Nanoscale Synergetic Effects on Ag-TiO2 Hybrid Substrate for Photoinduced Enhanced Raman Spectroscopy (PIERS) with Ultra-Sensitivity and Reusability.

Here, a 4N-in-1 hybrid substrate concept (nanocolumnar structures, nanocrack network, nanoscale mixed oxide phases, and nanometallic structures) for ultra-sensitive and reliable photo-induced-enhanced Raman spectroscopy (PIERS), is proposed. The use of the 4N-in-1 hybrid substrate leads to an ≈50-fold enhancement over the normal surface-enhanced Raman spectroscopy, which is recorded as the highest PIERS enhancement to date. In addition to an improved Raman signal, the 4N-in-1 hybrid substrate provides a high detection sensitivity which may be attributed to the activation possibility at extremely low UV irradiation dosage and prolonged relaxation time (long measurement time). Moreover, the 4N-in-1 hybrid substrate exhibits a superior photocatalytic degradation performance of analytes, allowing its reuse at least 18 times without any loss of PIERS activity. The use of the 4N-in-1 concept can be adapted to biomedicine, forensic, and security fields easily.

Adaptive Model for Magnetic Particle Mapping Using Magnetoelectric Sensors.

Imaging of magnetic nanoparticles (MNPs) is of great interest in the medical sciences. By using resonant magnetoelectric sensors, higher harmonic excitations of MNPs can be measured and mapped in space. The proper reconstruction of particle distribution via solving the inverse problem is paramount for any imaging technique. For this, the forward model needs to be modeled accurately. However, depending on the state of the magnetoelectric sensors, the projection axis for the magnetic field may vary and may not be known accurately beforehand. As a result, the projection axis used in the model may be inaccurate, which can result in inaccurate reconstructions and artifact formation. Here, we show an approach for mapping MNPs that includes sources of uncertainty to both select the correct particle distribution and the correct model simultaneously.

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.

Modeling and Parallel Operation of Exchange-Biased Delta-E Effect Magnetometers for Sensor Arrays.

Recently, Delta-E effect magnetic field sensors based on exchange-biased magnetic multilayers 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.

Magnetoelastic Coupling and Delta-E Effect in Magnetoelectric Torsion Mode Resonators.

Magnetoelectric resonators have been studied for the detection of small amplitude and low frequency magnetic fields via the delta-E effect, mainly in fundamental bending or bulk resonance modes. Here, we present an experimental and theoretical investigation of magnetoelectric thin-film cantilevers that can be operated in bending modes (BMs) and torsion modes (TMs) as a magnetic field sensor. A magnetoelastic macrospin model is combined with an electromechanical finite element model and a general description of the delta-E effect of all stiffness tensor components Cij is derived. Simulations confirm quantitatively that the delta-E effect of the C66 component has the promising potential of significantly increasing the magnetic sensitivity and the maximum normalized frequency change Δfr. However, the electrical excitation of TMs remains challenging and is found to significantly diminish the gain in sensitivity. Experiments reveal the dependency of the sensitivity and Δfr of TMs on the mode number, which differs fundamentally from BMs and is well explained by our model. Because the contribution of C11 to the TMs increases with the mode number, the first-order TM yields the highest magnetic sensitivity. Overall, general insights are gained for the design of high-sensitivity delta-E effect sensors, as well as for frequency tunable devices based on the delta-E effect.

Multi-Mode Love-Wave SAW Magnetic-Field Sensors.

A surface-acoustic-wave (SAW) magnetic-field sensor utilizing fundamental, first- and second-order Love-wave modes is investigated. A 4.5   µ m SiO2 guiding layer on an ST-cut quartz substrate is coated with a 200 n m (Fe90Co10)78Si12B10 magnetostrictive layer in a delay-line configuration. Love-waves are excited and detected by two interdigital transducers (IDT). The delta-E effect in the magnetostrictive layer causes a phase change with applied magnetic field. A sensitivity of 1250 ° / m T is measured for the fundamental Love mode at 263 M Hz . For the first-order Love mode a value of 45 ° / m T is obtained at 352 M Hz . This result is compared to finite-element-method (FEM) simulations using one-dimensional (1D) and two-and-a-half-dimensional (2.5 D) models. The FEM simulations confirm the large drop in sensitivity as the first-order mode is close to cut-off. For multi-mode operation, we identify as a suitable geometry a guiding layer to wavelength ratio of h GL / λ ≈ 1.5 for an IDT pitch of p = 12   µ m . For this layer configuration, the first three modes are sufficiently far away from cut-off and show good sensitivity.

Frequency Dependency of the Delta-E Effect and the Sensitivity of Delta-E Effect Magnetic Field Sensors.

In recent years the delta-E effect has been used for detecting low frequency and low amplitude magnetic fields. Delta-E effect sensors utilize a forced mechanical resonator that is detuned by the delta-E effect upon application of a magnetic field. Typical frequencies of operation are from several kHz to the upper MHz regime. Different models have been used to describe the delta-E effect in those devices, but the frequency dependency has mainly been neglected. With this work we present a simple description of the delta-E effect as a function of the differential magnetic susceptibility χ of the magnetic material. We derive an analytical expression for χ that permits describing the frequency dependency of the delta-E effect of the Young's modulus and the magnetic sensitivity. Calculations are compared with measurements on soft-magnetic (Fe90Co10)78Si12B10 thin films. We show that the frequency of operation can have a strong influence on the delta-E effect and the magnetic sensitivity of delta-E effect sensors. Overall, the delta-E effect reduces with increasing frequency and results in a stiffening of the Young's modulus above the ferromagnetic resonance frequency. The details depend on the Gilbert damping. Whereas for large Gilbert damping the sensitivity continuously decreases with frequency, typical damping values result in an amplification close to the ferromagnetic resonance frequency.

Localized Synthesis of Iron Oxide Nanowires and Fabrication of High Performance Nanosensors Based on a Single Fe2 O3 Nanowire.

A composed morphology of iron oxide microstructures covered with very thin nanowires (NWs) with diameter of 15-50 nm has been presented. By oxidizing metallic Fe microparticles at 255 °C for 12 and 24 h, dense iron oxide NW networks bridging prepatterned Au/Cr pads are obtained. X-ray photoelectron spectroscopy studies reveal formation of α-Fe2 O3 and Fe3 O4 on the surface and it is confirmed by detailed high-resolution transmission electron microscopy and selected area electron diffraction (SAED) investigations that NWs are single phase α-Fe2 O3 and some domains of single phase Fe3 O4 . Localized synthesis of such nano- and microparticles directly on sensor platform/structure at 255 °C for 24 h and reoxidation at 650 °C for 0.2-2 h, yield in highly performance and reliable detection of acetone vapor with fast response and recovery times. First nanosensors on a single α-Fe2 O3 nanowire are fabricated and studied showing excellent performances and an increase in acetone response by decrease of their diameter was developed. The facile technological approach enables this nanomaterial as candidate for a range of applications in the field of nanoelectronics such as nanosensors and biomedicine devices, especially for breath analysis in the treatment of diabetes patients.

Single target sputter deposition of alloy nanoparticles with adjustable composition via a gas aggregation cluster source.

Alloy nanoparticles with variable compositions add a new dimension to nanoscience and have many applications. Here we suggest a novel approach for the fabrication of variable composition alloy nanoparticles that is based on a Haberland type gas aggregation cluster source with a custom-made multicomponent target for magnetron sputtering. The approach, which was demonstrated here for gold-rich AgAu nanoparticles, combines a narrow nanoparticle size distribution with in operando variation of composition via the gas pressure as well as highly efficient usage of target material. The latter is particularly attractive for precious metals. Varying argon pressure during deposition, we achieved in operando changes of AgAu alloy nanoparticle composition of more than 13 at%. The alloy nanoparticles were characterized by x-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy. The characteristic plasmon resonances of multilayer nanoparticle composites were analyzed by UV-vis spectroscopy. Tuning of the number of particles per unit area (particle densities) within individual layers showed an additional degree of freedom to tailor the optical properties of multilayer nanocomposites. By extension of this technique to more complex systems, the presented results are expected to encourage and simplify further research based on plasmonic multi-element nanoparticles. The present method is by no means restricted to plasmonics or nanoparticle based applications, but is also highly relevant for conventional magnetron sputtering of alloys and can be extended to in operando control of alloy concentration by magnetic field.

X-ray spectroscopy characterization of azobenzene-functionalized triazatriangulenium adlayers on Au(111) surfaces.

Triazatriangulenium (TATA) platform molecules allow the preparation of functionalized surfaces with well-defined lateral spacings of freestanding functional groups. Using scanning tunneling microscopy, synchrotron-based X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and complementary density functional theory calculations the chemical composition and orientational order of adlayers of functionalized azobenzene containing TATA platform molecules were characterized. According to these studies the molecules are chemically intact on the surface after self-assembly from solution and exhibit a well-defined adsorption geometry where the azobenzene units are oriented almost perpendicular to the surface.

Decoupling of component diffusion in a glass-forming Zr(46.75)Ti(8.25)Cu(7.5)Ni(10)Be(27.5) melt far above the liquidus temperature.

We report (95)Zr and (57)Co radiotracer diffusivities and viscosity data in the equilibrium liquid state of a bulk metallic glass forming Zr(46.75)Ti(8.25)Cu(7.5)Ni(10)Be(27.5) melt (Vitreloy 4) far above the liquidus temperature T(l) that are not affected by convection, as evidenced via quasielastic neutron scattering. Zr diffusion is strongly decoupled from diffusion of the smaller components by more than a factor of 4 at T(l), although it obeys the Stokes-Einstein equation. The results suggest that, in the present Zr-based metallic glass forming systems, diffusion and viscous flow start to develop solidlike, i.e., energy-landscape-controlled, features already in the stable liquid state more than 300 K above the mode coupling temperature T(c).

Miniaturized double-wing ∆E-effect magnetic field sensors.

Magnetoelastic micro-electromechanical systems (MEMS) are integral elements of sensors, actuators, and other devices utilizing magnetostriction for their functionality. Their sensitivity typically scales with the saturation magnetostriction and inversely with magnetic anisotropy. However, large saturation magnetostriction and small magnetic anisotropy make the magnetoelastic layer highly susceptible to minuscule anisotropic stress. It is inevitably introduced during the release of the mechanical structure during fabrication and severely impairs the device's reproducibility, performance, and yield. To avoid the transfer of residual stress to the magnetic layer, we use a shadow mask deposition technology. It is combined with a free-free magnetoelectric microresonator design to minimize the influence of magnetic inhomogeneity on device performance. Magnetoelectric resonators are experimentally and theoretically analyzed regarding local stress anisotropy, magnetic anisotropy, and the ΔE-effect sensitivity in several resonance modes. The results demonstrate an exceptionally small device-to-device variation of the resonance frequency < 0.2% with large sensitivities comparable with macroscopic ΔE-effect magnetic field sensors. This development marks a promising step towards highly reproducible magnetoelastic devices and the feasibility of large-scale, integrated arrays.

Self-Modification of Defective TiO2 under Controlled H2/Ar Gas Environment and Dynamics of Photoinduced Surface Oxygen Vacancies.

In recent years, defective TiO2 has caught considerable research attention because of its potential to overcome the limits of low visible light absorption and fast charge recombination present in pristine TiO2 photocatalysts. Among the different synthesis conditions for defective TiO2, ambient pressure hydrogenation with the addition of Ar as inert gas for safety purposes has been established as an easy method to realize the process. Whether the Ar gas might still influence the resulting photocatalytic properties and defective surface layer remains an open question. Here, we reveal that the gas flow ratio between H2 and Ar has a crucial impact on the defective structure as well as the photocatalyic activity of TiO2. In particular, transmission electron microscopy (TEM) in combination with electron energy loss spectroscopy (EELS) revealed a larger width of the defective surface layer when using a H2/Ar (50 %-50 %) gas mixture over pure H2. A possible reason could be the increase in dynamic viscosity of the gas mixture when Ar is added. Additionally, photoinduced enhanced Raman spectroscopy (PIERS) is implemented as a complementary approach to investigate the dynamics of the defective structures under ambient conditions which cannot be effortlessly realized by vacuum techniques like TEM.

Numerical and Experimental Study of Colored Magnetic Particle Mapping via Magnetoelectric Sensors.

Colored imaging of magnetic nanoparticles (MNP) is a promising noninvasive method for medical applications such as therapy and diagnosis. This study investigates the capability of the magnetoelectric sensor and projected gradient descent (PGD) algorithm for colored particle detection. In the first step, the required circumstances for image reconstruction are studied via a simulation approach for different signal-to-noise ratios (SNR). The spatial accuracy of the reconstructed image is evaluated based on the correlation coefficient (CC) factor. The inverse problem is solved using the PGD method, which is adapted according to a nonnegativity constraint in the complex domain. The MNP characterizations are assessed through a magnetic particle spectrometer (MPS) for different types. In the experimental investigation, the real and imaginary parts of the MNP's response are used to detect the spatial distribution and particle type, respectively. The experimental results indicate that the average phase difference for CT100 and ARA100 particles is 14 degrees, which is consistent with the MPS results and could satisfy the system requirements for colored imaging. The experimental evaluation showed that the magnetoelectric sensor and the proposed approach could be potential candidates for color bio-imaging applications.

Modeling of Magnetoelectric Microresonator Using Numerical Method and Simulated Annealing Algorithm.

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 promising tool for modeling the dynamic behavior of MEMS systems, making it a strong candidate for real-world applications.

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.

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.

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.

Surface segregation in TiO2-based nanocomposite thin films.

The morphology of nanocomposites plays a pivotal role in understanding their functionality and determines their capabilities for applications. The use of nanocomposite coatings requires a study of the size effects on their functional properties. Noble metal nanoparticles are promising candidates for nanocomposite thin film applications due to their antibacterial, plasmonic and photocatalytic properties. In this contribution, the morphology of Ag-TiO(2) and Au-TiO(2) nanocomposite thin films has been investigated experimentally using electron tomography in transmission electron microscopy in combination with UV/vis spectroscopy. Based on the additional 3D information obtained from tomography, we propose a two-step model towards the observed bimodal particle size in these nanocomposite thin films prepared by co-sputtering from two different sources. Furthermore, we show that the optical properties exhibit a well-defined relation with the morphology of the nanocomposite thin films. The present investigations demonstrate the potential of electron tomography for revealing the complex structure and formation processes of functional nanocomposites.