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Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures. In situ VSFG spectro-electrochemistry measurements correlate the CoIIâCoIII oxidation with the flip of the bridging CN ligand from Co-NC-Fe coordination mode to a Co-CN-Fe one. Photoluminescence measurements and X-ray photoelectron spectroscopy reveal that this unprecedented linkage isomerism originates from surface defects, which act as oxidation sites for the PBA. The presence of such surface defects is correlated with the fabrication temperature for PBA/ZnO. Thus, this contribution identifies the interplay between the surface states of the ZnO substrates and the chemical composition of PBA at the ZnO surface, suggesting an easily accessible approach to control the chemical composition of the interface.
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In this work, we demonstrate the optical heating modulation of soliton-based supercontinuum generation through the employment of multi-walled carbon nanotubes (MW-CNTs) acting as fast and efficient heat generators. By utilizing highly dispersion-sensitive liquid-core fibers in combination with MW-CNTs coated to the outer wall of the fiber, spectral tuning of dispersive waves with response times below one second via exploiting the strong thermo-optic response of the core liquid was achieved. Local illumination of the MW-CNTs coated fiber at selected points allowed modulation of the waveguide dispersion, thus controlling the soliton fission process. Experimentally, a spectral shift of the two dispersive waves towards the region of anomalous dispersion was observed at increasing temperatures. The presented tuning concept shows great potential in the context of nonlinear photonics, as complex and dynamically reconfigurable dispersion profiles can be generated by using structured light fields. This allows investigating nonlinear frequency conversion processes under unconventional conditions, and realizing nonlinear light sources that are reconfigurable quickly.
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We present a tabletop setup for extreme ultraviolet (EUV) reflection spectroscopy in the spectral range from 40 to 100 eV by using high-harmonic radiation. The simultaneous measurements of reference and sample spectra with high energy resolution provide precise and robust absolute reflectivity measurements, even when operating with spectrally fluctuating EUV sources. The stability and sensitivity of EUV reflectivity measurements are crucial factors for many applications in attosecond science, EUV spectroscopy, and nano-scale tomography. We show that the accuracy and stability of our in situ referencing scheme are almost one order of magnitude better in comparison to subsequent reference measurements. We demonstrate the performance of the setup by reflective near-edge x-ray absorption fine structure measurements of the aluminum L2/3 absorption edge in α-Al2O3 and compare the results to synchrotron measurements.
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We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N2 atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I3- species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.
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In order to facilitate the design freedom for the implementation of textile-integrated electronics, we seek flexible transparent conductive electrodes (TCEs) that can withstand not only the mechanical stresses encountered during use but also the thermal stresses of post-treatment. The transparent conductive oxides (TCO) typically used for this purpose are rigid in comparison to the fibers or textiles they are intended to coat. In this paper, a TCO, specifically aluminum-doped zinc oxide (Al:ZnO), is combined with an underlying layer of silver nanowires (Ag-NW). This combination brings together the advantages of a closed, conductive Al:ZnO layer and a flexible Ag-NW layer, forming a TCE. The result is a transparency of 20-25% (within the 400-800 nm range) and a sheet resistance of 10 Ω/sq that remains almost unchanged, even after post-treatment at 180 °C.
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Antireflective (AR) nanostructures offer an effective, broadband alternative to conventional AR coatings that could be used even under extreme conditions. In this publication, a possible fabrication process based on colloidal polystyrene (PS) nanosphere lithography for the fabrication of such AR structures on arbitrarily shaped fused silica substrates is presented and evaluated. Special emphasis is placed on the involved manufacturing steps in order to be able to produce tailored and effective structures. An improved Langmuir-Blodgett self-assembly lithography technique enabled the deposition of 200 nm PS spheres on curved surfaces, independent of shape or material-specific characteristics such as hydrophobicity. The AR structures were fabricated on planar fused silica wafers and aspherical planoconvex lenses. Broadband AR structures with losses (reflection + transmissive scattering) of <1% per surface in the spectral range of 750-2000 nm were produced. At the best performance level, losses were less than 0.5%, which corresponds to an improvement factor of 6.7 compared to unstructured reference substrates.
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Laser safety is starting to play an increasingly important role, especially when the laser is used as a tool. Passive laser safety systems quickly reach their limits and, in some cases, provide inadequate protection. To counteract this, various active systems have been developed. Flexible and especially textile-protective materials pose a special challenge. The market still lacks personal protective equipment (PPE) for active laser safety. Covering these materials with solar cells as large-area optical detectors offers a promising possibility. In this work, an active laser protection fabric with amorphous silicon solar cells is presented as a large-scale sensor for continuous wave and pulsed lasers (down to ns). First, the fabric and the solar cells were examined separately for irradiation behavior and damage. Laser irradiation was performed at wavelengths of 245, 355, 532, and 808 nm. The solar cell sensors were then applied directly to the laser protection fabric. The damage and destruction behavior of the active laser protection system was investigated. The results show that the basic safety function of the solar cell is still preserved when the locally damaged or destroyed area is irradiated again. A simple automatic shutdown system was used to demonstrate active laser protection within 50 ms.
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Plasmonic nanoparticle arrays with a specific lattice arrangement can support surface lattice resonances (SLRs). SLR exhibits a sharp spectral peak and finds many applications including optical sensing and plasmonic lasers. To optimize SLR for application, a robust method that allows the mass production of plasmonic nanoparticle arrays with refined particle morphology and well-defined lattice arrangement is required. In this work, we combine nanosphere lithography (NSL) with thermal annealing or nanosecond-pulsed laser treatment to refine plasmonic nanoparticles in a honeycomb lattice. We comparatively study the effects of the two treatment methods on the particle morphology and lattice arrangement of mono (Ag and Pd) and bi-metallic (Ag-Pd) nanoparticle lattices. In general, thermal annealing preserves the lattice arrangement but fairly changes the particle roundness, while laser treatment produces particles with varying morphologies and spatial distribution. We also theoretically and experimentally investigate the optical responses of Ag nanoparticle lattices produced by different treatment methods. The observed difference in spectra can be attributed to the varying particle morphology, which shifts the localized surface plasmon resonance differently, resulting in a significant change in SLR. These findings provide valuable insights for optimizing plasmonic nanoparticle arrays for various applications.
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The integration of electronic functionalities into textiles for use as wearable sensors, energy harvesters, or coolers has become increasingly important in recent years. A special focus is on efficient thermoelectric materials. Copper iodide as a p-type thermoelectrically active, nontoxic material is attractive for energy harvesting and energy generation because of its transparency and possible high-power factor. The deposition of CuI on polyester spacer fabrics by wet chemical processes represents a great potential for use in textile industry for example as flexible thermoelectric energy generators in the leisure or industrial sector as well as in medical technologies. The deposited material on polyester yarn is investigated by electron microscopy, x-ray diffraction and by thermoelectric measurements. The Seebeck coefficient was observed between 112 and 153 µV/K in a temperature range between 30 °C and 90 °C. It is demonstrated that the maximum output power reached 99 nW at temperature difference of 65.5 K with respect to room temperature for a single textile element. However, several elements can be connected in series and the output power can be linear upscaled. Thus, CuI coated on 3D spacer fabrics can be attractive to fabricate thermoelectric devices especially in the lower temperature range for textile medical or leisure applications.
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Nanoparticles consisting of a mixture of several metals and also porous nanoparticles due to their special structure exhibit properties that find applications in spectroscopic detection or catalysis. Different approaches of top down or bottom up technologies exist for the fabrication of such particles. We present a novel combined approach for the fabrication of spherical porous gold nanoparticles on low-cost glass substrates under ambient conditions using a UV-laser induced particle preparation process with subsequent wet chemical selective etching. In this preparation route, nanometer-sized branched structures are formed in spherical particles. The laser process, which is applied to a silver/gold bilayer system with different individual layer thicknesses, generates spherical mixed particles in a nanosecond range and influences the properties of the fabricated nanoparticles, such as the size and the mixture and thus the spectral response. The subsequent etching process is performed by selective wet chemical removal of silver from the nanoparticles with diluted nitric acid. The gold to silver ratio was investigated by energy-dispersive X-ray spectroscopy. The porosity depends on laser parameters and film thickness as well as on etching parameters such as time. After etching, the surface area of the remaining Au nanoparticles increases which makes these particles interesting for catalysis and also as carrier particles for substances. Such substances can be positioned at defined locations or be released in appropriate environments. Absorbance spectra are also analyzed to show how the altered fractured shape of the particles changes localized plasmon resonances of the resultingt particles.
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We report on the localization of the initially excited electronic state within the molecular framework of a series of [Ru(bpy)2dppz]2+ derivatives (bpy:2,2'-bipyridine, dppz: dipyrido-phenazine) as sensitizers in NiO based photocathodes. The introduction of conjugated linkers with phenylene and triazole moieties in the bpy ligand sphere separates the NiO surface from the metal center and hence is considered to stabilize the charge separated state, which results from light-driven hole injection. However, introduction of the conjugated linkers also alters the localization of the excess electron density in the excited state within the ligand sphere and impacts the extent to which the charge-separated state is formed. The study emphasizes that tuning the ligand with the lowest-energy π* orbital distal or proximal to the NiO surface significantly affects the initial charge-separation and the solar cell performance. The stability of the charge-separated state correlates with the observed photocurrents in dye-sensitized solar cells. Furthermore, the study challenges the widely accepted concept that the introduction of extended anchoring groups, i.e. increasing Ru - NiO distance, stabilizes the charge-separated state and suppresses charge recombination at the metal-oxide molecule interface.
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In this contribution, inspired by the excellent resource management and material transport function of leaf veins, the electrical transport function of metallized leaf veins is mimicked from the material transport function of the vein networks. By electroless copper plating on real leaf vein networks with copper thickness of only several hundred nanometre up to several micrometre, certain leaf veins can be converted to transparent conductive electrodes with an ultralow sheet resistance 100 times lower than that of state-of-the-art indium tin oxide thin films, combined with a broadband optical transmission of above 80% in the UV-VIS-IR range. Additionally, the resource efficiency of the vein-like electrode is characterized by the small amount of material needed to build up the networks and the low copper consumption during metallization. In particular, the high current density transport capability of the electrode of > 6000 A cm-2 was demonstrated. These superior properties of the vein-like structures inspire the design of high-performance transparent conductive electrodes without using critical materials and may significantly reduce the Ag consumption down to < 10% of the current level for mass production of solar cells and will contribute greatly to the electrode for high power density concentrator solar cells, high power density Li-ion batteries, and supercapacitors.
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A series of thiocyanate-free bis(tridentate) ruthenium(II) complexes incorporating 1,2,3-triazole-derived NNN-, NCN-, and CNC-coordinating ligands has been employed for sensitizing ZnO photoanodes for dye-sensitized solar cells (DSSCs). Additionally, the first use of the TEMPO+ /TEMPO (2,2,6,6-tetramethyl-piperidine-1-oxyl) redox mediator as a surrogate for the I3 - /I- redox couple in ZnO nanostructured DSSCs is presented. Compared with I3 - /I- -based electrolytes, shorter charge lifetimes and diffusion lengths were determined for the TEMPO+ /TEMPO-based electrolyte. Nonetheless, similar power conversion efficiencies (PCEs) were achieved with both electrolytes for the RuNCN and RuCNC complexes, whereas higher PCEs are enabled by the iodine-free electrolyte in case of RuNNN. The combination of the molecular sensitizers and the TEMPO-based electrolyte exhibits relatively high external quantum efficiency (EQE) and promising PCEs, ranging from 4.48 to 1.47 %, which are-in part-comparable to that of ZnO-DSSCs with the benchmark N749 black dye. The TEMPO-based electrolyte also exhibits less absorption compared with its I3 - /I- counterpart, a favorable feature for enhancing the light harvesting ability of the photoanode. Furthermore, the results show the effect of the dye-sensitization procedure on the PCE values: The use of ethanol as the solvent compared with methanol increases the DSSC's efficiency, which is attributed to improved chemisorption of the sensitizer onto the ZnO surface.