Alternative nano-lithographic tools for shell-isolated nanoparticle enhanced Raman spectroscopy substrates.

Chemically synthesized metal nanoparticles (MNPs) have been widely used as surface-enhanced Raman spectroscopy (SERS) substrates for monitoring catalytic reactions. In some applications, however, the SERS MNPs, besides being plasmonically active, can also be catalytically active and result in Raman signals from undesired side products. The MNPs are typically insulated with a thin (∼3 nm), in principle pin-hole-free shell to prevent this. This approach, which is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), offers many advantages, such as better thermal and chemical stability of the plasmonic nanoparticle. However, having both a high enhancement factor and ensuring that the shell is pin-hole-free is challenging because there is a trade-off between the two when considering the shell thickness. So far in the literature, shell insulation has been successfully applied only to chemically synthesized MNPs. In this work, we alternatively study different combinations of chemical synthesis (bottom-up) and lithographic (top-down) routes to obtain shell-isolated plasmonic nanostructures that offer chemical sensing capabilities. The three approaches we study in this work include (1) chemically synthesized MNPs + chemical shell, (2) lithographic substrate + chemical shell, and (3) lithographic substrate + atomic layer deposition (ALD) shell. We find that ALD allows us to fabricate controllable and reproducible pin-hole-free shells. We showcase the ability to fabricate lithographic SHINER substrates which report an enhancement factor of 7.5 × 103 ± 17% for our gold nanodot substrates coated with a 2.8 nm aluminium oxide shell. Lastly, by introducing a gold etchant solution to our fabricated SHINER substrate, we verified that the shells fabricated with ALD are truly pin-hole-free.

Alanine Formation in a Zero-Gap Flow Cell and the Role of TiO2/Ti Electrocatalysts.

The electrochemical synthesis of α ${\alpha }$ -amino acids at room temperature and pressure is a sustainable alternative to conventional methods like microbial fermentation and Strecker synthesis. A custom-built zero-gap flow electrolyzer was used to study the electrosynthesis of alanine via the electrocatalytic reductive amination (ERA) of the corresponding biomass-derivable α ${\alpha }$ -keto acid precursor - pyruvic acid (PA), and hydroxylamine (NH2OH) at very low pH. Non-toxic, abundant, and easy to prepare TiO2/Ti electrocatalysts were utilized as the cathode. Three TiO2/Ti felt electrodes with different oxide thicknesses were prepared and their characterization results were correlated with their respective electrochemical performance in terms of Faradaic efficiency η ${\eta }$ , and partial current density j ‾ ${\left|\overline{j}\right|}$ . Cyclic voltammetry indicated a different electrocatalytic reduction process on hydrothermally treated electrodes, compared to thermally oxidized ones. Hydrothermally treated electrodes were also found to have the thickest porous anatase layer and achieved 50-75 % alanine conversion efficiencies. Optimization showed that the cell potential, reactant flow rate and the PA: NH2OH ratio were crucial parameters in determining the conversion efficiency. η ${\eta }$ and j ‾ ${\left|\overline{j}\right|}$ were found to significantly decrease when an excess of is used and, an optimal alanine η ${\eta }$ of 75 % was achieved at 2.0 V applied cell potential and 10 mL/h reactant flow rate.

Enhanced Performance of an Acoustofluidic Device by Integrating Temperature Control.

Acoustofluidics is an emerging research field wherein either mixing or (bio)-particle separation is conducted. High-power acoustic streaming can produce more intense and rapid flow patterns, leading to faster and more efficient liquid mixing. However, without cooling, the temperature of the piezoelectric element that is used to supply acoustic power to the fluid could rise above 50% of the Curie point of the piezomaterial, thereby accelerating its aging degradation. In addition, the supply of excessive heat to a liquid may lead to irreproducible streaming effects and gas bubble formation. To control these phenomena, in this paper, we present a feedback temperature control system integrated into an acoustofluidic setup using bulk acoustic waves (BAWs) to elevate mass transfer and manipulation of particles. The system performance was tested by measuring mixing efficiency and determining the average velocity magnitude of acoustic streaming. The results show that the integrated temperature control system keeps the temperature at the set point even at high acoustic powers and improves the reproducibility of the acoustofluidic setup performance when the applied voltage is as high as 200 V.

3D-Architected Alkaline-Earth Perovskites.

3D ceramic architectures are captivating geometrical features with an immense demand in optics. In this work, an additive manufacturing (AM) approach for printing alkaline-earth perovskite 3D microarchitectures is developed. The approach enables custom-made photoresists suited for two-photon lithography, permitting the production of alkaline-earth perovskite (BaZrO3 , CaZrO3 , and SrZrO3 ) 3D structures shaped in the form of octet-truss lattices, gyroids, or inspired architectures like sodalite zeolite, and C60 buckyballs with micrometric and nanometric feature sizes. Alkaline-earth perovskite morphological, structural, and chemical characteristics are studied. The optical properties of such perovskite architectures are investigated using cathodoluminescence and wide-field photoluminescence emission to estimate the lifetime rate and defects in BaZrO3 , CaZrO3 , and SrZrO3 . From a broad perspective, this AM methodology facilitates the production of 3D-structured mixed oxides. These findings are the first steps toward dimensionally refined high-refractive-index ceramics for micro-optics and other terrains like (photo/electro)catalysis.

Influence of Wettability and Geometry on Contact Electrification between Nonionic Insulators.

Contact electrification is an interfacial process in which two surfaces exchange electrical charges when they are in contact with one another. Consequently, the surfaces may gain opposite polarity, inducing an electrostatic attraction. Therefore, this principle can be exploited to generate electricity, which has been precisely done in triboelectric nanogenerators (TENGs) over the last decades. The details of the underlying mechanisms are still ill-understood, especially the influence of relative humidity (RH). Using the colloidal probe technique, we convincingly show that water plays an important role in the charge exchange process when two distinct insulators with different wettability are contacted and separated in <1 s at ambient conditions. The charging process is faster, and more charge is acquired with increasing relative humidity, also beyond RH = 40% (at which TENGs have their maximum power generation), due to the geometrical asymmetry (curved colloid surface vs planar substrate) introduced in the system. In addition, the charging time constant is determined, which is found to decrease with increasing relative humidity. Altogether, the current study adds to our understanding of how humidity levels affect the charging process between two solid surfaces, which is even enhanced up to RH = 90% as long as the curved surface is hydrophilic, paving the way for designing novel and more efficient TENGs, eco-energy harvesting devices which utilize water and solid charge interaction mechanism, self-powered sensors, and tribotronics.

Low-Variance Surface-Enhanced Raman Spectroscopy Using Confined Gold Nanoparticles over Silicon Nanocones.

Surface-enhanced Raman spectroscopy (SERS) substrates are of utmost interest in the analyte detection of biological and chemical diagnostics. This is primarily due to the ability of SERS to sensitively measure analytes present in localized hot spots of the SERS nanostructures. In this work, we present the formation of 67 ± 6 nm diameter gold nanoparticles supported by vertically aligned shell-insulated silicon nanocones for ultralow variance SERS. The nanoparticles are obtained through discrete rotation glancing angle deposition of gold in an e-beam evaporating system. The morphology is assessed through focused ion beam tomography, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. The optical properties are discussed and evaluated through reflectance measurements and finite-difference time-domain simulations. Lastly, the SERS activity is measured by benzenethiol functionalization and subsequent Raman spectroscopy in the surface scanning mode. We report a homogeneous analytical enhancement factor of 2.2 ± 0.1 × 107 (99% confidence interval for N = 400 grid spots) and made a comparison to other lithographically derived assemblies used in SERS. The strikingly low variance (4%) of our substrates facilitates its use for many potential SERS applications.

Structured microgroove columns as a potential solution to obtain perfectly ordered particle beds.

We report on a novel concept to produce ordered beds of spherical particles in a suitable format for liquid chromatography. In this concept, spherical particles are either positioned individually (single-layer column) or stacked (multi-layer column) in micromachined pockets that form an interconnected array of micro-grooves acting as a perfectly ordered chromatographic column. As a first step towards realizing this concept, we report on the breakthrough we realized by obtaining a solution to uniformly fill the micro-groove arrays with spherical particles. We show this can be achieved in a few sweeps using a dedicated rubbing approach wherein a particle suspension is manually rubbed over a silicon chip. In addition, numerical calculations of the dispersion in the newly introduced column format have been carried out and demonstrate the combined advantage of order and reduced flow resistance the newly proposed concept has over the conventional packed bed. For fully-porous particles and a zone retention factor of k'' = 2, the hmin decreases from hmin = 1.9 for the best possible packed bed column to around hmin = 1.0 for the microgroove array, while the interstitial velocity-based separation impedance Ei (a direct measure for the required analysis time) decreases from 1450 to 200. The next steps will focus on the removal of occasional particles remaining on the sides of the micro-pockets, the addition of a cover substrate to seal the column and the subsequent conduction of actual chromatographic separations.

Stress-dependent macromolecular crowding in the mitochondrial matrix.

Macromolecules of various sizes induce crowding of the cellular environment. This crowding impacts on biochemical reactions by increasing solvent viscosity, decreasing the water-accessible volume and altering protein shape, function, and interactions. Although mitochondria represent highly protein-rich organelles, most of these proteins are somehow immobilized. Therefore, whether the mitochondrial matrix solvent exhibits macromolecular crowding is still unclear. Here, we demonstrate that fluorescent protein fusion peptides (AcGFP1 concatemers) in the mitochondrial matrix of HeLa cells display an elongated molecular structure and that their diffusion constant decreases with increasing molecular weight in a manner typical of macromolecular crowding. Chloramphenicol (CAP) treatment impaired mitochondrial function and reduced the number of cristae without triggering mitochondrial orthodox-to-condensed transition or a mitochondrial unfolded protein response. CAP-treated cells displayed progressive concatemer immobilization with increasing molecular weight and an eightfold matrix viscosity increase, compatible with increased macromolecular crowding. These results establish that the matrix solvent exhibits macromolecular crowding in functional and dysfunctional mitochondria. Therefore, changes in matrix crowding likely affect matrix biochemical reactions in a manner depending on the molecular weight of the involved crowders and reactants.

White emission in 3D-printed phosphor microstructures.

Microscale functional materials permit advanced applications in optics and photonics. This work presents the additive manufacturing of three-dimensional structured phosphors emitting red, green, blue, and white. The development is a step forward to realizing additive colour synthesis within complex architectures of relevance in integrated optics or light-emitting sources.

A compact permanent magnet for microflow NMR relaxometry.

We design and demonstrate a compact, robust, and simple to assemble and tune permanent magnet suitable for NMR relaxometry measurements of microfluidic flows. Soft-magnetic stainless-steel plates, incorporated inside the magnet airgap, are key for obtaining substantially improved and tunable field homogeneity. The design is scalable for different NMR probe sizes with the region of suitable field homogeneity, less than 200 ppm, achievable in a capillary length of about 50 % of the total magnet length. The built physical prototype, having 3.5x3.5x8.0 cm3 in size and 5 mm high airgap, provides a field strength of 0.5 T and sufficient field homogeneity for NMR relaxometry measurements in capillaries up to 1.6 mm i.d. and 20 mm long. The magnet was used for test flow rate measurements in a wide range, from 0.001 ml/min to 20 ml/min.

Self-Aligned Crystallographic Multiplication of Nanoscale Silicon Wedges for High-Density Fabrication of 3D Nanodevices.

High-density arrays of silicon wedges bound by {111} planes on silicon (100) wafers have been created by combining convex corner lithography on a silicon dioxide hard mask with anisotropic, crystallographic etching in a repetitive, self-aligned multiplication procedure. A mean pitch of around 30 nm has been achieved, based on an initial pitch of ∼120 nm obtained through displacement Talbot lithography. The typical resolution of the convex corner lithography was reduced to the sub-10 nm range by employing an 8 nm silicon dioxide mask layer (measured on the {111} planes). Nanogaps of 6 nm and freestanding silicon dioxide flaps as thin as 1-2 nm can be obtained when etching the silicon at the exposed apices of the wedges. To enable the repetitive procedure, it was necessary to protect the concave corners between the wedges through "concave" corner lithography. The produced high-density arrays of wedges offer a promising template for the fabrication of large arrays of nanodevices in various domains with relevant details in the sub-10 nm range.

Triboelectric Charging of Particles, an Ongoing Matter: From the Early Onset of Planet Formation to Assembling Crystals.

Triboelectrification is the spontaneous charging of two bodies when released from contact. Even though its manifestation is commonplace, in for instance triboelectric nanogenerators, scientists find the tribocharging mechanism a mystery. The primary aim of this mini-review is to provide an overview of different tribocharging concepts that have been applied to study and realize the formation of ordered stable structures using different objects on various length scales. Relevance spans from materials to planet formations. Especially, dry assembly methods of particles of different shapes based on tribocharging to obtain crystal structures or monolayers are considered. In addition, the current technology employed to examine tribocharging in (semi)dry environments is discussed as well as the relevant forces playing a role in the assembly process. In brief, this mini-review is expected to provide a better understanding of tribocharging in assembling objects on the nano- and micrometer scales.

Large Dense Periodic Arrays of Vertically Aligned Sharp Silicon Nanocones.

Convex cylindrical silicon nanostructures, also referred to as silicon nanocones, find their value in many applications ranging from photovoltaics to nanofluidics, nanophotonics, and nanoelectronic applications. To fabricate silicon nanocones, both bottom-up and top-down methods can be used. The top-down method presented in this work relies on pre-shaping of silicon nanowires by ion beam etching followed by self-limited thermal oxidation. The combination of pre-shaping and oxidation obtains high-density, high aspect ratio, periodic, and vertically aligned sharp single-crystalline silicon nanocones at the wafer-scale. The homogeneity of the presented nanocones is unprecedented and may give rise to applications where numerical modeling and experiments are combined without assumptions about morphology of the nanocone. The silicon nanocones are organized in a square periodic lattice, with 250 nm pitch giving arrays containing 1.6 billion structures per square centimeter. The nanocone arrays were several mm2 in size and located centimeters apart across a 100-mm-diameter single-crystalline silicon (100) substrate. For single nanocones, tip radii of curvature < 3 nm were measured. The silicon nanocones were vertically aligned, baring a height variation of < 5 nm (< 1%) for seven adjacent nanocones, whereas the height inhomogeneity is < 80 nm (< 16%) across the full wafer scale. The height inhomogeneity can be explained by inhomogeneity present in the radii of the initial columnar polymer mask. The presented method might also be applicable to silicon micro- and nanowires derived through other top-down or bottom-up methods because of the combination of ion beam etching pre-shaping and thermal oxidation sharpening. A novel method is presented where argon ion beam etching and thermal oxidation sharpening are combined to tailor a high-density single-crystalline silicon nanowire array into a vertically aligned single-crystalline silicon nanocones array with < 3 nm apex radius of curvature tips, at the wafer scale.

Evaluation of Gas Chromatography Columns with Radially Elongated Pillars as Second-Dimension Columns in Comprehensive Two-Dimensional Gas Chromatography.

The present study investigated the use of a dedicated gas chromatography (GC) column (L = 70 cm, 75 µm deep, and 6.195 mm wide) with radially elongated pillars (REPs) as the second column in a comprehensive two-dimensional gas chromatography (GC × µGC) system. Three stationary phases [apolar polydimethylsiloxane (PDMS), medium polar room-temperature ionic liquid (RTIL) based on monocationic phosphonium, and polar polyethylene glycol (PEG-1000)] have been coated using the static method at constant pressure or using an original vacuum pressure program (VPP) from 400 to 4 mbar. The best efficiency reached up to N = 62,000 theoretical plates for a film thickness of 47 nm at 100 °C for an iso-octane peak (k = 0.16) at an optimal flow rate of 4.8 mL/min. The use of the VPP improved the efficiency by approximately 15%. Efficiencies up to 28,000 and 47,000 were obtained for PEG-1000 and RTIL, respectively. A temperature-programmed separation of a mixture of 11 volatile compounds on a PDMS-coated chip was obtained in less than 36 s. The PDMS-, PEG-1000-, and RTIL-coated chips were tested as the second column using a microfluidic reverse fill/flush flow modulator in a GC × µGC system. The REP columns were highly compatible with the operating conditions in terms of flow rate and with more than 30,000 plates for the iso-octane peak. Moreover, a commercial solvent called white spirit containing alkanes and aromatic compounds was injected in three sets of columns in normal and reverse modes, demonstrating the great potential of the chip as a second-dimension separation column.

Oil Displacement in Calcite-Coated Microfluidic Chips via Waterflooding at Elevated Temperatures and Long Times.

In microfluidic studies of improved oil recovery, mostly pore networks with uniform depth and surface chemistry are used. To better mimic the multiple porosity length scales and surface heterogeneity of carbonate reservoirs, we coated a 2.5D glass microchannel with calcite particles. After aging with formation water and crude oil (CRO), high-salinity Water (HSW) was flooded at varying temperatures and durations. Time-resolved microscopy revealed the CRO displacements. Precise quantification of residual oil presented some challenges due to calcite-induced optical heterogeneity and brine-oil coexistence at (sub)micron length scales. Both issues were addressed using pixel-wise intensity calibration. During waterflooding, most of the ultimately produced oil gets liberated within the first pore volume (similar to glass micromodels). Increasing temperature from 22 °C to 60 °C and 90 °C produced some more oil. Waterflooding initiated directly at 90 °C produced significantly more oil than at 22 °C. Continuing HSW exposure at 90 °C for 8 days does not release additional oil; although, a spectacular growth of aqueous droplets is observed. The effect of calcite particles on CRO retention is weak on flat surfaces, where the coverage is ~20%. The calcite-rich pore edges retain significantly more oil suggesting that, in our micromodel wall roughness is a stronger determinant for oil retention than surface chemistry.

Enhanced Photocatalytic Hydrogen Evolution from Water Splitting on Ta2O5/SrZrO3 Heterostructures Decorated with CuxO/RuO2 Cocatalysts.

Photocatalytic H2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta2O5/SrZrO3 heterostructure with Ru and Cu (RuO2/CuxO/Ta2O5/SrZrO3) using solid-state chemistry methods to achieve a high H2 production of 5164 µmol g-1 h-1 under simulated solar light, 39 times higher than that produced using SrZrO3. The heterostructure performance is compared with other Ta2O5/SrZrO3 heterostructure compositions loaded with RuO2, CuxO, or Pt. CuxO is used to showcase the usage of less costly cocatalysts to produce H2. The photocatalytic activity toward H2 by the RuO2/CuxO/Ta2O5/SrZrO3 heterostructure remains the highest, followed by RuO2/Ta2O5/SrZrO3 > CuxO/Ta2O5/SrZrO3 > Pt/Ta2O5/SrZrO3 > Ta2O5/SrZrO3 > SrZrO3. Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO2 or CuxO) and are even higher for the binary catalyst (RuO2/CuxO). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta2O5/SrZrO3, improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO3-based heterostructures for photocatalytic H2 production by solar water splitting.

Wafer-Scale Particle Assembly in Connected and Isolated Micromachined Pockets via PDMS Rubbing.

The present contribution reports on a study aiming to find the most suitable rubbing method for filling arrays of separated and interconnected micromachined pockets with individual microspheres on rigid, uncoated silicon substrates without breaking the particles or damaging the substrate. The explored dry rubbing methods generally yielded unsatisfactory results, marked by very large percentages of empty pockets and misplaced particles. On the other hand, the combination of wet rubbing with a patterned rubbing tool provided excellent results (typically <1% of empty pockets and <5% of misplaced particles). The wet method also did not leave any damage marks on the silicon substrate or the particles. When the pockets were aligned in linear grooves, markedly the best results were obtained when the ridge pattern of the rubbing tool was moved under a 45° angle with respect to the direction of the grooves. The method was tested for both silica and polystyrene particles. The proposed assembly method can be used in the production of medical devices, antireflective coatings, and microfluidic devices with applications in chemical analysis and/or catalysis.

Self-organization of agitated microspheres on various substrates.

The vibration dynamics of relatively large granular grains is extensively treated in the literature, but comparable studies on the self-assembly of smaller agitated beads are lacking. In this work, we investigate how the particle properties and the properties of the underlying substrate surface affect the dynamics and self-organization of horizontally agitated monodisperse microspheres with diameters between 3 and 10 µm. Upon agitation, the agglomerated hydrophilic silica particles locally leave traces of particle monolayers as they move across the flat uncoated and fluorocarbon-coated silicon substrates. However, on the micromachined silicon tray with relatively large surface roughness, the agitated silica agglomerates form segregated bands reminiscent of earlier studies on granular suspensions or Faraday heaps. On the other hand, the less agglomerated hydrophobic polystyrene particles form densely occupied monolayer arrangements regardless of the underlying substrate. We explain the observations by considering the relevant adhesion and friction forces between particles and underlying substrates as well as those among the particles themselves. Interestingly, for both types of microspheres, large areas of the fluorocarbon-coated substrates are covered with densely occupied particle monolayers. By qualitatively examining the morphology of the self-organized particle monolayers using the Voronoi approach, it is understood that these monolayers are highly disordered, i.e., multiple symmetries coexist in the self-organized monolayers. However, more structured symmetries are identified in the monolayers of the agitated polystyrene microspheres on all the substrates, albeit not all precisely positioned on a hexagonal lattice. On the other hand, both the silica and polystyrene monolayers on the bare silicon substrates transition into less disordered structures as time progresses. Using Kelvin probe force microscopy measurements, we show that due to the tribocharging phenomenon, the formation of particle monolayers is promoted on the fluorocarbon surface, i.e., a local electrostatic attraction exists between the particle and the substrate.

Overcoming Voltage Losses in Vanadium Redox Flow Batteries Using WO3 as a Positive Electrode.

Vanadium redox flow batteries (VRFBs) are appealing large-scale energy storage systems due to their unique properties of independent energy/power design. The VRFBs stack design is crucial for technology deployment in power applications. Besides the design, the stack suffers from high voltage losses caused by the electrodes. The introduction of active sites into the electrode to facilitate the reaction kinetic is crucial in boosting the power rate of the VRFBs. Here, an O-rich layer has been applied onto structured graphite felt (GF) by depositing WO3 to increase the oxygen species content. The oxygen species are the active site during the positive reaction (VO2 +/VO2+) in VRFB. The increased electrocatalytic activity is demonstrated by the monoclinic (m)-WO3/GF electrode that minimizes the voltage losses, yielding excellent performance results in terms of power density output and limiting current density (556 mWcm-2@800 mAcm-2). The results confirm that the m-WO3/GF electrode is a promising electrode for high-power in VRFBs, overcoming the performance-limiting issues in a positive half-reaction.

Color Tuning of Electrochromic TiO2 Nanofibrous Layers Loaded with Metal and Metal Oxide Nanoparticles for Smart Colored Windows.

Co-axial electrospinning was applied for the structuring of non-woven webs of TiO2 nanofibers loaded with Ag, Au, and CuO nanoparticles. The composite layers were tested in an electrochromic half-cell assembly. A clear correlation between the nanoparticle composition and electrochromic effect in the nanofibrous composite is observed: TiO2 loaded with Ag reveals a black-brown color, Au shows a dark-blue color, and CuO shows a dark-green color. For electrochromic applications, the Au/TiO2 layer is the most promising choice, with a color modulation time of 6 s, transmittance modulation of 40%, coloration efficiency of 20 cm2/C, areal capacitance of 300 F/cm2, and cyclic stability of over 1000 cycles in an 18 h period. In this study, an unexplored path for the rational design of TiO2-based electrochromic device is offered with unique color-switching and optical efficiency gained by the fibrous layer. It is also foreseen that co-axial electrospinning can be an alternative nanofabrication technique for smart colored windows.