also benefit the collection of charge carriers. Thus, this paper provides a comprehensive perspective on the roles of plasmonic particles in organic solar cells and insights into the photo energy conversion process in the plasmonic surroundings

Binary Nano-structuring: Concept, Strategies, Features and Devices

Nanostrukturarrays, bestehend aus den zwei Unterteilungen „Nanostruktur“ und „Array“, sind elementar für viele moderne und zukünftige technologische Anwendungen oder Systeme. Binäre Nanostrukturarrays, in denen beide, die „Nanostruktur“ und die „Array“, unabhängig voneinander eingestellt und genutzt werden können, könnten einen neuen Horizont durch Interaktionen zwischen den Sub-Arrays, welche unter Einfach-Arrays unzugänglich sind, eröffnen. Eine allgemeine Methode wird entwickelt um verschiedene Nanostrukturarrays (z.B. Nanowire/Nanowire, Nanotube/Nanowire, Nanotube/Nanotube, Nanodot/Nanodot) mit struktureller Flexibilität und hoher Steuerbarkeit für jedes der Sub-Arrays individuell herzustellen. Der Schlüssel zu dieser Methode basiert auf den charakteristischen binären Poren von anodischen Aluminium Templaten, welche beidseitig entgegengesetzte Barriere-Oxid-Schichten besitzen. Mittels desselben Mechanismus kann das Templat zu einem Viel-Array-Templat (z.B. dreifach oder vierfach) in einer Matrix mit noch höheren Porendichten und weiteren morphologischen Möglichkeiten erweitert werden. Die Vielseitigkeit der binären Nanostrukturierung wird untersucht für die Realisierung innovativer Anwendungen, wie zum Beispiel makroskopische Titandioxid/Kupfer(I)-oxid Z-Schema Photosyntheseeinheiten und nanoskopisch große adressierbare Zinkoxid/Aluminiumzinkoxid vertikale Nanodraht-Transistoren. Des Weiteren wird Nanoengineering von Einfacharrays durchgeführt, dazu werden leistungsstarke Superkondensatoren basierend auf Platin/Manganoxid-Core/Shell-Nanotubearrays und photoelektrochemische Zellen basierend auf Nano-Gold/Pb(Zr,Ti)O3 Hybriden nachgegangen durch welche die optimale Struktur und Zusammensetzung der Einfacharrays wichtige Informationen für multifunktionale Anwendungen basierend auf binären Nanostrukturarrays liefern.Nanostructure arrays, composed by two subdivisions of ‘nanostructure’ and ‘array’, are the fundamental for many modern and future devices or systems. Binary nanostructure arrays, in which both of the ‘nanostructure’ and the ‘array’ can be freely manipulated and utilized, could raise a new horizon by introducing the interactions between the sub-arrays that are inaccessible for the single ‘array’s. A general technique is developed to fabricate diverse binary nanostructure arrays (e.g., nanowire/nanowire, nanotube/nanowire, nanotube/nanotube, nanodot/nanodot) with morphologic versatility and highly structural controllability for each of the sub-array individually. The key of this technique is based on a distinctive binary-pore anodic aluminum oxide template, possessing double side barrier oxide layers located at the opposite sides of the template. Under the same mechanism, the template can be further upgraded to multi-pore template (e.g., ternary and quadruple) in one matrix with even higher pore densities and more morphologic options. The versatility of binary-nanostructuring is being explored to realize innovative devices, such as macroscopic ‘titanium dioxide/cuprous oxide’ Z-scheme photosynthesis unit and nanoscopic ‘zinc oxide/aluminum doped zinc oxide’ addressable vertical nanowire transistor. Furthermore, nanoengineering of single ‘array’s are conducted to pursuit high-performance supercapactior based on platinum/manganese oxide core/shell nanotube array and photoelectrochemical cell based on nano-gold/Pb(Zr,Ti)O3 hybrid, in which the optimal structure and composition of the single ‘array’s could provide valuable guidance for addressing multi-functionalized devices based on the binary nanostructure arrays

Enhanced CO2 Electroreduction to Multi‐Carbon Products on Copper via Plasma Fluorination

Abstract The electroreduction of carbon dioxide (CO2) to multi‐carbon (C2+) compounds offers a viable approach for the up‐conversion of greenhouse gases into valuable fuels and feedstocks. Nevertheless, current industrial applications face limitations due to unsatisfactory conversion efficiency and high overpotential. Herein, a facile and scalable plasma fluorination method is reported. Concurrently, self‐evolution during CO2 electroreduction is employed to control the active sites of Cu catalysts. The copper catalyst modified with fluorine exhibits an impressive C2+ Faradaic efficiency (FE) of 81.8% at a low potential of −0.56 V (vs a reversible hydrogen electrode) in an alkaline flow cell. The presence of modified fluorine leads to the exposure and stabilization of high‐activity Cu+ species, enhancing the adsorption of *CO intermediates and the generation of *CHO, facilitating the subsequent dimerization. This results in a notably improved conversion efficiency of 13.1% and a significant reduction in the overpotential (≈100 mV) for the C2+ products. Furthermore, a superior C2+ FE of 81.6% at 250 mA cm−2, coupled with an energy efficiency of 31.0%, can be achieved in a two‐electrode membrane electrode assembly electrolyzer utilizing the fluorine‐modified copper catalyst. The strategy provides novel insights into the controllable electronic modification and surface reconstruction of electrocatalysts with practical potential

Label-Free LSPR-Vertical Microcavity Biosensor for On-Site SARS-CoV-2 Detection

Cost-effective, rapid, and sensitive detection of SARS-CoV-2, in high-throughput, is crucial in controlling the COVID-19 epidemic. In this study, we proposed a vertical microcavity and localized surface plasmon resonance hybrid biosensor for SARS-CoV-2 detection in artificial saliva and assessed its efficacy. The proposed biosensor monitors the valley shifts in the reflectance spectrum, as induced by changes in the refractive index within the proximity of the sensor surface. A low-cost and fast method was developed to form nanoporous gold (NPG) with different surface morphologies on the vertical microcavity wafer, followed by immobilization with the SARS-CoV-2 antibody for capturing the virus. Modeling and simulation were conducted to optimize the microcavity structure and the NPG parameters. Simulation results revealed that NPG-deposited sensors performed better in resonance quality and in sensitivity compared to gold-deposited and pure microcavity sensors. The experiment confirmed the effect of NPG surface morphology on the biosensor sensitivity as demonstrated by simulation. Pre-clinical validation revealed that 40% porosity led to the highest sensitivity for SARS-CoV-2 pseudovirus at 319 copies/mL in artificial saliva. The proposed automatic biosensing system delivered the results of 100 samples within 30 min, demonstrating its potential for on-site coronavirus detection with sufficient sensitivity

Programmable multiple plasmonic resonances of nanoparticle superlattice for enhancing photoelectrochemical activity

Building nanoparticle (NP) superlattices formed in a complex fashion by subsets that can be explored separately presents a promising approach to realize the next generation of superlattices for different applications. Here, by incorporating self‐aligned and geometrically different subsets of Au NPs into one matrix with the assistance of multi‐pore anodic alumina oxide templates, scaled‐up NP superlattices are constructed with programmable multiple plasmonic resonances. The inter‐peak spectral distance is tailored in a broad wavelength range from less than 50 nm up to about 1000 nm through altering not only the size and height of each subset, but also the number and nature of the NP subset. Importantly, a mechanical oscillator model is developed to elucidate the microscopic origin of the spectral programmability and to reproduce the parameter dependence of the multiple plasmonic resonances. A photoelectrochemical cell using Au NP superlattice embedded photoanodes is investigated as a proof‐of‐concept, demonstrating a high photoresponse improvement of about 260% compared to that of bare film reference. In light of the compatibility of this technique with other plasmonic materials and the geometrical tunability, these findings enable systematic optical controlling toward optical devices with multimodal plasmonics