Exchange biased delta-E effect enables the detection of low frequency pT magnetic fields with simultaneous localization.

Delta-E effect sensors are based on magnetoelectric resonators that detune in a magnetic field due to the delta-E effect of the magnetostrictive material. In recent years, such sensors have shown the potential to detect small amplitude and low-frequency magnetic fields. Yet, they all require external magnetic bias fields for optimal operation, which is highly detrimental to their application. Here, we solve this problem by combining the delta-E effect with exchange biased multilayers and operate the resonator in a low-loss torsion mode. It is comprehensively analyzed experimentally and theoretically using various kinds of models. Due to the exchange bias, no external magnetic bias fields are required, but still low detection limits down to [Formula: see text] at 25 Hz are achieved. The potential of this concept is demonstrated with a new operating scheme that permits simultaneous measurement and localization, which is especially desirable for typical biomedical inverse solution problems. The sensor is localized with a minimum spatial resolution of 1 cm while measuring a low-frequency magnetic test signal that can be well reconstructed. Overall, we demonstrate that this class of magnetic field sensors is a significant step towards first biomedical applications and compact large number sensor arrays.

The impact of O2/Ar ratio on morphology and functional properties in reactive sputtering of metal oxide thin films.

Morphology is a critical parameter for various thin film applications, influencing properties like wetting, catalytic performance and sensing efficiency. In this work, we report on the impact of oxygen partial flow on the morphology of ceramic thin films deposited by pulsed DC reactive magnetron sputtering. The influence of O2/Ar ratio was studied on three different model systems, namely Al2O3, CuO and TiO2. The availability of oxygen during reactive sputtering is a key parameter for a versatile tailoring of thin film morphology over a broad range of nanostructures. TiO2 thin films with high photocatalytic performance (up to 95% conversion in 7 h) were prepared, exhibiting a network of nanoscopic cracks between columnar anatase structures. In contrast, amorphous thin films without such crack networks and with high resiliency to crystallization even up to 950 °C were obtained for Al2O3. Finally, we report on CuO thin films with well aligned crystalline nanocolumns and outstanding gas sensing performance for volatile organic compounds as well as hydrogen gas, showing gas responses up to 35% and fast response in the range of a few seconds.

Self-organized nanocrack networks: a pathway to enlarge catalytic surface area in sputtered ceramic thin films, showcased for photocatalytic TiO2.

Sputter deposited photocatalytic thin films offer high adherence and mechanical stability, but typically are outperformed in their photocatalytic properties by colloidal TiO2 nanostructures, which in turn typically suffer from problematic removal. Here we report on thermally controlled nanocrack formation as a feasible and batch applicable approach to enhance the photocatalytic performance of well adhering, reactively sputtered TiO2 thin films. Networks of nanoscopic cracks were induced into tailored columnar TiO2 thin films by thermal annealing. These deep trenches are separating small bundles of TiO2 columns, adding their flanks to the overall catalytically active surface area. The variation of thin film thickness reveals a critical layer thickness for initial nanocrack network formation, which was found to be about 400 nm in case of TiO2. The columnar morphology of the as deposited TiO2 layer with weak bonds between respective columns and with strong bonds to the substrate is of crucial importance for the formation of nanocrack networks. A beneficial effect of nanocracking on the photocatalytic performance was experimentally observed. It was correlated by a simple geometric model for explaining the positive impact of the crack induced enlargement of active surface area on photocatalytic efficiency. The presented method of nanocrack network formation is principally not limited to TiO2 and is therefore seen as a promising candidate for utilizing increased surface area by controlled crack formation in ceramic thin films in general.

Extreme tuning of wetting on 1D nanostructures: from a superhydrophilic to a perfect hydrophobic surface.

The tuning of wetting over an extreme range, from superhydrophilic to superhydrophobic, was demonstrated on 1D Al/Al2O3 nanostructures. While chaotic and tangled 1D Al/Al2O3 nanostructures exhibited complete wetting, they became water repellent (with a water contact angle (CA) ≥173°) after the infiltration of poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PTFEP) solution. This simple strategy allows the achievement of two extreme wetting regimes, perfect wetting and non-wetting, without altering the nanostructured surface topography. The same surface was also found to exhibit repellency towards artificial blood and hexadecane.

Light-induced Conductance Switching in Photomechanically Active Carbon Nanotube-Polymer Composites.

Novel, optically responsive devices with a host of potential applications have been demonstrated by coupling carbon nanomaterials with photochromic molecules. For light-induced conductance switching in particular, we have recently shown that carbon nanotube-polymer nanocomposites containing azobenzene are very attractive and provide stable and non-degradable changes in conductivity over time at standard laboratory conditions. In these composites, the photoswitching mechanisms are based on light-induced changes in electronic properties and related to the Pool-Frenkel conduction mechanism. However, no link between conductivity switching and the molecular motion of azobenzene chromophores could be found due to application of high elastic modulus polymer matrices. Here we report on single wall carbon nanotube-polymer nanocomposites with a soft polycaprolactone polymer host. Such a system clearly shows the transfer of light-induced, nano-sized molecular motion to macroscopic thickness changes of the composite matrix. We demonstrate that these photomechanical effects can indeed overshadow the electronic effects in conductivity switching behavior and lead to a reversion of the conductivity switching direction near the percolation threshold.

The hybrid concept for realization of an ultra-thin plasmonic metamaterial antireflection coating and plasmonic rainbow.

We report on the design, simulation, fabrication, and characterization of a novel two layer anti-reflective coating (ARC) based on a plasmonic metamaterial and a dielectric. Promoted by the strong material dispersion of the plasmonic metamaterial, our novel concept (called hybrid ARC) combines two possible arrangements for layers in an anti-reflection coating into a single structure; albeit at two different wavelengths. This, however, causes a broadband reduction of reflection that is less sensitive against oblique incidence when compared to traditional antireflective coatings. Furthermore, we show that the current metamaterial on a metal reflector can be used for the visualization of different coloration such as plasmonic rainbow despite its sub-wavelength thickness.

Study of cobalt clusters with very narrow size distribution deposited by high-rate cluster source.

Co nanoparticles with an average diameter of 4.8 nm and a very narrow size distribution were prepared in a self-built gas aggregation cluster source without a size-selective filtering system. Ferromagnetic nanoparticle films with a thickness of several hundreds of nanometres were prepared at deposition rates up to 600 nm min(-1). Cluster properties and deposition characteristics were investigated for different deposition parameters. The as-deposited films exhibit high porosity compared to conventionally DC-sputtered films.

Nanostructural and functional properties of Ag-TiO2 coatings prepared by co-sputtering deposition technique.

Ag-TiO2 nanocomposite coatings with varying Ag content were prepared by co-sputtering from two separate sputter sources. This technique allows to prepare coatings not only with a large variation of Ag content and different gradient but also allows much better control of nanocomposite thickness and nanostructure compared with mostly used techniques based on wet chemical approaches. Various thicknesses of nanocomposite layers with different deposition parameters were studied to obtain a better understanding on the growth of Ag nanostructures in the TiO2 films. The metal-volume-fraction was varied between 15% and 47%. Structural and microstructural investigations of the nanocomposite films were carried out by transmission electron microscopy. Special attention was paid to surface segregation of Ag and its suppression. The observed segregation on TiO2 contrasts sharply with the well known embedding tendency of Ag clusters on polymers. Functionality of the Ag-TiO2 nanocomposites was demonstrated via UV-Vis spectroscopy and antibacterial tests. It was shown that a thin layer of TiO2 can be used as an effective barrier to tailor the release behaviour of Ag ions.

Synthesis and characterization of Ag-polymer nanocomposites.

We report the synthesis of Ag nanoparticles in polyethylene terephthalate (PET) matrix using atom beam co-sputtering. Metal filling factor was evaluated by Rutherford backscattering spectrometry. Microstructural evolutions of the nanocomposites films were investigated by transmission electron microscopy, which confirmed the formation of irregular shaped Ag nanoparticles. The X-ray photoelectron spectroscopy measurements of the sputter deposited PET film and co-sputtered deposited Ag-PET as well as PET bulk foil (from Goodfellows) were performed to study chemical composition of the nanocomposite films. The optical properties of these nanocomposites were studied by light absorption/transmission, which revealed a narrow transmission of UV light approximately 320 nm and a broad surface plasmon resonance absorption extending up to infrared region (approximately 2400 nm). Swift heavy ion irradiation of Ag-PET nanocomposite resulted in narrowing the full width at half maximum of transmission band.

Free volume from positron lifetime and pressure-volume-temperature experiments in relation to structural relaxation of van der Waals molecular glass-forming liquids.

Positron annihilation lifetime spectroscopy (PALS) is employed to characterize the temperature dependence of the free volume in two van der Waals liquids: 1, 1'-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1, 1'-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC). From the PALS spectra analysed with the routine LifeTime9.0, the size (volume) distribution of local free volumes (subnanometer size holes), its mean, [v(h)], and mean dispersion, σ(h), were calculated. A comparison with the macroscopic volume from pressure-volume-temperature (PV T) experiments delivered the hole density and the specific hole free volume and a complete characterization of the free volume microstructure in that sense. These data are used in correlation with structural (α) relaxation data from broad-band dielectric spectroscopy (BDS) in terms of the Cohen-Grest and Cohen-Turnbull free volume models. An extension of the latter model allows us to quantify deviations between experiments and theory and an attempt to systematize these in terms of T(g) or of the fragility. The experimental data for several fragile and less fragile glass formers are involved in the final discussion. It was concluded that, for large differences in the fragility of different glass formers, the positron lifetime mirrors clearly the different character of these materials. For small differences in the fragility, additional properties like the character of bonds and chemical structure of the material may affect size, distribution and thermal behaviour of the free volume.

Free Volume and Swelling in Thin Films of Poly(N-isopropylacrylamide) End-Capped with n-Butyltrithiocarbonate.

The free volume in thin films of poly(N-isopropylacrylamid) end-capped with n-butyltriocarbonate (nbc-PNIPAM) is probed with positron annihilation lifetime spectroscopy (PALS). The PALS measurements are performed as function of energy to obtain depth profiles of the free volume of nbc-PNIPAM films. The range of nbc-PNIPAM films with thicknesses from 40 to 200 nm is focused. With decreasing film thickness the free volume increases in good agreement with an increase in the maximum swelling capability of the nbc-PNIPAM films. Thus in thin hydrogel films the sorption and swelling behavior is governed by free volume.

The temperature dependence of free volume in phenyl salicylate and its relation to structural dynamics: a positron annihilation lifetime and pressure-volume-temperature study.

Positron annihilation lifetime spectroscopy (PALS) and pressure-volume-temperature (PVT) experiments were performed to characterize the temperature dependent microstructure of the hole free volume in the low molecular weight glass-former phenyl salicylate (salol). The PALS spectra were analyzed with the new routine LT9.0 and the volume distribution of subnanometer size holes characterized by its mean and standard deviation sigma(h) was calculated. Crystallization of the amorphous sample was observed in the temperature range above 250 K, which leads to a vanishing of the positronium formation. The positronium signal recovered after melting at 303 K. A combination of PALS with PVT data enabled us to calculate the specific density N(h)('), the specific volume V(f), and the fraction of holes f(h) in the amorphous state. From comparison with dielectric measurements in the temperature range above T(B)=265 K, it was found that the primary structural relaxation slows down with temperature, faster than the shrinkage of the hole free volume V(f) would predict, on the basis of the Cohen-Turnbull (CT) free volume theory. CT plots can be linearized by replacing V(f) of the CT theory by (V(f)-DeltaV), where DeltaV is a volume correction term. This was interpreted as indication that the lower wing of the hole size distribution contains holes too small to show a liquidlike behavior in their surroundings. Peculiarities of the relaxation behavior below T(B)=265 K and the possible validity of the Cohen-Grest free volume model are discussed.

Equal intensity double plasmon resonance of bimetallic quasi-nanocomposites based on sandwich geometry.

We report a strategy to achieve a material showing equal intensity double plasmon resonance (EIDPR) based on sandwich geometry. We studied the interaction between localized plasmon resonances associated with different metal clusters (Au/Ag) on Teflon AF (TAF) in sandwich geometry. Engineering the EIDPR was done by tailoring the amount of Au/Ag and changing the TAF thickness. The samples were investigated by transmission electron microscopy (TEM) and UV-visible spectroscopy. Interestingly, and in agreement with the dipole-surface interaction, the critical barrier thickness for an optimum EIDPR was observed at 3.3 nm. The results clearly show a plasmon sequence effect and visualize the role of plasmon decay.

Surface glass transition in bimodal polystyrene mixtures.

Using the cluster-embedding method of V. Zaporojchenko et al. (Macromolecules 34, 1125 (2000)), we measured the glass transition temperature T (g) at the polystyrene/vacuum interface of bimodal mixtures of monodisperse polystyrenes of 3.5k and 1000k. Embedding of approximately 1 nm Au clusters was monitored in situ by X-ray photoelectron spectroscopy (XPS). The clusters were formed by evaporation of Au onto the polymer surface. Only one glass transition was observed in the mixtures. The surface glass transition temperatures are correlated to but are below the bulk values of the mixtures and obey the Gordon-Taylor equation. The results suggest that the earlier reported molecular-weight dependence of the surface glass transition is not due to segregation of short chains to the surface.

Plasmonic properties of Ag nanoclusters in various polymer matrices.

Nanocomposite films containing Ag nanoparticles embedded in a polymer matrix of Teflon AF, poly(methyl methacrylate) (PMMA) and Nylon 6 were prepared by vapour phase co-deposition in high vacuum. A large variation of the particle plasmon resonance frequency in the visible region was obtained by increasing the Ag volume fraction from 4-80%. The metal volume fraction was measured by energy dispersive x-ray spectrometry (EDX) and the film thickness was measured by surface profilometry. The position, width and strength of the plasmon resonance depend strongly on the metal filling factor, cluster size and interparticle distance. The microstructure of the nanocomposites (shape, size, size distribution and interparticle separation of metal clusters) was determined by transmission electron microscopy. The effect of the surrounding dielectric medium on the optical properties of nanocomposites was investigated by comparing the Teflon AF/Ag, PMMA/Ag and Nylon/Ag composites.

The distribution of the unoccupied volume in glassy polymers.

The aim of this paper is to present an improved method to describe the unoccupied volume in glassy polymers. The method is able to treat atoms with non-spherical symmetry. The fineness of the raster points scanning the unit cell can be as small as 0.01 nm. This method was used to determine the unoccupied volume of molecular dynamic simulations of poly(amide imide) unit cells by probing it with a tracer atom. Since the reachable unoccupied volume strongly depends on the tracer radius, we used tracer radii between 0.03 and 0.17 nm. The poly(amide imide)s were used in the present work because they are well characterized, especially there already exist free volume data determined by positron lifetime experiments.

X-ray reflectivity study on the surface and bulk glass transition of polystyrene.

The surfaces of polystyrene (PS) films decorated with gold nanoclusters were investigated by x-ray reflectivity measurements. The thicknesses of the films are much larger than the radii of gyration of the different PS samples. By annealing the films above the glass transition temperature T(g) an embedding process of the clusters into the polymer is detected which is accompanied by a substantial increase in the cluster layer thickness due to Brownian motion. These processes start at a sufficiently low viscosity and may be regarded as a probe of the glass transition in the near surface region of the PS films. Simultaneously the thermal expansion of the entire film and hence its approximate bulk behavior were monitored. Two samples of different molecular weight do not show a significant difference between the surface and bulk T(g) values.

Evidence of highly collective Co diffusion in the whole stability range of Co-Zr glasses

Using a radiotracer technique, we have measured the isotope effect E = dln(D)/dln(m(1/2)) of Co diffusion in CoxZr1-x glasses for 0. 31