Using Machine Learning and Silver Nanoparticle-Based Surface-Enhanced Raman Spectroscopy for Classification of Cardiovascular Disease Biomarkers.

Characterizing 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. It is thus critical to determine how different SERS experimental methodologies and workflow parameters can potentially impact ML disease classification of clinical samples. In this study, a label-free, broadband, Ag nanoparticle-based SERS platform was coupled with ML to assess simulated clinical samples for cardiovascular disease (CVD), containing randomized combinations of five key CVD biomarkers at clinically relevant concentrations in serum. Raman spectra obtained at 532, 633, and 785 nm from up to 300 unique samples were classified into physiological and pathological categories using two standard ML models. Label-free SERS and ML could correctly classify randomized CVD samples with high accuracies of up to 90.0% at 532 nm using as few as 200 training samples. Spectra obtained at 532 nm produced the highest accuracies with no significant increase achieved using multiwavelength SERS. Sample preparation and measurement methodologies (e.g., different SERS substrate lots, sample volumes, sample sizes, and known variations in randomization and experimental handling) were shown to strongly influence the ML classification and could artificially increase classification accuracies by as much as 27%. This detailed investigation into the proper application of ML techniques for CVD classification can lead to improved data set acquisition required for the SERS community, such that ML on labeled and robust SERS data sets can be practically applied for future point-of-care testing in patients.

Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation.

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Haynes-Shockley experiment analogs in surface and optoelectronics: Tunable surface electric field extracting nearly all photocarriers.

Photocarriers 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. A Schottky junction is used to tune the silicon near-surface electric field strength that varies over several orders of magnitude and simultaneously observe variations in broadband photocarrier extraction. Schottky barrier height and surface potential are both modulated. Work function tunable indium tin oxide (ITO) is developed to precisely regulate the barrier height and collect photocarriers at 0 V bias, thus avoiding the photocurrent gain effect. All experiments demonstrate >98% broadband internal quantum efficiency. The experiments are further extended to wave interference photonic crystals and random pyramids, paving a way to estimate the photogeneration rate of diverse surface light-trapping topologies by collecting nearly all photocarriers. The insights reported here provide a systematic experimental basis to investigate interfacial effects on photocarrier spatial generation and collection.

Facilely Achieved Self-Biased Black Silicon Heterojunction Photodiode with Broadband Quantum Efficiency Approaching 100.

Photodiodes 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. Herein, an approach that virtually overcomes this 100% EQE challenge via low-aspect-ratio nanostructures and drift-dominated photocarrier transport in a heterojunction photodiode is proposed. Broadband near-ideal EQE is achieved in nanocrystal indium tin oxide/black silicon (nc-ITO/b-Si) Schottky photodiodes. The b-Si comprises nanostalagmites which balance the antireflection effect and surface morphology. The built-in electric field is explored to match the optical generation profile, realizing enhanced photocarrier transport over a broadband of photogeneration. The devices exhibit unprecedented EQE among the reported leading-edge heterojunction photodiodes: average EQE surpasses ≈98% for wavelengths of 570-925 nm, while overall EQE is greater than ≈95% from 500 to 960 nm. Further, only elementary fabrication techniques are explored to achieve these excellent device properties. A heart rate sensor driven by nanowatt faint light is demonstrated, indicating the enormous potential of this near-ideal b-Si photodiode for low power consuming applications.

Large area stimulated emission luminescent solar concentrators modelled using detailed balance consistent rate equations.

Stimulated 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. In this work, we introduce a rate-equation model with inversion requirements compatible with detailed balance limits and apply this model to the numerical modelling of window-sized SELSCs. We find that the optimal pump photon energy for both LSCs and SELSCs is 1.35 eV and the potential improvement of SELSCs over LSCs is found to be 19.3%. The efficiencies found are much lower than those specified in previous work due to the increase in Stokes shift required for a highly luminescent material. We also find that SELSCs are more attractive at higher matrix losses, that emission linewidths <0.05  eV are desirable, and that SELSC devices can potentially achieve performance equal to LSCs at low illumination levels and simultaneously exceed it by up to 16.5% at 1-sun illumination.

A one-step, tunable method of selective reactive sputter deposition as a wrinkling approach for silver/polydimethylsiloxane for electrically conductive pliable surfaces.

The 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. This hardens the immediate surface of PDMS, with a quadratic increase in the Young's modulus as a function of the sputtering flow ratio. The increase in the critical strain mismatch and the corresponding presence of folds in the nitrogen-modified wrinkled silver film form a suitable plasmonic platform for surface-enhanced Raman spectroscopy (SERS), yielding an enhancement factor of 4.8 × 105 for detecting lipids. This enhancement is linked to the emergence of electromagnetic hotspots from surface plasmon polariton coupling between the folds/wrinkles, which in turn enables the detection of low concentrations of organics using SERS. Furthermore, when strained, the nitrogen-modified wrinkles enhance electrical conductivity by a factor of 12 compared with unmodified films. Finally, the optical properties of the substrate can be tuned by altering the N2 content. The simple addition of nonreactive nitrogen to silver sputtering enables simultaneous PDMS hardening and growth of the silver film and together provide a new avenue for tuning wrinkling parameters and enhancing the electrical conductivity of pliable surfaces.

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation.

Metamaterials 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. The combination of plasmonics and broadband absorption elevates the weak electric field intensities across the nonplasmonic absorption range. This feedback between optical excitation and plasmonic excitation dramatically enhances light-to-dark catalytic rates by up to a factor of 181 times, compared to a 3 times photoenhancement of ZnO/Cu nanoparticles or films, and with angular invariance. These results show that metamaterial catalysts can act as a singular light harvesting device that substantially enhances photocatalysis of important reactions.

Protein capture and SERS detection on multiwavelength rainbow-trapping width-graded nano-gratings.

Surface-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. Cc was not detectable on the Ag nano-gratings without surface functionalization at 1µM concentration. Upon charge reversal functionalization of the Ag nano-gratings, 1µM Cc was detectable albeit not reliably. By further crosslinking 1µM Cc to the functionalized Ag nano-gratings, the analyte-capture detection scheme greatly improved the SERS signal strength and reliability at both excitation wavelengths and allowed for quantification of their coefficients of variation with values down to 27%.

Integrated Assembly and Photopreservation of Topographical Micropatterns.

Micromanipulation 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. The integrated, optical assembly/preservation method described here is accessible, versatile, and applicable for a wide range of materials and structures, suggesting utility for myriad microassembly and microfabrication applications in the future.

Construction of New Active Sites: Cu Substitution Enabled Surface Frustrated Lewis Pairs over Calcium Hydroxyapatite for CO2 Hydrogenation.

Calcium hydroxyphosphate, Ca10 (PO4 )6 (OH)2 , 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 Ca2+ ions by Cu2+ ions especially at very low levels of exchange created new analogs of molecular surface frustrated Lewis pairs (SFLPs) in Cux Ca10-x (PO4 )6 (OH)2 , thereby boosting its performance metrics in heterogeneous CO2 photocatalytic hydrogenation. In situ Fourier transform infrared spectroscopy characterization and density functional theory calculations provided fundamental insights into the catalytically active SFLPs defined as proximal Lewis acidic Cu2+ and Lewis basic OH- . The photocatalytic pathway proceeds through a formate reaction intermediate, which is generated by the reaction of CO2 with heterolytically dissociated H2 on the SFLPs. Given the wealth of information thus uncovered, it is highly likely that this work will spur the further development of similar classes of materials, leading to the advancement and, ultimately, large-scale application of photocatalytic CO2 reduction technologies.

Detailed balance limits for inversion in solar-pumped lasers and allied systems.

Solar-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. Lett.8, 271 (1983)OPLEDP0146-959210.1364/OL.8.000271], where they determined the minimum Stokes shift and the minimum ratio of pump band to emission band absorption constants-based on independent consideration of the emission at pump and emission frequencies. In contrast, the derivation here simultaneously accounts for emission in both the pump and emission bands, which in turn leads to a single consolidated inequality that serves to establish the revised threshold requirements for inversion. Upon applying this new unified relationship to solar-pumped devices, a large increase in the minimum required Stokes shifts for 1-sun devices, particularly at larger pump energies and smaller ratios of αp0/αe0, is found. The maximum possible efficiencies of solar-pumped devices are calculated using this new relation.

Waveguide photoreactor enhances solar fuels photon utilization towards maximal optoelectronic - photocatalytic synergy.

A 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 H2+CO2 atmosphere, a coating of defect engineered In2O3-x(OH)y nanorod Reverse Water Gas Shift solar-fuel catalyst on an optical waveguide outperforms a coated plane by a factor of 2.2. Further, light distribution along the length of the waveguide increases optical pathlengths of the weakly absorptive green and yellow wavelengths, which increases CO product rate by a factor of 8.1-8.7 in the visible. Synergistically pairing with thinly doped silicon on the waveguide enhances the CO production rate by 27% over the visible. In addition, the persistent photoconductivity behavior of the In2O3-x(OH)y system enables CO production at a comparable rate for 2 h after turning off photo-illumination, enhancing yield with 44-62% over thermal only yield. The practical utility of persistent photocatalysis was demonstrated through outdoor solar concentrator tests, which after a day-and-night cycle showed CO yield increase of 19% over a day-light only period.

Adiabatic mode transformation in width-graded nano-gratings enabling multiwavelength light localization.

We 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). By juxtaposing the resonance modes of width-graded and non-graded gratings and defining the adiabaticity condition, we demonstrate the criticality of w and d in achieving adiabatic mode transformation among the grooves. We observe that the resonant wavelength of a graded grating corresponds to the properties of a single groove when the grooves are adiabatically coupled. We show that L plays an important function in defining the span of localized wavelengths. Specifically, we show that multiwavelength resonant modes with intensity enhancement exceeding three orders of magnitude are possible with w < 30 nm and 300 nm < d < 900 nm for a range of fixed values of L. This study presents a novel paradigm of deep-subwavelength adiabatically-coupled width-graded gratings-illustrating its versatility in design, hence its viability for applications ranging from surface enhanced Raman spectroscopy to multispectral imaging.

Tunable rainbow light trapping in ultrathin resonator arrays.

Rainbow 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. We couple this design technique with fabrication through multilayer thin-film deposition and focused ion beam milling, which enables the realisation of unprecedented feature sizes down to 5 nm and corresponding extreme normalised local field enhancements up to 103. We demonstrate rainbow trapping within the devices through hyperspectral microscopy and show agreement between the experimental results and simulation. The combination of expeditious design and precise fabrication underpins the implementation of these nanogroove arrays for manifold applications in sensing and nanoscale optics.

Plasmonic Titanium Nitride Facilitates Indium Oxide CO2 Photocatalysis.

Nanoscale 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, In2 O3- x (OH)y , is a semiconducting material capable of photocatalyzing the hydrogenation of gaseous CO2 ; 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@TiO2 @In2 O3- x (OH)y are combined. This heterostructured material synergistically couples the metallic TiN and semiconducting In2 O3- x (OH)y phases via an interfacial semiconducting TiO2 layer, allowing it to drive the light-assisted reverse water gas shift reaction at a conversion rate greatly surpassing that of its individual components or any binary combinations thereof.

Relating surface defect energetics with reactant gas adsorption during the photo-catalytic reduction of CO2 by partially hydrolyzed In2O3 nanorods.

Photo-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 0.11 eV from H2 to a CO2 + H2 mixture, which correlates with binding energy shifts of the OH shoulder of the O1s spectra. These results show the reactivity link between the various OH groups, oxygen vacancies and trap energies of In2O3-x(OH)y in the reactant gas atmosphere components.

Hydrogen Spillover to Oxygen Vacancy of TiO2-xHy/Fe: Breaking the Scaling Relationship of Ammonia Synthesis.

Optimizing 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 N2 dissociation and NHz (z = 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. Described herein is a second example that is counterintuitively founded upon a strong-strong N-bonding pair unveiled in a bifunctional nanoscale catalyst TiO2-xHy/Fe (where 0.02 ≤ x ≤ 0.03 and 0 < y < 0.03), in which hydrogen spillover (H) from Fe to cascade oxygen vacancies (OV-OV) results in the trapped form of OV-H on the TiO2-xHy component. The Fe component thus enables facile activation of N2, while the OV-H in TiO2-xHy hydrogenates the N or NHz to NH3 easily.

Black indium oxide a photothermal CO2 hydrogenation catalyst.

Nanostructured forms of stoichiometric In2O3 are proving to be efficacious catalysts for the gas-phase hydrogenation of CO2. 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 In2O3 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. Herein, we present a synthetic route to tune the color of In2O3 to pitch black by controlling its degree of non-stoichiometry. Black indium oxide comprises amorphous non-stoichiometric domains of In2O3-x on a core of crystalline stoichiometric In2O3, and has 100% selectivity towards the hydrogenation of CO2 to CO with a turnover frequency of 2.44 s-1.

Synergistic Coupling of Photo and Thermal Conditions for Enhancing CO2 Reduction Rates in the Reverse Water Gas Shift Reaction.

The photocatalytic activity of nanostructured In2O3-x(OH)y for the reverse water gas shift (RWGS) reaction CO2 + H2 → CO + H2O can be greatly enhanced by substitution of Bi(III) for In(III) in the lattice of BizIn2-zO3-x(OH)y. 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 BizIn2-zO3-x(OH)y 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 H2 as an initial gas input under photo and thermal conditions before introducing CO2. Hence, the chemical interplay between environment parameters such as photoillumination, thermal input, and gas reactant components with the effects of Bi substitution is unclear. Reported herein, glovebox-protected X-ray photoelectron spectroscopy (XPS) interrogates this photochemical RWGS reaction transiting from vacuum state to similar conditions in a photocatalytic reactor, under dark and ambient temperatures, 150°C in dark and 150 °C under photoillumination. Binding energy shifts were used to correlate the material system's Lewis basicity response to these acidic probe gases. In-situ gas electronic sensitivity and in-situ UV-vis-derived band-gap trends confirm the trends shown in the XPS results, hence showing its equivalency with in situ methods. The enhanced photocatalytic reduction rate of CO2 with H2 with a low doped 0.05% a.t Bi system is thus associated with an increased gas sensitivity in H2 + CO2, a greater expansion in the OH shoulder than that of the undoped system under heat and light conditions, as well as a greater thermal stability of dissociated H adatoms. The photoinduced expansion of the OH shoulder and the increased positive binding energy shifts show the important role of photoillumination over that of thermal conditions. The poor catalytic performance of the high doped system can be attributed to a competing H2 reduction of In3+. The results provide new insight into how pairing photo and thermal conditions with the methodical tuning of the Lewis acidity and Lewis basicity of surface frustrated Lewis acid-base pair sites by varying z amount in BizIn2-zO3-x(OH)y enables optimization of the rate of the photochemical RWGS.

Plasmonics of Diffused Silver Nanoparticles in Silver/Nitride Optical Thin Films.

Metal-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 SiNx/Ag/SiNx 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. Based on experimental depth profiles, we model the multilayer's silver concentration profile as two complementary error functions: one for the diffused Ag nanoparticles and one for the interface roughness. We apply the Maxwell-Garnett and Bruggeman effective medium theories to determine that diffusion characteristics dominate the experimental absorption spectra. The newfound metal nanoparticle diffusion phenomenon effectively creates a hybrid structure characteristic of both metal-dielectric multilayer and metal-dielectric composite.