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The integration of silver thin films into optoelectronic devices has gained much interest due to their exceptional properties in terms of conductivity and compatibility with flexible substrates. For this type of application, ultrathin layers are desirable, because of their optical transparency. Standard direct current magnetron sputtering (DCMS) is known to lead to undesirable formation of islands at low effective film thicknesses on typical substrates like SiO2 or polystyrene (PS). Therefore, in this study, we explore high-power impulse magnetron sputtering (HiPIMS) with optional further acceleration of metal ions by biasing the substrate or an additional positive pulse (bipolar HiPIMS) for the fabrication of ultra-thin silver layers. The morphology and electrical properties of ultra-thin silver layers with selected effective thicknesses are characterized on SiO2 and PS substrates. The growth evolution of characteristic parameters is further investigated by in-situ grazing-incidence small-angle Xray scattering (GISAXS). The results show that HiPIMS deposition yields films with a higher density of clusters than DCMS leading to a percolation threshold at lower effective film thicknesses. This effect is amplified by further ion acceleration. Thus, we suggest HiPIMS as a promising technique for fabricating ultra-thin, conductive layers on organic and oxide substrates., QC 20240704

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. The pristine micellar pattern of the diblock copolymer PS-b-P4VP degrades upon drying of a water droplet, which can be stabilized and inhibited upon deposition of silver clusters., QC 20231030

A comprehensive understanding of the linear/nonlinear dynamic behavior of wireless microresonators is essential for micro-electromechanical systems (MEMS) design optimization. This study investigates the dynamic behaviour of a magnetoelectric (ME) microresonator, using a finite element method (FEM) and machine learning algorithm. First, the linear/nonlinear behaviour of a fabricated thin-film ME microactuator is assessed in both the time domain and frequency spectrum. Next, a data driven system identification (DDSI) procedure and simulated annealing (SA) method are implemented to reconstruct differential equations from measured datasets. The Duffing equation is employed to replicate the dynamic behavior of the ME microactuator. The Duffing coefficients such as mass, stiffness, damping, force amplitude, and excitation frequency are considered as input parameters. Meanwhile, the microactuator displacement is taken as the output parameter, which is measured experimentally via a laser Doppler vibrometer (LDV) device. To determine the optimal range and step size for input parameters, the sensitivity analysis is conducted using Latin hypercube sampling (LHS). The peak index matching (PIM) and correlation coefficient (CC) are considered assessment criteria for the objective function. The data-driven developed models are subsequently employed to reconstruct/predict mode shapes and the vibration amplitude over the time domain. The effect of driving signal nonlinearity and total harmonic distortion (THD) is explored experimentally under resonance and sub-resonance conditions. The vibration measurements reveal that as excitation levels increase, hysteresis variations become more noticeable, which may result in a higher prediction error in the Duffing array model. The verification test indicates that the first bending mode reconstructs reasonably with a prediction accuracy of about 92 percent. This proof-of-concept study demonstrates that the simulated annealing approach is a p

Ordered porous gold/titanium dioxide (Au/TiO2) hybrid nanostructured films are specifically interesting in large-scale applications using localized surface plasmon resonances (LSPRs) and surface-enhanced Raman scattering (SERS). Deposition of Au nanoparticles via sputter deposition is one of the promising technologies to establish optically active sites at low cost in combination with nanostructured TiO2 films. In this work, we investigate the optical response of sputter-deposited Au/TiO2 nanohybrid thin films with a focus on the plasmonic response and application as molecular sensors. The LSPR peak red shifts with an increasing thickness of deposited Au. The Raman intensity of deposited molecules, probed with rhodamine 6G (R6G), depends on the deposited gold thickness. It has its maximum at an effective Au thickness of 3.4 nm. To elucidate the origin of this behavior, we apply in situ grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the growth kinetics of Au on a TiO2 template during sputter deposition. On the basis of time-resolved GISAXS, the growth characteristics of sputter-deposited Au on a TiO2 template with a final effective Au layer thickness around the percolation threshold is described with the well-known four-stage model of nucleation and cluster formation, diffusion-mediated growth, adsorption-mediated growth, and grain growth. The maximum in SERS intensity is corroborated by the existence and optimal size of hot spots in the narrow space occurring between the sputter-deposited Au clusters, on staying below the percolation threshold. On the basis of the growth laws extracted, we give a guideline for tailoring the ordered porous Au/TiO2 nanohybrid thin films for SERS sensor applications., QC 20220818

Tailoring of plasmon resonances is essential for applications in anticounterfeiting. This is readily achieved by tuning the composition of alloyed metal clusters; in the simplest case, binary alloys are used. Yet, one challenge is the correlation of cluster morphology and composition with the changing optoelectronic properties. Hitherto, the early stages of metal alloy nanocluster formation in immiscible binary systems such as silver and copper have been accessible by molecular dynamics (MD) simulations and transmission electron microscopy (TEM). Here, we investigate in real time the formation of supported silver, copper, and silver-copper-alloy nanoclusters during sputter deposition on poly(methyl methacrylate) by combining in situ surface-sensitive X-ray scattering with optical spectroscopy. While following the transient growth morphologies, we quantify the early stages of phase separation at the nanoscale, follow the shifts of surface plasmon resonances, and quantify the growth kinetics of the nanogranular layers at different thresholds. We are able to extract the influence of scaling effects on the nucleation and phase selection. The internal structure of the alloy cluster shows a copper-rich core/silver-rich shell structure because the copper core yields a lower mobility and higher crystallization tendency than the silver fraction. We compare our results to MD simulation and TEM data. This demonstrates a route to tailor accurately the plasmon resonances of nanosized, polymer-supported clusters which is a crucial prerequisite for anticounterfeiting., QC 20220610

© 2019, The Author(s). Bulk polytetrafluoroethylene (PTFE) possesses excellent chemical stability and dielectric properties. Indeed, thin films with these same characteristics would be ideal for electret applications. Previously, the electret properties of PTFE-like thin films produced by rf sputtering or plasma enhanced chemical vapor deposition were found to deteriorate due to structural changes and surface oxidation. In this article, the technique of initiated chemical vapor deposition (iCVD) is evaluated for electret applications for the first time. The iCVD method is known for its solvent-free deposition of conformal, pinhole-free polymer thin films in mild process conditions. It is shown that PTFE thin films prepared in this way, show excellent agreement to commercial bulk PTFE with regard to chemical properties and dielectric dissipation factors. After ion irradiation in a corona discharge the iCVD PTFE thin films exhibit stable electret properties, which can be tailored by the process parameters. Due to the mild deposition conditions, the iCVD technique is suitable for deposition on flexible organic substrates for the next-generation electret devices. It is also compatible with state-of-the-art microelectronic processing lines due to the characteristics of conformal growth and easy scaling up to larger size substrates.

Recently, Delta-E effect magnetic field sensors based on exchange-biased magnetic multi-layers have shown the potential of detecting low-frequency and small-amplitude magnetic fields. Their design is compatible with microelectromechanical system technology, potentially small, and therefore, suitable for arrays with a large number N of sensor elements. In this study, we explore the prospects and limitations for improving the detection limit by averaging the output of N sensor elements operated in parallel with a single oscillator and a single amplifier to avoid additional electronics and keep the setup compact. Measurements are performed on a two-element array of exchange-biased sensor elements to validate a signal and noise model. With the model, we estimate requirements and tolerances for sensor elements using larger N. It is found that the intrinsic noise of the sensor elements can be considered uncorrelated, and the signal amplitude is improved if the resonance frequencies differ by less than approximately half the bandwidth of the resonators. Under these conditions, the averaging results in a maximum improvement in the detection limit by a factor of√ N. A maximum N ≈ 200 exists, which depends on the read-out electronics and the sensor intrinsic noise. Overall, the results indicate that significant improvement in the limit of detection is possible, and a model is presented for optimizing the design of delta-E effect sensor arrays in the future.

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.

Semiconducting metal oxide - based gas sensors exhibit outstanding sensitivity, although humidity in the analyte typically hampers precise measurements. In this work it was shown that a 5−6 nm thin Al2O3 nano-layer is particularly beneficial in reducing the interference due to humidity of p-type conductivity copper oxide-based gas sensors. An effective approach from chemical solutions at 75 °C and thermal annealing at 600 °C was used to grow copper oxide nano-crystallite layers. The Al2O3 nano-layers were subsequently deposited on top of copper oxide by atomic layer deposition in a high-aspect-ratio regime at 75 °C. The morphological, structural, chemical, vibrational, electronical and sensor characteristics of the heterostructured nano-crystallite layers have been studied. The final nano-Al2O3/CuO heterostructure showed an increase in the response to H2 gas by 140 %, while long-term stability at low and high relative humidity was observed. The initial sensing response varied by only 10 % for an Al2O3 layer of 5−6 nm on top of CuO with a post-thermal annealing at 600 °C acting as an effective barrier for water vapor and oxygen. A comparison with CuO nanocrystallite layers covered by ALD with 6 nm and 15 nm of Al2O3 ultra-thin films on top demonstrates an exceptional stability of the hydrogen gas response at high relative humidity (84 % RH). Density functional theory-based calculations showed that the H2 molecule spontaneously dissociates over the formed Al2O3/CuO heterostructure, interacting strongly with the surface Al atoms, showing different behavior compared to the pristine CuO (111) surface, where H2 gas molecules are known to form water over the surface. The present study demonstrates that a thorough optimization of technology and surface properties due to coverage and formation of heterostructu

Heterojunctions are used in solar cells and optoelectronics applications owing to their excellent electrical and structural properties. Recently, these energy-efficient systems have also been employed as sensors to distinguish between individual gases within mixtures. Through a simple and versatile functionalization approach using noble metal nanoparticles, the sensing properties of heterojunctions can be controlled at the nanoscopic scale. This work reports the nanoparticle surface functionalization of TiO2/CuO/Cu2O mixed oxide heterostructures, where the gas sensing selectivity of the material is tuned to achieve versatile sensors with ultra-low power consumption. Functionalization with Ag or AgPt-nanoclusters (5–15 nm diameter), changed the selectivity from ethanol to butanol vapour, whereas Pd-nanocluster functionalization shifts the selectivity from the alcohols to hydrogen. The fabricated sensors show excellent low power consumption below 1 nW. To gain insight into the selectivity mechanism, density functional theory (DFT) calculations have been carried out to simulate the adsorption of H2, C2H5OH and n-C4H9OH at the noble metal nanoparticle decorated ternary heterostructure interface. These calculations also show a decrease in the work function by ~2.6 eV with respect to the pristine ternary heterojunctions. This work lays the foundation for the production of a highly versatile array of sensors of ultra-low power consumption with applications for the detection of individual gases in a mixture.

TiO2/Cu2O/CuO multi-nanolayers highly sensitive toward volatile organic compounds (VOCs) and H2 have been grown in various thicknesses by a cost-effective and reproducible combined spray-sputtering-annealing approach. The ultrathin TiO2 films were deposited by spray pyrolysis on top of sputtered-annealed Cu2O/CuO nanolayers to enhance their gas sensing performance and improve their protection against corrosion at high operating temperatures. The prepared heterostructures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ultraviolet visible (UV-vis) and micro-Raman spectroscopy. The gas sensing properties were measured at several operating temperatures, where the nanolayered sensors with oxide thicknesses between 20 and 30 nm (Cu2O/CuO nanolayers) exhibited a high response and an excellent selectivity to ethanol vapor after thermal annealing the samples at 420 °C. The results obtained at an operating temperature of 350 °C demonstrate that the CuO/Cu2O nanolayers with thicknesses between 20 and 30 nm are sensitive mainly to ethanol vapor, with a response of ∼150. The response changes from ethanol vapors to hydrogen gas as the thickness of the CuO/Cu2O nanolayers changes from 50 to 20 nm. Density functional theory-based calculations were carried out for the geometries of the CuO(1¯ 11)/Cu2O(111) and TiO2(111)/CuO(1¯ 11)/Cu2O(111) heterostructures and their sensing mechanism toward alcohols of different chain lengths and molecular hydrogen. The reconstructed hexagonal Cu2O(111) surface and the reconstructed monoclinic CuO(1¯ 11) and TiO2(111) facets, all of which terminate in an O layer, lead to the lowest surface energies for each isolated material. We studied the formation of the binary and ternary heteroepitaxial interfaces for the surface planes with the best-matching lattices. Despite the impact of the Cu2O(111) substrate in lowering the atomic charges of the CuO(1¯ 11) adlayer in the binary sensor, we found that it is the

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., QC 20220221

Polymer-metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics (OPVs). The polymer components used in these devices are mostly nanostructured conductive polymers with conjugated pi-electron systems. Enhanced OPV's power conversion efficiencies or sensor sensitivity can be achieved by selective metal deposition on or into polymer templates. In this study, we exploit time-resolved grazing-incidence X-ray scattering to observe the metal-polymer interface formation and the cluster crystallite size in situ during silver (Ag) sputter deposition on a poly(3-hexylthiophene-2,5-diyl)-b-poly(methyl methacrylate) (PMMA-b-P3HT) template. We compare the arising nanoscale morphologies with electronic properties, determine Ag growth regimes, and quantify the selective Ag growth for the diblock copolymer (DBC) template using the corresponding homopolymer thin films (P3HT and PMMA) as a reference. Hence, we are able to describe the influence of the respective polymer blocks and substrate effects on the Ag cluster percolation: the percolation threshold is correlated with the insulator-to-metal transition measured in situ with resistance measurements during the sputter deposition. The Ag cluster percolation on PMMA-b-P3HT starts already on the network of the hexagonal P3HT domain before a complete metal film covers the polymer surface, which is complemented by microscopic measurements. In general, this study demonstrates a possible method for the selective Ag growth as a scaffold for electrode preparation in nanoelectronics and for energy harvesting applications., QC 20210604

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 indepth 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., QC 20210510

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., QC 20210329

© 2019, The Author(s). Bulk polytetrafluoroethylene (PTFE) possesses excellent chemical stability and dielectric properties. Indeed, thin films with these same characteristics would be ideal for electret applications. Previously, the electret properties of PTFE-like thin films produced by rf sputtering or plasma enhanced chemical vapor deposition were found to deteriorate due to structural changes and surface oxidation. In this article, the technique of initiated chemical vapor deposition (iCVD) is evaluated for electret applications for the first time. The iCVD method is known for its solvent-free deposition of conformal, pinhole-free polymer thin films in mild process conditions. It is shown that PTFE thin films prepared in this way, show excellent agreement to commercial bulk PTFE with regard to chemical properties and dielectric dissipation factors. After ion irradiation in a corona discharge the iCVD PTFE thin films exhibit stable electret properties, which can be tailored by the process parameters. Due to the mild deposition conditions, the iCVD technique is suitable for deposition on flexible organic substrates for the next-generation electret devices. It is also compatible with state-of-the-art microelectronic processing lines due to the characteristics of conformal growth and easy scaling up to larger size substrates.

Tailoring the optical and electronic properties of nanostructured polymer-metal composites demonstrates great potential for efficient fabrication of modern organic optical and electronic devices such as flexible sensors, transistors, diodes, or photovoltaics. Self-assembled polymer metal nanocomposites offer an excellent perspective for creating hierarchical nanostructures on macroscopic scales by simple bottom-up processes. We investigate the growth processes of nanogranular silver (Ag) layers on diblock copolymer thin film templates during sputter deposition. The Ag growth is strongly driven by self-assembly and selective wetting on the lamella structure of polystyrene-block-poly (methyl methacrylate). We correlate the emerging nanoscale morphologies with collective optical and electronic properties and quantify the difference in Ag growth on the corresponding homopolymer thin films. Thus, we are able to determine the influence of the respective polymer template and observe substrate effects on the Ag cluster percolation threshold, which affects the insulator-to-metal transition (IMT). Optical spectroscopy in the UV-vis regime reveals localized surface plasmon resonance for the metal polymer composite. Their maximum absorption is observed around the IMT due to the subsequent long-range electron conduction in percolated nanogranular Ag layers. Using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, we identify the oxidation of Ag at the acrylate side chains as an essential influencing factor driving the selective wetting behavior in the early growth stages. The results of polymer-templated cluster growth are corroborated by atomic force microscopy and field emission scanning electron microscopy., QC 20190912

Magnetron discharge in a cold buffer gas represents a liquid-free approach to the synthesis of metal nanoparticles (NPs) with tailored structure, chemical composition and size. Despite a large number of metal NPs that were successfully produced by this method, the knowledge of the mechanisms of their nucleation and growth in the discharge is still limited, mainly because of the lack of in situ experimental data. In this work, we present the results of in situ Small Angle X-ray Scattering measurements performed in the vicinity of a Cu magnetron target with Ar used as a buffer gas. Condensation of atomic metal vapours is found to occur mainly at several mm distance from the target plane. The NPs are found to be captured preferentially within a region circumscribed by the magnetron plasma ring. In this capture zone, the NPs grow to the size of 90 nm whereas smaller ones sized 10-20 nm may escape and constitute a NP beam. Time-resolved measurements of the discharge indicate that the electrostatic force acting on the charged NPs may be largely responsible for their capturing nearby the magnetron., QC 20181210

The reproducible low-cost fabrication of functional polymer-metal-nanocomposites with tailored optoelectronic properties remains a major issue in applied nanotechnology. In order to obtain full control over the nanostructural evolution at the metal-polymer interface and its impact on optoelectronic properties, we employed the combination of in-situ time-resolved GISAXS [1] with in-situ surface differential reflectivity spectrometry during sputter deposition of gold on thin polystyrene films. We correlate the evolution of the metallic layer morphology with changes in the key scattering. This enabled us to identify the different growth regimes with their specific thresholds and permits a better understanding of the growth kinetics of gold clusters on polymer substrates. Our study opens up the opportunity to improve nanofabrication of tailored metal-polymer nanostructures for organic electronics like photovoltaic applications and plasmonic-based technologies.

Although it is well established in industry and important for many applications the sputter deposition of metals onto organic surfaces is yet to be completely understood. Due to the inherent complexity (e.g. bombardment of the organic surfaces by energetic ions) of the sputtering process the basic mechanisms determining the final microstructure are still to be identified. The complexity of sputter deposition and the post-deposition changes which are to be expected necessitate the use of in-situ methods. In-situ grazing incidence small angle scattering (GISAXS) has been used to extract structural information with high spatial and temporal resolution from a growing Au-film deposited via RF-sputter deposition onto a P(VDF-TrFE)-film. The Au-P(VDF-TrFE) system has been chosen as a model system of a relatively inert metal-polymer pair. Analysis of the GISAXS data yields information about the morphology of the growing Au-film. Comparing these results to simulated scattering data provides further information about the basic growth mechanisms acting at different stages of the growth of the metal film.

In organic-inorganic nanocomposites, interfacial regions are primarily influenced by the dispersion uniformity of nanoparticles and the strength of interfacial bonds between the nanoparticles and the polymer matrix. The insulating performance of organic-inorganic dielectric nanocomposites is highly influenced by the characteristics of interfacial regions. In this study, we prepare polyethylene oxide (PEO)-like functional layers on silica nanoparticles through plasma polymerization. Epoxy resin/silica nanocomposites are subsequently synthesized with these plasma-polymerized nanoparticles. It is found that plasma at a low power (i.e., 10 W) can significantly increase the concentration of C-O bonds on the surface of silica nanoparticles. This plasma polymerized thin layer can not only improve the dispersion uniformity by increasing the hydrophilicity of the nanoparticles, but also provide anchoring sites to enable the formation of covalent bonds between the organic and inorganic phases. Furthermore, electrical tests reveal improved electrical treeing resistance and decreased dielectric constant of the synthesized nanocomposites, while the dielectric loss of the nanocomposites remains unchanged as compared to the pure epoxy resin.