High-Power Impulse Magnetron Sputter Deposition of Ag on Self-Assembled Au Nanoparticle Arrays at Low-Temperature Dewetting Conditions.

Plasmons have facilitated diverse analytical applications due to the boosting signal detectability by hot spots. In practical applications, it is crucial to fabricate straightforward, large-scale, and reproducible plasmonic substrates. Dewetting treatment, via applying direct thermal annealing of metal films, has been used as a straightforward method in the fabrication of such plasmonic nanostructures. However, tailoring the evolution of the dewetting process of metal films poses considerable experimental complexities, mainly due to nanoscale structure formation. Here, we use grazing-incidence small- and wide-angle X-ray scattering for the in situ investigation of the high-power impulse magnetron sputter deposition of Ag on self-assembled Au nanoparticle arrays at low-temperature dewetting conditions. This approach allows us to examine both the direct formation of binary Au/Ag nanostructure and the consequential impact of the dewetting process on the spatial arrangement of the bimetallic nanoparticles. It is observed that the dewetting at 100 °C is sufficient to favor the establishment of a homogenized structural configuration of bimetallic nanostructures, which is beneficial for localized surface plasmon resonances (LSPRs). The fabricated metal nanostructures show potential application for the surface-enhanced Raman scattering (SERS) detection of rhodamine 6G molecules. As SERS platform, bimetallic nanostructures formed with dewetting conditions turn out to be superior to those without dewetting conditions. The method in this work is envisioned as a facile strategy for the fabrication of plasmonic nanostructures.

Plasma-Driven Tuning of Dielectric Permittivity in Graphene.

Materials with tunable negative electromagnetic performance, i.e., where dielectric permittivity becomes negative, have long been pursued in materials research due to their peculiar electromagnetic (EM) characteristics. Here, this promising feature is reported in materials on the case of plasma-synthesized nitrogen-doped graphene sheets with tunable permittivity over a wide (1-40 GHz) frequency range. Selectively incorporated nitrogen atoms in a graphene scaffold tailor the electronic structure in a way that provides an ultra-low energy (0.5-2 eV) 2D surface plasmon excitation, leading to subunitary and negative dielectric constant values in the Ka-band, from 30 up to 40 GHz. By allowing the tailoring of structures at atomic scale, this novel plasma-based approach creates a new paradigm for designing 2D nanomaterials like nanocarbons with controllable and tunable permittivity, opening a path to the next generation of 2D metamaterials.

Molybdenum(0)-Tricarbonyl Complex Supported by an Azacalix-pyridine Ligand: Synthesis, Characterization, Surface Deposition and Conversion to a Molybdenum(VI)-Trioxo Complex with O2.

Adsorption of metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans-effect" a dome-shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum-evaporable complex both activates CO and reacts with molecular oxygen (O2) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer. The molybdenum tricarbonyl- and trioxo complexes are investigated in the solid state, in homogeneous solution and on noble metal surfaces (Cu, Au) employing a range of spectroscopic and analytical methods.

Diblock copolymer pattern protection by silver cluster reinforcement.

Pattern fabrication by self-assembly of diblock copolymers is of significant interest due to the simplicity in fabricating complex structures. In particular, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) is a fascinating base material as it forms an ordered micellar structure on silicon surfaces. In this work, silver (Ag) is applied using direct current magnetron sputter deposition and high-power impulse magnetron sputter deposition on an ordered micellar PS-b-P4VP layer. The fabricated hybrid materials are structurally analyzed by field emission scanning electron microscopy, atomic force microscopy, and grazing incidence small angle X-ray scattering. When applying simple aqueous posttreatment, the pattern is stable and reinforced by Ag clusters, making micellar PS-b-P4VP ordered layers ideal candidates for lithography.

Two-in-One Sensor Based on PV4D4-Coated TiO2 Films for Food Spoilage Detection and as a Breath Marker for Several Diseases.

Certain molecules act as biomarkers in exhaled breath or outgassing vapors of biological systems. Specifically, ammonia (NH3) can serve as a tracer for food spoilage as well as a breath marker for several diseases. H2 gas in the exhaled breath can be associated with gastric disorders. This initiates an increasing demand for small and reliable devices with high sensitivity capable of detecting such molecules. Metal-oxide gas sensors present an excellent tradeoff, e.g., compared to expensive and large gas chromatographs for this purpose. However, selective identification of NH3 at the parts-per-million (ppm) level as well as detection of multiple gases in gas mixtures with one sensor remain a challenge. In this work, a new two-in-one sensor for NH3 and H2 detection is presented, which provides stable, precise, and very selective properties for the tracking of these vapors at low concentrations. The fabricated 15 nm TiO2 gas sensors, which were annealed at 610 °C, formed two crystal phases, namely anatase and rutile, and afterwards were covered with a thin 25 nm PV4D4 polymer nanolayer via initiated chemical vapor deposition (iCVD) and showed precise NH3 response at room temperature and exclusive H2 detection at elevated operating temperatures. This enables new possibilities in application fields such as biomedical diagnosis, biosensors, and the development of non-invasive technology.

Tuning the Selectivity of Metal Oxide Gas Sensors with Vapor Phase Deposited Ultrathin Polymer Thin Films.

Metal oxide gas sensors are of great interest for applications ranging from lambda sensors to early hazard detection in explosive media and leakage detection due to their superior properties with regard to sensitivity and lifetime, as well as their low cost and portability. However, the influence of ambient gases on the gas response, energy consumption and selectivity still needs to be improved and they are thus the subject of intensive research. In this work, a simple approach is presented to modify and increase the selectivity of gas sensing structures with an ultrathin polymer thin film. The different gas sensing surfaces, CuO, Al2O3/CuO and TiO2 are coated with a conformal < 30 nm Poly(1,3,5,7-tetramethyl-tetravinyl cyclotetrasiloxane) (PV4D4) thin film via solvent-free initiated chemical vapor deposition (iCVD). The obtained structures demonstrate a change in selectivity from ethanol vapor to 2-propanol vapor and an increase in selectivity compared to other vapors of volatile organic compounds. In the case of TiO2 structures coated with a PV4D4 thin film, the increase in selectivity to 2-propanol vapors is observed even at relatively low operating temperatures, starting from >200 °C. The present study demonstrates possibilities for improving the properties of metal oxide gas sensors, which is very important in applications in fields such as medicine, security and food safety.

A novel method for the synthesis of core-shell nanoparticles for functional applications based on long-term confinement in a radio frequency plasma.

A novel combined setup of a Haberland type gas aggregation source and a secondary radio frequency discharge is used to generate, confine, and coat nanoparticles over much longer time scales than traditional in-flight treatment. The process is precisely monitored using localized surface plasmon resonance and Fourier-transform infrared spectroscopy as in situ diagnostics. They indicate that both untreated and treated particles can be confined for extended time periods (at least one hour) with minimal losses. During the entire confinement time, the particle sizes do not show considerable alterations, enabling multiple well-defined modifications of the seed nanoparticles in this synthesis approach. The approach is demonstrated by generating Ag@SiO2 nanoparticles with a well-defined surface coating. The in situ diagnostics provide insights into the growth kinetics of the applied coating and are linked to the coating properties by using ex situ transmission electron microscopy and energy dispersive X-ray spectroscopy. Surface coating is shown to occur in two phases: first, singular seeds appear on the particle surface which then grow to cover the entire particle surface over 3 to 5 minutes. Afterwards, deposition occurs via surface growth which coincides with lower deposition rates. Our setup offers full control for various treatment options, which is demonstrated by coating the nanoparticles with a SiO2 layer followed by the etching of the part of the applied coating using hydrogen. Thus, complex multi-step nanofabrication, e.g., using different monomers, as well as very large coating thicknesses is possible.

Brain-like critical dynamics and long-range temporal correlations in percolating networks of silver nanoparticles and functionality preservation after integration of insulating matrix.

Random networks of nanoparticle-based memristive switches enable pathways for emulating highly complex and self-organized synaptic connectivity together with their emergent functional behavior known from biological neuronal networks. They therefore embody a distinct class of neuromorphic hardware architectures and provide an alternative to highly regular arrays of memristors. Especially, networks of memristive nanoparticles (NPs) poised at the percolation threshold are promising due to their capabilities of showing brain-like activity such as critical dynamics or long-range temporal correlation (LRTC), which are closely connected to the computational capabilities in biological neuronal networks. Here, we adapt this concept to networks of Ag-NPs poised at the electrical percolation threshold, where the memristive properties are governed by electro-chemical metallization. We show that critical dynamics and LRTC are preserved although the nature of individual memristive gaps throughout the network is fundamentally changed by filling the gaps with an insulating matrix. The results in this work generate important contributions towards the practical applicability of critical dynamics and LRTC in percolating NP networks by elucidating the consequences of NP network encapsulation, which is considered as an important step towards device integration.

Correlating Optical Reflectance with the Topology of Aluminum Nanocluster Layers Growing on Partially Conjugated Diblock Copolymer Templates.

Large-scale fabrication of metal cluster layers for usage in sensor applications and photovoltaics is a huge challenge. Physical vapor deposition offers large-scale fabrication of metal cluster layers on templates and polymer surfaces. In the case of aluminum (Al), only little is known about the formation and interaction of Al clusters during sputter deposition. Complex polymer surface morphologies can tailor the deposited Al cluster layer. Here, a poly(methyl methacrylate)-block-poly(3-hexylthiophen-2,5-diyl) (PMMA-b-P3HT) diblock copolymer template is used to investigate the nanostructure formation of Al cluster layers on the different polymer domains and to compare it with the respective homopolymers PMMA and P3HT. The optical properties relevant for sensor applications are monitored with ultraviolet-visible (UV-vis) measurements during the sputter deposition. The formation of Al clusters is followed in situ with grazing-incidence small-angle X-ray scattering (GISAXS), and the chemical interaction is revealed by X-ray photoelectron spectroscopy (XPS). Furthermore, atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) yield topographical information about selective wetting of Al on the P3HT domains and embedding in the PMMA domains in the early stages, followed by four distinct growth stages describing the Al nanostructure formation.

Epileptic Seizure Detection on an Ultra-Low-Power Embedded RISC-V Processor Using a Convolutional Neural Network.

The treatment of refractory epilepsy via closed-loop implantable devices that act on seizures either by drug release or electrostimulation is a highly attractive option. For such implantable medical devices, efficient and low energy consumption, small size, and efficient processing architectures are essential. To meet these requirements, epileptic seizure detection by analysis and classification of brain signals with a convolutional neural network (CNN) is an attractive approach. This work presents a CNN for epileptic seizure detection capable of running on an ultra-low-power microprocessor. The CNN is implemented and optimized in MATLAB. In addition, the CNN is also implemented on a GAP8 microprocessor with RISC-V architecture. The training, optimization, and evaluation of the proposed CNN are based on the CHB-MIT dataset. The CNN reaches a median sensitivity of 90% and a very high specificity over 99% corresponding to a median false positive rate of 6.8 s per hour. After implementation of the CNN on the microcontroller, a sensitivity of 85% is reached. The classification of 1 s of EEG data takes t=35 ms and consumes an average power of P≈140 µW. The proposed detector outperforms related approaches in terms of power consumption by a factor of 6. The universal applicability of the proposed CNN based detector is verified with recording of epileptic rats. This results enable the design of future medical devices for epilepsy treatment.

Revealing the growth of copper on polystyrene-block-poly(ethylene oxide) diblock copolymer thin films with in situ GISAXS.

Copper (Cu) as an excellent electrical conductor and the amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-b-PEO) as a polymer electrolyte and ionic conductor can be combined with an active material in composite electrodes for polymer lithium-ion batteries (LIBs). As interfaces are a key issue in LIBs, sputter deposition of Cu contacts on PS-b-PEO thin films with high PEO fraction is investigated with in situ grazing-incidence small-angle X-ray scattering (GISAXS) to follow the formation of the Cu layer in real-time. We observe a hierarchical morphology of Cu clusters building larger Cu agglomerates. Two characteristic distances corresponding to the PS-b-PEO microphase separation and the Cu clusters are determined. A selective agglomeration of Cu clusters on the PS domains explains the origin of the persisting hierarchical morphology of the Cu layer even after a complete surface coverage is reached. The spheroidal shape of the Cu clusters growing within the first few nanometers of sputter deposition causes a highly porous Cu-polymer interface. Four growth stages are distinguished corresponding to different kinetics of the cluster growth of Cu on PS-b-PEO thin films: (I) nucleation, (II) diffusion-driven growth, (III) adsorption-driven growth, and (IV) grain growth of Cu clusters. Percolation is reached at an effective Cu layer thickness of 5.75 nm.

Tailoring the Optical Properties of Sputter-Deposited Gold Nanostructures on Nanostructured Titanium Dioxide Templates Based on In Situ Grazing-Incidence Small-Angle X-ray Scattering Determined Growth Laws.

Gold/titanium dioxide (Au/TiO2) nanohybrid materials have been widely applied in various fields because of their outstanding optical and photocatalytic performance. By state-of-the-art polymer templating, it is possible to make uniform nanostructured TiO2 layers with potentially large-scale processing methods. We use customized polymer templating to achieve TiO2 nanostructures with different morphologies. Au/TiO2 hybrid thin films are fabricated by sputter deposition. An in-depth understanding of the Au morphology on the TiO2 templates is achieved with in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition. The resulting Au nanostructure is largely influenced by the TiO2 template morphology. Based on the detailed understanding of the Au growth process, characteristic distances can be selected to achieve tailored Au nanostructures at different Au loadings. For selected sputter-deposited Au/TiO2 hybrid thin films, the optical response with a tailored localized surface plasmon resonance is demonstrated.

Molecular Insight into Real-Time Reaction Kinetics of Free Radical Polymerization from the Vapor Phase by In-Situ Mass Spectrometry.

The combination of organic chemistry and chemical vapor deposition enables a unique way to deposit conformal, high quality polymer thin films from the vapor phase. Particularly initiated chemical vapor deposition (iCVD) has recently shown its great potential in many different application fields. With the ever-increasing demands on the process, the need for additional process refinement is also growing. In this study the enhancement of the iCVD process by in-situ mass spectrometry is presented. The approach enables insight into real-time reaction kinetics during the deposition process as well as identification of reaction pathways. Furthermore, the composition of the gas phase can be precisely controlled and spontaneously adjusted if necessary. Particularly the deposition of thin films with thicknesses in the low nanometer range and the deposition of copolymers can benefit from this approach. The presented approach enables enhanced process control as well as the ability to perform extensive kinetic studies.

Enhancing Reliability of Studies on Single Filament Memristive Switching via an Unconventional cAFM Approach.

Memristive devices are highly promising for implementing neuromorphic functionalities in future electronic hardware, and direct insights into memristive phenomena on the nanoscale are of fundamental importance to reaching this. Conductive atomic force microscopy (cAFM) has proven to be an essential tool for probing memristive action locally on the nanoscale, but the significance of the acquired data frequently suffers from the nonlocality associated with the thermal drift of the tip in ambient conditions. Furthermore, comparative studies of different configurations of filamentary devices have proven to be difficult, because of an immanent variability of the filament properties between different devices. Herein, these problems are addressed by constraining the memristive action directly at the apex of the probe through functionalization of a cAFM tip with an archetypical memristive stack, which is comprised of Ag/Si3N4. The design of such functionalized cantilevers (entitled here as "memtips") allowed the capture of the long-term intrinsic current response, identifying temporal correlations between switching events, and observing emerging spiking dynamics directly at the nanoscale. Utilization of an identical memtip for measurements on different counter electrodes made it possible to directly compare the impact of different device configurations on the switching behavior of the same filament. Such an analytical approach in ambient conditions will pave the way towards a deeper understanding of filamentary switching phenomena on the nanoscale.

Neutron spectroscopy study of the diffusivity of hydrogen in MoS2.

The diffusion of hydrogen adsorbed inside layered MoS2 crystals has been studied by means of quasi-elastic neutron scattering, neutron spin-echo spectroscopy, nuclear reaction analysis, and X-ray photoelectron spectroscopy. The neutron time-of-flight and neutron spin-echo measurements demonstrate fast diffusion of hydrogen molecules parallel to the basal planes of the two dimensional crystal planes. At room temperature and above, this intra-layer diffusion is of a similar speed to the surface diffusion that has been observed in earlier studies for hydrogen atoms on Pt surfaces. A significantly slower hydrogen diffusion was observed perpendicular to the basal planes using nuclear reaction analysis.

Molybdenum tricarbonyl complex functionalised with a molecular triazatriangulene platform on Au(111): surface spectroscopic characterisation.

Transition metal complexes form the basis for small molecule activation and are relevant for electrocatalysis. To combine both approaches the attachment of homogeneous catalysts to metallic surfaces is of significant interest. Towards this goal a molybdenum tricarbonyl complex supported by a tripodal phosphine ligand was covalently bound to a triazatriangulene (TATA) platform via an acetylene unit and the resulting TATA-functionalised complex was deposited on a Au(111) surface. The corresponding self-assembled monolayer was characterised with scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS). The vibrational properties of the surface-adsorbed complexes were investigated with the help of infrared reflection absorption spectroscopy (IRRAS), and the frequency/intensity changes with respect to the bulk spectrum were analysed. A full vibrational analysis was performed with the help of DFT.

Real-time insight into nanostructure evolution during the rapid formation of ultra-thin gold layers on polymers.

Ultra-thin metal layers on polymer thin films attract tremendous research interest for advanced flexible optoelectronic applications, including organic photovoltaics, light emitting diodes and sensors. To realize the large-scale production of such metal-polymer hybrid materials, high rate sputter deposition is of particular interest. Here, we witness the birth of a metal-polymer hybrid material by quantifying in situ with unprecedented time-resolution of 0.5 ms the temporal evolution of interfacial morphology during the rapid formation of ultra-thin gold layers on thin polystyrene films. We monitor average non-equilibrium cluster geometries, transient interface morphologies and the effective near-surface gold diffusion. At 1 s sputter deposition, the polymer matrix has already been enriched with 1% gold and an intermixing layer has formed with a depth of over 3.5 nm. Furthermore, we experimentally observe unexpected changes in aspect ratios of ultra-small gold clusters growing in the vicinity of polymer chains. For the first time, this approach enables four-dimensional insights at atomic scales during the gold growth under non-equilibrium conditions.

Influence of Cleaning Methods on Resin Bonding to Contaminated Translucent 3Y-TZP ceramic.

PURPOSE: To evaluate the influence of different cleaning methods on the resin bond strength to contaminated translucent 3Y-TZP ceramic. MATERIALS AND METHODS: A total of 133 airborne-particle abraded (0.1 MPa) zirconia specimens were divided into 7 groups. Uncontaminated zirconia specimens were either not cleaned (UN) or cleaned with cleaning paste (Ivoclean) (UP1). After contamination by saliva and blood immersion, zirconia specimens were cleaned using either distilled water rinsing (CW), 99% isopropanol in an ultrasonic bath (CI), cleaning paste according to manufacturer's instructions (CP1), cleaning paste with additional rubbing (CP2), or additional airborne-particle abrasion at 0.1 MPa (CA). Three specimens from each group were examined by x-ray photoelectron spectroscopy (XPS). For each group, sixteen Plexiglas tubes filled with composite resin (Clearfil FII, Kuraray Noritake) were bonded to the zirconia specimens using a primer (Clearfil Ceramic Primer Plus, Kuraray Noritake) and luting composite (Panavia V5, Kuraray Noritake). Before measuring tensile bond strength, specimens were stored in distilled water for 3 or 150 days plus 37,500 thermal cycles. RESULTS: After 3 days, no group showed significantly different TBS compared to the control group UN (p > 0.05). However, groups CW and CI showed significantly lower TBS than all other groups after 150 days (p ≤ 0.05). XPS analysis revealed more organic residue on zirconia surfaces of groups CW and CI than on the other groups. CONCLUSION: Cleaning with the cleaning paste and airborne-particle abrasion were effective in removing saliva and blood contamination and enhancing bond strength.

Low-temperature low-power PECVD synthesis of vertically aligned graphene.

The need for 2D vertical graphene nanosheets (VGNs) is driven by its great potential in diverse energy, electronics, and sensor applications, wherein many cases a low-temperature synthesis is preferred due to requirements of the manufacturing process. Unfortunately, most of today's known methods, including plasma, require either relatively high temperatures or high plasma powers. Herein, we report on a controllable synthesis of VGNs at a pushed down low-temperature boundary for synthesis, the low temperatures (450 °C) and low plasma powers (30 W) using capacitively coupled plasma (CCP) driven by radio-frequency power at 13.56 MHz. The strategies implemented also include unrevealing the role of Nickel (Ni) catalyst thin film on the substrates (Si/Al). It was found that the Ni catalyst on Si/Al initiates the nucleation/growth of VGNs at 450 °C in comparison to the substrates without Ni catalyst. With increasing temperature, the graphene nanosheets become bigger in size, well-structured and well separated. The role of Ni catalysts is hence to boost the growth rate, density, and quality of the growing VGNs. Furthermore, this CCP method can be used to synthesize VGNs at the lowest temperatures possible so far on a variety of substrates and provide new opportunities in the practical application of VGNs.

Photodeposition of Au Nanoclusters for Enhanced Photocatalytic Dye Degradation over TiO2 Thin Film.

Au nanoparticle (NP) decorated heterogeneous TiO2 catalysts are known to be effective in the degradation of various organic pollutants. The photocatalytic performance of such Au-TiO2 structures remarkably depends on the size, morphology, and surface coverage of the Au NPs decorating TiO2. Here we propose an effective way of preparing a highly active Au nanocluster (NC) decorated TiO2 thin film by a novel photodeposition method. By altering the solvent type as well as the illumination time, we achieved well-controlled surface coverage of TiO2 by Au NCs, which directly influences the photocatalytic performance. Here the Au NCs coverage affects both the electron store capacity and the optical absorption of the hybrid Au-TiO2 system. At low surface coverage, 19.2-29.5%, the Au NCs seem to enhance significantly the optical adsorption of TiO2 at UV wavelengths which therefore leads to a higher photocatalytic performance.