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The advent of metasurfaces has revolutionized the design of optical instruments, and recent advancements in fabrication techniques are further accelerating their practical applications. However, conventional top-down fabrication of intricate nanostructures proves to be expensive and time-consuming, posing challenges for large-scale production. Here, we propose a cost-effective bottom-up approach to create nanostructure arrays with arbitrarily complex meta-atoms displaying single nanoparticle lateral resolution over submillimeter areas, minimizing the need for advanced and high-cost nanofabrication equipment. By utilizing air/water interface assembly, we transfer nanoparticles onto templated polydimethylsiloxane (PDMS) irrespective of nanopattern density, shape, or size. We demonstrate the robust assembly of nanocubes into meta-atoms with diverse configurations generally unachievable by conventional methods, including U, L, cross, S, T, gammadion, split-ring resonators, and Pancharatnam-Berry metasurfaces with designer optical functionalities. We also show nanocube epitaxy at near ambient temperature to transform the meta-atoms into complex continuous nanostructures that can be swiftly transferred from PDMS to various substrates via contact printing. Our approach potentially offers a large-scale manufacturing alternative to top-down fabrication for metal nanostructuring, unlocking possibilities in the realm of nanophotonics.

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The fabrication of high quality nanophotonic surfaces for integration in optoelectronic devices remains a challenge because of the complexity and cost of top-down nanofabrication strategies. Combining colloidal synthesis with templated self-assembly emerged as an appealing low-cost solution. However, it still faces several obstacles before integration in devices can become a reality. This is mostly due to the difficulty in assembling small nanoparticles (<50 nm) in complex nanopatterns with a high yield. In this study, a reliable methodology is proposed to fabricate printable nanopatterns with an aspect ratio varying from 1 to 10 and a lateral resolution of 30 nm via nanocube assembly and epitaxy. Investigating templated assembly via capillary forces, a new regime was identified that was used to assemble 30-40 nm nanocubes in a patterned polydimethylsiloxane template with a high yield for both Au and Ag with multiple particles per trap. This new method relies on the generation and control of an accumulation zone at the contact line that is thin as opposed to dense, displaying higher versatility. This is in contrast with conventional wisdom, identifying a dense accumulation zone as a requirement for high-yield assembly. In addition, different formulations are proposed that can be used for the colloidal dispersion, showing that the standard water-surfactant solutions can be replaced by surfactant-free ethanol solutions, with good assembly yield. This allows to minimize the presence of surfactants that can affect electronic properties. Finally, it is shown that the obtained nanocube arrays can be transformed into continuous monocrystalline nanopatterns via nanocube epitaxy at near ambient temperature, and transferred to different substrates via contact printing. This approach opens new doors to the templated assembly of small colloids and could find potential applications in various optoelectronic devices ranging from solar cells to light-emitting diodes and displays.

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Large scale and low-cost nanopatterning of materials is of tremendous interest for optoelectronic devices. Nanoimprint lithography has emerged in recent years as a nanofabrication strategy that is high-throughput and has a resolution comparable to that of electron-beam lithography (EBL). It is enabled by pattern replication of an EBL master into polydimethylsiloxane (PDMS), that is then used to pattern a resist for further processing, or a sol-gel that could be calcinated into a solid material. Although the sol-gel chemistry offers a wide spectrum of material compositions, metals are still difficult to achieve. This gap could be bridged by using colloidal nanoparticles as resist, but deep understanding of the key parameters is still lacking. Here, we use supported metallic nanocubes as a model resist to gain fundamental insights into nanoparticle imprinting. We uncover the major role played by the surfactant layer trapped between nanocubes and substrate, and measure its thickness with subnanometer resolution by using gap plasmon spectroscopy as a metrology platform. This enables us to quantify the van der Waals (VDW) interactions responsible for the friction opposing the nanocube motion, and we find that these are almost in quantitative agreement with the Stokes drag acting on the nanocubes during nanoimprint, that is estimated with a simplified fluid mechanics model. These results reveal that a minimum thickness of surfactant is required, acting as a spacer layer mitigating van der Waals forces between nanocubes and the substrate. In the light of these findings we propose a general method for resist preparation to achieve optimal nanoparticle mobility and show the assembly of printable Ag and Au nanocube grids, that could enable the fabrication of low-cost transparent electrodes of high material quality upon nanocube epitaxy.

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Plasmonic nanoparticles of the highest quality can be obtained via colloidal synthesis at low-cost. Despite the strong potential for integration in nanophotonic devices, the geometry of colloidal plasmonic nanoparticles is mostly limited to that of platonic solids. This is in stark contrast to nanostructures obtained by top-down methods that offer unlimited capability for plasmon resonance engineering, but present poor material quality and have doubtful perspectives for scalability. Here, an approach that combines the best of the two worlds by transforming assemblies of single-crystal gold nanocube building blocks into continuous monocrystalline plasmonic nanostructures with an arbitrary shape, via epitaxy in solution at near ambient temperature, is introduced. Nanocube dimers are used as a nanoreactor model system to investigate the mechanism in operando, revealing competitive redox processes of oxidative etching at the nanocube corners and simultaneous heterogeneous nucleation at their surface, that ensure filling of the sub-nanometer gap in a self-limited manner. Applying this procedure to nanocube arrays assembled in a patterned poly(dimethylsiloxane) (PDMS) substrate, it is able to obtain printable monocrystalline nanoantenna arrays that can be swiftly integrated in devices. This may lead to the implementation of low-cost nanophotonic surfaces of the highest quality in industrial products.

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Lead halide perovskite solar cells have been gaining more and more interest. In only a decade, huge research efforts from interdisciplinary communities enabled enormous scientific advances that rapidly led to energy conversion efficiency near that of record silicon solar cells, at an unprecedented pace. However, while for most materials the best solar cells were achieved with single crystals (SC), for perovskite the best cells have been so far achieved with polycrystalline (PC) thin films, despite the optoelectronic properties of perovskite SC are undoubtedly superior. Here, by taking as example monocrystalline methylammonium lead halide, the authors elaborate the literature from material synthesis and characterization to device fabrication and testing, to provide with plausible explanations for the relatively low efficiency, despite the superior optoelectronics performance. In particular, the authors focus on how solar cell performance is affected by anisotropy, crystal orientation, surface termination, interfaces, and device architecture. It is argued that, to unleash the full potential of monocrystalline perovskite, a holistic approach is needed in the design of next-generation device architecture. This would unquestionably lead to power conversion efficiency higher than those of PC perovskites and silicon solar cells, with tremendous impact on the swift deployment of renewable energy on a large scale.

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The emergence of two-dimensional transition metal dichalcogenide materials has sparked intense activity in valleytronics, as their valley information can be encoded and detected with the spin angular momentum of light. We demonstrate the valley-dependent directional coupling of light using a plasmonic nanowire-tungsten disulfide (WS2) layers system. We show that the valley pseudospin in WS2 couples to transverse optical spin of the same handedness with a directional coupling efficiency of 90 ± 1%. Our results provide a platform for controlling, detecting, and processing valley and spin information with precise optical control at the nanoscale.

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Monocrystalline materials are essential for optoelectronic devices such as solar cells, LEDs, lasers, and transistors to reach the highest performance. Advances in synthetic chemistry now allow for high quality monocrystalline nanomaterials to be grown at low temperature in solution for many materials; however, the realization of extended structures with control over the final 3D geometry still remains elusive. Here, a new paradigm is presented, which relies on epitaxy between monocrystalline nanocube building blocks. The nanocubes are assembled in a predefined pattern and then epitaxially connected at the atomic level by chemical growth in solution, to form monocrystalline nanopatterns on arbitrary substrates. As a first demonstration, it is shown that monocrystalline silver structures obtained with such a process have optical properties and conductivity comparable to single-crystalline silver. This flexible multiscale process may ultimately enable the implementation of monocrystalline materials in optoelectronic devices, raising performance to the ultimate limit.

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Nanoscale materials are promising for optoelectronic devices because their physical dimensions are on the order of the wavelength of light. This leads to a variety of complex optical phenomena that, for instance, enhance absorption and emission. However, quantifying the performance of these nanoscale devices frequently requires measuring absolute absorption at the nanoscale, and remarkably, there is no general method capable of doing so directly. Here, we present such a method based on an integrating sphere but modified to achieve submicron spatial resolution. We explore the limits of this technique by using it to measure spatial and spectral absorptance profiles on a wide variety of nanoscale systems, including different combinations of weakly and strongly absorbing and scattering nanomaterials (Si and GaAs nanowires, Au nanoparticles). This measurement technique provides quantitative information about local optical properties that are crucial for improving any optoelectronic device with nanoscale dimensions or nanoscale surface texturing.

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Three-dimensional (3D) characterization of nanomaterials is traditionally performed by either cross-sectional milling with a focused ion beam (FIB), or transmission electron microscope tomography. While these techniques can produce high quality reconstructions, they are destructive, or require thin samples, often suspended on support membranes. Here, we demonstrate a complementary technique allowing non-destructive investigation of the 3D structure of samples on bulk substrates. This is performed by imaging backscattered electron (BSE) emission at multiple primary beam energies - as the penetration depth of primary electrons is proportional to the beam energy, depth information can be obtained through variations in the beam acceleration. The detected signal however consists of a mixture of the penetrated layers, meaning the structure's three-dimensional geometry can only be retrieved after deconvolving the BSE emission profile from the observed BSE images. This work demonstrates this novel approach by applying a blind source separation deconvolution algorithm to multi-energy acquired BSE images. The deconvolution can thereby allow a 3D reconstruction to be produced from the acquired images of an arbitrary sample, showing qualitative agreement with the true depth structure, as verified through FIB cross-sectional imaging.

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Photoelectrochemical water splitting is a promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the efficiency of this energy conversion process is low because of the limited light absorption and rapid bulk recombination of charge carriers. In this study, the combination of a novel ternary sensitizer AgFeS2 , having a narrow bandgap of 0.9 eV, with a BiVO4 electrode is presented for the enhancement of the solar-energy-to-hydrogen conversion efficiency. The photoelectrochemical properties of this combined material were investigated and the photocurrent densities of AgFeS2 -BiVO4 composite electrodes were greatly enhanced compared with pristine BiVO4 (15 times higher at 0.6 V vs. Ag/AgCl under AM 1.5G illumination). The enhanced photoelectrochemical properties arise from extended light absorption, fast charge transfer and appropriate energy gap alignment. It was demonstrated that AgFeS2 nanowires are promising inorganic sensitizers for improving the efficiency of solar water splitting.

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A transparent conducting film composed of regular networks of silver nanowires is obtained by combining a soft solution process (Tollens' reaction) and nanoimprint lithography. The solution-grown nanowire networks show a threefold higher conductivity than grids obtained by metal evaporation. This is due to the larger grain size in the solution-grown nanowires, which results in a strong reduction of electron scattering by grain boundaries.

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We report on the synthesis of semiconducting AgFeS2 nanowires, obtained from the conversion of Ag nanowires. The study of the conversion process shows that the formation of Ag2S nanowires, as an intermediate step, precedes the conversion into AgFeS2 nanowires. The chemical properties of AgFeS2 nanowires were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy at intermediate steps of the conversion process and show that the temperature at which the reaction takes place is critical to obtaining nanowires as opposed to nanotubes. Optical measurements on nanowire ensembles confirm the semiconducting nature of AgFeS2, with a direct band gap of 0.88 eV.

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The epitaxial growth of monocrystalline semiconductors on metal nanostructures is interesting from both fundamental and applied perspectives. The realization of nanostructures with excellent interfaces and material properties that also have controlled optical resonances can be very challenging. Here we report the synthesis and characterization of metal-semiconductor core-shell nanowires. We demonstrate a solution-phase route to obtain stable core-shell metal-Cu2O nanowires with outstanding control over the resulting structure, in which the noble metal nanowire is used as the nucleation site for epitaxial growth of quasi-monocrystalline Cu2O shells at room temperature in aqueous solution. We use X-ray and electron diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence spectroscopy, and absorption spectroscopy, as well as density functional theory calculations, to characterize the core-shell nanowires and verify their structure. Metal-semiconductor core-shell nanowires offer several potential advantages over thin film and traditional nanowire architectures as building blocks for photovoltaics, including efficient carrier collection in radial nanowire junctions and strong optical resonances that can be tuned to maximize absorption.

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In this paper, the covalent immobilization and luminescence enhancement of a europium (Eu(III)) complex in a porous silicon (pSi) layer with a microcavity (pSiMC) structure are demonstrated. The alkyne-pendant arm of the Eu(III) complex was covalently immobilized on the azide-modified surface via ligand-assisted "click" chemistry. The design parameters of the microcavity were optimized to obtain an efficient luminescence-enhancing device. Luminescence enhancements by a factor of 9.5 and 3.0 were observed for Eu(III) complex bound inside the pSiMC as compared to a single layer and Bragg reflector of identical thickness, respectively, confirming the increased interaction between the immobilized molecules and the electric field in the spacer of the microcavity. When comparing pSiMCs with different resonance wavelength position, luminescence was enhanced when the resonance wavelength overlapped with the maximum emission wavelength of the Eu(III) complex at 614 nm, allowing for effective coupling between the confined light and the emitting molecules. The pSiMC also improved the spectral color purity of the Eu(III) complex luminescence. The ability of a pSiMC to act as an efficient Eu(III) luminescence enhancer, combined with the resulting sharp linelike emission, can be exploited for the development of ultrasensitive optical biosensors.

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A dip biosensor is realized by depositing metallic nanoparticles onto the tip of a cleaved optical fiber. Light coupled into the fiber interacts with the localized surface plasmons within the nanoparticles at the tip; a portion of the scattered light recouples into the optical fiber and is analyzed by a spectrometer. Characterization of the sensor demonstrates an inverse relationship between the sensitivity and the number of particles deposited onto the surface, with smaller quantities leading to greater sensitivity. The results obtained showed also that by depositing nanoparticles with distinct localized surface plasmon resonance signatures with limited overlap, as for the case of gold and silver nanospheres, a multiplexed dip biosensor can be realized by simply functionalizing the different nanoparticles with different antibodies after the fashion of an immunoassay. In this way different localized surface plasmons resonance bands responsive to different target analytes can be separately monitored, as further presented below, requiring a minimal quantity of reagents both for the functionalization process and for the sample analysis.

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Surface plasmon resonance (SPR)-based sensors enable the rapid, label-free and highly sensitive detection of a large range of biomolecules. We have previously shown that, using silver-coated optical fibers with a high surface roughness, re-scattering of light from the surface plasmons is possible, turning SPR into a radiative process. The efficacy of this platform has proven for the detection of large biomolecules such as viruses, proteins and enzymes. Here, we demonstrate that by bringing together this novel emission-based fiber SPR platform with an improved surface functionalization process aimed at properly orienting the antibodies, it is possible to rapidly and specifically detect the regulation of human apolipoprotein E (apoE), a low-molecular-weight protein (~39 kDa) known to be involved in cardiovascular diseases, Alzheimer's disease and gastric cancer. The results obtained clearly show that this new sensing platform has the potential to serve as a tool for point-of-decision medical diagnostics. FROM THE CLINICAL EDITOR: In this study, a novel emission-based surface plasmon resonance platform using silver-coated optical fibers is described. Properly orienting antibodies on the surface enables rapid and specific detection of human apolipoprotein E (apoE).

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A nanostructured porous silicon chip functionalized with dichlorofluorescein is employed as a nanoreactor to respond to Reactive Oxygen Species (ROS) and to real-time studying redox reactions.

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The high stability of Salonen's thermally carbonized porous silicon (TCPSi) has attracted attention for environmental and biochemical sensing applications, where corrosion-induced zero point drift of porous silicon-based sensor elements has historically been a significant problem. Prepared by the high temperature reaction of porous silicon with acetylene gas, the stability of this silicon carbide-like material also poses a challenge--many sensor applications require a functionalized surface, and the low reactivity of TCPSi has limited the ability to chemically modify its surface. This work presents a simple reaction to modify the surface of TCPSi with an alkyl carboxylate. The method involves radical coupling of a dicarboxylic acid (sebacic acid) to the TCPSi surface using a benzoyl peroxide initiator. The grafted carboxylic acid species provides a route for bioconjugate chemical modification, demonstrated in this work by coupling propylamine to the surface carboxylic acid group through the intermediacy of pentafluorophenol and 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC). The stability of the carbonized porous Si surface, both before and after chemical modification, is tested in phosphate buffered saline solution and found to be superior to either hydrosilylated (with undecylenic acid) or thermally oxidized porous Si surfaces.

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The coupling of optical Bloch surface waves at the truncated end of one dimensional porous silicon photonic crystals is exploited for fast vapour sensing. Self-standing multilayered membranes bound to transparent substrates were fabricated by electrochemical etching and used in an attenuated total reflection configuration to resonantly excite the surface waves and perform real-time sensing.