Numerical study of the plasmonic slab lens for improving direct-write nano lithography.

Plasmonic direct-write lithography (PDWL) provides a potential tool for the fabrication and manufacturing at the nano scale due to its high-resolution and low-cost. However, the shallow exposure depth hinders its practical application. Here, we incorporate the plasmonic slab lenses (PSLs) into PDWL to amplify and compensate evanescent waves, leading to improved light intensity, depth, resolution and better tolerance to the air gap beyond the near field optical lithography. Two typical plasmonic probes with different nanostructure and localized plasmonic resonance mechanisms are designed and fabricated as representatives, the local intensity enhancement of which mainly depend on the oscillations of transverse and longitudinal electric field components, respectively. Optimizations considering the PSL structure, material and the illuminating wavelength are performed to amplify different field components and figure out the best lithography configuration. Simulation results indicate that Ag-Ag cavity PSL and 355 nm illumination is the best combination for the lithography with bowknot aperture probe, while the semi-ring probe exhibits better performance under the condition of Ag-Al cavity PSL and 405 nm illumination. The semi-ring probe in combination with a plasmonic cavity, for instance, is demonstrated to enhance the light intensity by 4 times at the bottom layer of the photoresist compared to that without PSL and realize a lithography resolution of 23 nm. Our scheme is believed to boost the application of PDWL as a high-resolution and low-cost nanofabrication technology, and it may even serve as an alternative for the high-cost scanning method, such as focused ion beam and electron beam lithography.

Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction.

CO2 electroreduction (CO2 R) operating in acidic media circumvents the problems of carbonate formation and CO2 crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic CO2 R, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali-cation-free CO2 R in pure acid. However, without alkali cations, stabilizing *CO2 intermediates by catalyst itself at the acidic interface poses as a challenge. Herein, we first demonstrate that a carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc@CNT) catalyst provides the Co single-atom active site with energetically localized d states to strengthen the adsorbate-surface interactions, which stabilizes *CO2 intermediates at the acidic interface (pH=1). As a result, we realize CO2 conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO2 is successfully converted in cation exchanged membrane-based electrode assembly with a faradaic efficiency of 73 %. For CoPc@CNT, acidic conditions also promote the intrinsic activity of CO2 R compared to alkaline conditions, since the potential-limiting step, *CO2 to *COOH, is pH-dependent. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts and devices for acidic CO2 R.

An integrated n-Si/BiVO4 photoelectrode with an interfacial bi-layer for unassisted solar water splitting.

Integrated n-Si/BiVO4 is one of the most promising candidates for unbiased photoelectrochemical water splitting. However, a direct connection between n-Si and BiVO4 will not attain overall water splitting due to the small band offset as well as the interfacial defects at the n-Si/BiVO4 interface that severely impede carrier separation and transport, limiting the photovoltage generation. This paper describes the design and fabrication of an integrated n-Si/BiVO4 device with enhanced photovoltage extracted from the interfacial bi-layer for unassisted water splitting. An Al2O3/indium tin oxide (ITO) interfacial bi-layer was inserted at the n-Si/BiVO4 interface, which promotes the interfacial carrier transport by enlarging the band offset while healing interfacial defects. When coupled to a separate cathode for hydrogen evolution, spontaneous water splitting could be realized with this n-Si/Al2O3/ITO/BiVO4 tandem anode, with an average solar-to-hydrogen (STH) efficiency of 0.62% for over 1000 hours.

Experimental Realization and Computational Investigations of B2S2 as a New 2D Material with Potential Applications.

A new two-dimensional material B2S2 has been successfully synthesized for the first time and validated using first-principles calculations, with fundamental properties analyzed in detail. B2S2 has a similar structure as transition-metal dichalcogenides (TMDs) such as MoS2, and the experimentally prepared free-standing B2S2 nanosheets show a uniform height profile lower than 1 nm. A thickness-modulated and unique oxidation-level dependent band gap of B2S2 is revealed by theoretical calculations, and vibration signatures are determined to offer a practical scheme for the characterization of B2S2. It is shown that the functionalized B2S2 is able to provide favorable sites for lithium adsorption with low diffusion barriers, and the prepared B2S2 shows a wide band photoluminescence response. These findings offer a feasible new and lighter member for the TMD-like 2D material family with potential for various aspects of applications, such as an anode material for Li-ion batteries and electronic and optoelectronic devices.

Spatial decoupling of light absorption and reaction sites in n-Si photocathodes for solar water splitting.

Metal-insulator-semiconductor (MIS) photocathodes offer a simple alternative to p-n junction photocathodes in photoelectrochemical water splitting. However, the parasitic light absorption of catalysts and metal layers in the MIS junction, as well as the lack of low work function metals to form a large band offset with p-Si, severely limit their performance. This paper describes an MIS photocathode fabricated from n-Si, rather than the commonly used p-Si, to spatially decouple light absorption from reaction sites, which enables the majority carriers, instead of the commonly used minority carriers, to drive the surface reaction, making it possible to place the reaction sites far away from the light absorption region. Thus, the catalysts could be moved to the backside of the MIS junction to avoid light shielding. Moreover, the adoption of n-Si unlocks a variety of high work function materials for photovoltage generation. The obtained n-Si MIS photocathode exhibits an applied bias photon-to-current efficiency of 10.26% with a stability up to 300 h.

Enriched Surface Oxygen Vacancies of Photoanodes by Photoetching with Enhanced Charge Separation.

A facile photoetching approach is described that alleviates the negative effects from bulk defects by confining the oxygen vacancy (Ovac ) at the surface of BiVO4 photoanode, by 10-minute photoetching. This strategy could induce enriched Ovac at the surface of BiVO4 , which avoids the formation of excessive bulk defects. A mechanism is proposed to explain the enhanced charge separation at the BiVO4  /electrolyte interface, which is supported by density functional theory (DFT) calculations. The optimized BiVO4 with enriched surface Ovac presents the highest photocurrent among undoped BiVO4 photoanodes. Upon loading FeOOH/NiOOH cocatalysts, photoetched BiVO4 photoanode reaches a considerable water oxidation photocurrent of 3.0 mA cm-2 at 0.6 V vs. reversible hydrogen electrode. An unbiased solar-to-hydrogen conversion efficiency of 3.5 % is realized by this BiVO4 photoanode and a Si photocathode under 1 sun illumination.