The ability to move and self-organize in response to external stimuli is a fascinating feature of living active matter. Here, the metallo-dielectric rod-shaped microswimmers are shown to have a similar behavior in the presence of an AC electric field. The silica-copper Janus microrods were fabricated using the physical vapor deposition-based glancing angle deposition technique (GLAD).
View Article and Find Full Text PDFCharacterizing complex biofluids using surface-enhanced Raman spectroscopy (SERS) coupled with machine learning (ML) has been proposed as a powerful tool for point-of-care detection of clinical disease. ML is well-suited to categorizing otherwise uninterpretable, patient-derived SERS spectra that contain a multitude of low concentration, disease-specific molecular biomarkers among a dense spectral background of biological molecules. However, ML can generate false, non-generalizable models when data sets used for model training are inadequate.
View Article and Find Full Text PDFPhotocarriers predominantly recombine at semiconductor surfaces and interfaces, assuming high bulk carrier lifetime. Consequently, understanding the extraction of photocarriers via surfaces is critical to optoelectronics. Here, we propose Haynes-Shockley experiment analogs to investigate photocarrier surface extraction.
View Article and Find Full Text PDFPhotodiodes are fundamental components in modern optoelectronics. Heterojunction photodiodes, simply configured by two different contact materials, have been a hot research topic for many years. Currently reported self-biased heterojunction photodiodes routinely have external quantum efficiency (EQE) significantly below 100% due to optical and electrical losses.
View Article and Find Full Text PDFStimulated emission luminescent solar concentrators (SELSCs) have the potential to reduce escape cone losses in luminescent solar concentrators (LSCs). However, a functional SELSC is yet to be demonstrated. Previous numerical studies and detailed balance limits provide guidance, but they also contradict and likely overestimate performance and underestimate requirements.
View Article and Find Full Text PDFThe design of simple microrobotic systems with capabilities to address various applications like cargo transportation, as well as biological sample capture and manipulation in an individual unit, provides a novel route for designing advanced multifunctional microscale systems. Here, we demonstrate a facile approach to fabricate such multifunctional and fully controlled light-driven microrobots. The microrobots are titanium dioxide-silica Janus particles that are propelled in aqueous hydroquinone/benzoquinone fuel when illuminated by low-intensity UV light.
View Article and Find Full Text PDFThe wrinkle period and morphology of a metal thin film on an elastic substrate is typically controlled by modifying the substrate before carrying out additional metal deposition steps. Herein, we show that a simultaneously selective and reactive sputtering plasma that modifies the surface of a polydimethylsiloxane (PDMS) substrate while not reacting with the metal during the deposition process decreases the wrinkle wavelength and induces additional wrinkling components and features such as ripples or folds. The selective reaction of the nitrogen plasma with PDMS functionalizes the siloxane surface into silicon oxynitride.
View Article and Find Full Text PDFMetamaterials are a new class of artificial materials that can achieve electromagnetic properties that do not occur naturally, and as such they can also be a new class of photocatalytic structures. We show that metal-based catalysts can achieve electromagnetic field amplification and broadband absorption by decoupling optical properties from the material composition as exemplified with a ZnO/Cu metamaterial surface comprising periodically arranged nanocubes. Through refractive index engineering close to the index of air, the metamaterial exhibits near-perfect 98% absorption.
View Article and Find Full Text PDFSurface-enhanced Raman scattering (SERS) substrates with multiwavelength rainbow-trapping properties hold the potential for a one-size-fits-all platform for rapid and multiplexed disease detection. We present the first report on the utilization of rainbow-trapping width-graded nano-gratings, a new class of chirped metamaterials, to detect protein biomarkers. Using cytochrome c (Cc), a charged analyte with inherent difficulty in adsorbing onto sputtered silver films, we investigated methods of binding Cc on the silver nano-grating in order to improve the SERS signal strength at both 532 and 638 nm excitation.
View Article and Find Full Text PDFMicromanipulation techniques that are capable of assembling nano/micromaterials into usable structures such as topographical micropatterns (TMPs) have proliferated rapidly in recent years, holding great promise in building artificial electronic and photonic microstructures. Here, a method is reported for forming TMPs based on optoelectronic tweezers in either "bottom-up" or "top-down" modes, combined with in situ photopolymerization to form permanent structures. This work demonstrates that the assembled/cured TMPs can be harvested and transferred to alternate substrates, and illustrates that how permanent conductive traces and capacitive circuits can be formed, paving the way toward applications in microelectronics.
View Article and Find Full Text PDFCalcium hydroxyphosphate, Ca (PO ) (OH) , is commonly known as hydroxyapatite (HAP). The acidic calcium and basic phosphate/hydroxide sites in HAP can be modified via isomorphous substitution of calcium and/or hydroxide ions to enable a cornucopia of catalyzed reactions. Herein, isomorphic substitution of Ca ions by Cu ions especially at very low levels of exchange created new analogs of molecular surface frustrated Lewis pairs (SFLPs) in Cu Ca (PO ) (OH) , thereby boosting its performance metrics in heterogeneous CO photocatalytic hydrogenation.
View Article and Find Full Text PDFSolar-pumped lasers and optical amplifiers continue to draw research interest with advances in nanomaterials science and technology. Establishing accurate detailed balance limits for inversion in these systems is essential. In this Letter, we re-examine the threshold limits for inversion in broadband-pumped lasers, with reference to those provided by Roxlo and Yablonvitch [Opt.
View Article and Find Full Text PDFA conventional light management approach on a photo-catalyst is to concentrate photo-intensity to enhance the catalytic rate. We present a counter-intuitive approach where light intensity is distributed below the electronic photo-saturation limit under the principle of light maximization. By operating below the saturation point of the photo-intensity induced hydroxide growth under reactant gaseous H+CO atmosphere, a coating of defect engineered InO(OH) nanorod Reverse Water Gas Shift solar-fuel catalyst on an optical waveguide outperforms a coated plane by a factor of 2.
View Article and Find Full Text PDFWe delineate the four principal surface plasmon polariton coupling and interaction mechanisms in subwavelength gratings, and demonstrate their significant roles in shaping the optical response of plasmonic gratings. Within the framework of width-graded metal-insulator-metal nano-gratings, electromagnetic field confinement and wave guiding result in multiwavelength light localization provided conditions of adiabatic mode transformation are satisfied. The field is enhanced further through fine tuning of the groove-width (w), groove-depth (L) and groove-to-groove-separation (d).
View Article and Find Full Text PDFRainbow light trapping in plasmonic devices allows for field enhancement of multiple wavelengths within a single device. However, many of these devices lack precise control over spatial and spectral enhancement profiles and cannot provide extremely high localised field strengths. Here we present a versatile, analytical design paradigm for rainbow trapping in nanogroove arrays by utilising both the groove-width and groove-length as tuning parameters.
View Article and Find Full Text PDFNanoscale titanium nitride TiN is a metallic material that can effectively harvest sunlight over a broad spectral range and produce high local temperatures via the photothermal effect. Nanoscale indium oxide-hydroxide, In O (OH) , is a semiconducting material capable of photocatalyzing the hydrogenation of gaseous CO ; however, its wide electronic bandgap limits its absorption of photons to the ultraviolet region of the solar spectrum. Herein, the benefits of both nanomaterials in a ternary heterostructure: TiN@TiO @In O (OH) are combined.
View Article and Find Full Text PDFPhoto-Induced Transient Current Spectroscopy (PICTS) is a versatile technique for measurements of defect state energies and densities in photo-active materials. It is suitable for investigating the surface-gas adsorbate behavior and the defect characteristics of defect laden In2O3-x(OH)y nanorods, having oxygen vacancies and hydroxide surface groups, under in situ reactor conditions of dark ambient temperature, dark 150 °C and photo-illuminated 150 °C, for the photo-assisted Reverse Water Gas Shift reaction. From glovebox-protected X-ray Photoelectron Spectroscopy and in situ PICTS measurements we determined that the reduction of CO2 is associated with heterolytic dissociation of H2 into In-H§- and HO-H§+ centres accompanied by an increase in average carrier trap energies; increased carbonate formation in a photo/thermal reactor state of H2 + CO2, and an average trap energy decrease of 0.
View Article and Find Full Text PDFOptimizing kinetic barriers of ammonia synthesis to reduce the energy intensity has recently attracted significant research interest. The motivation for the research is to discover means by which activation barriers of N dissociation and NH ( = 1-2, surface intermediates) destabilization can be reduced simultaneously, that is, breaking the "scaling relationship". However, by far only a single success has been reported in 2016 based on the discovery of a strong-weak N-bonding pair: transition metals (nitrides)-LiH.
View Article and Find Full Text PDFNanostructured forms of stoichiometric InO are proving to be efficacious catalysts for the gas-phase hydrogenation of CO. These conversions can be facilitated using either heat or light; however, until now, the limited optical absorption intensity evidenced by the pale-yellow color of InO has prevented the use of both together. To take advantage of the heat and light content of solar energy, it would be advantageous to make indium oxide black.
View Article and Find Full Text PDFMetal-dielectric multilayers are versatile optical devices that can be designed to combine the visible transmittance of dielectrics with the electronic properties of metals for plasmonic and meta-material applications. However, their performances are limited by an interfacial optical absorption often attributed entirely to the metal surface roughness. Here, we show that during deposition of AlN/Ag/AlN and SiN/Ag/SiN multilayers, significant diffusion of Ag into the top dielectric layer form Ag nanoparticles which excite localized surface plasmon resonances that are primarily responsible for the interfacial optical absorption.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2020
The photocatalytic activity of nanostructured InO(OH) for the reverse water gas shift (RWGS) reaction CO + H → CO + HO can be greatly enhanced by substitution of Bi(III) for In(III) in the lattice of BiInO(OH). This behavior was hypothesized as the effect of the population and location of Bi(III) on the Lewis acidity and Lewis basicity of proximal hydroxide and coordinately unsaturated metal surface sites in BiInO(OH) acting synergistically as a frustrated Lewis acid-base pair reaction. Nonetheless, such photocatalytic activity is usually optimized in a specific batch reactor setup sequence, with H as an initial gas input under photo and thermal conditions before introducing CO.
View Article and Find Full Text PDFAdv Sci (Weinh)
November 2019
To achieve substantial reductions in CO emissions, catalysts for the photoreduction of CO into value-added chemicals and fuels will most likely be at the heart of key renewable-energy technologies. Despite tremendous efforts, developing highly active and selective CO reduction photocatalysts remains a great challenge. Herein, a metal oxide heterostructure engineering strategy that enables the gas-phase, photocatalytic, heterogeneous hydrogenation of CO to CO with high performance metrics (i.
View Article and Find Full Text PDFIn the study reported herein, glovebox-protected X-ray photoelectron spectroscopy (XPS) and in situ Hall charge carrier measurements provide new insights into the surface physical chemistry of gaseous H, CO, and H+CO combined with nanostructured InO(OH) nanorods, which ensue under photochemical and thermochemical operating conditions. Heterolytic dissociation of H in H-only atmosphere appears to occur mainly under dark and ambient temperature conditions, while the greatest amount of OH shoulder expansion in H+CO atmosphere appears to mainly occur under photoilluminated conditions. These results correlate with those of the Hall measurements, which show that the prevalence of homolytic over heterolytic dissociation at increasing temperatures leads to a steeper rate of increase in carrier concentrations; and that H adsorption is more prevalent than CO in H+CO photoillumination conditions.
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