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.

Nanoscale electromechanical and electronic properties of free-standing ZnO nano- and microstructured platelets.

The piezoelectric response, conductivity and surface potential of individual grains and grain boundaries in free-standing polycrystalline ZnO nano- and microstructured platelets is studied using scanning probe based techniques on the nanoscale. We find that applied dc electric fields can alter the piezoresponse in individual grains, as well as the local nanoscale conductivity, and invert the relative surface potential at grain boundaries. This can be attributed to defect accumulation at the grain surfaces and at grain boundaries and the associated density of carriers. Together with recently observed below-bandgap photoconductivity at grain boundaries, the presented observation opens new venues for potential nanoelectronic applications that rely on grain and grain boundary engineering and functionality in a wide-bandgap transparent material.

Functional NiTi grids for in situ straining in the TEM.

In situ measurements are a pivotal extension of conventional transmission electron microscopy (TEM). By means of the shape memory alloy NiTi thin film Functional Grids were produced for in situ straining as alternative or at least complement of expensive commercial holders. Due to the martensite-austenite transition temperature straining effects can be observed by use of customary heating holders in the range of 50 to 100°C. The grids can be produced in diversified designs to fit for different strain situations. Micro tensile tests were performed and compared with finite element simulations to estimate the applied forces on the sample and to predict the functionality of different grid designs. As a first example of this Functional Grid technology, we demonstrate the impact of applying a strain to a network of ZnO tetrapods.

Hybridization of Zinc Oxide Tetrapods for Selective Gas Sensing Applications.

In this work, the exceptionally improved sensing capability of highly porous three-dimensional (3-D) hybrid ceramic networks toward reducing gases is demonstrated for the first time. The 3-D hybrid ceramic networks are based on doped metal oxides (MexOy and ZnxMe1-xOy, Me = Fe, Cu, Al) and alloyed zinc oxide tetrapods (ZnO-T) forming numerous junctions and heterojunctions. A change in morphology of the samples and formation of different complex microstructures is achieved by mixing the metallic (Fe, Cu, Al) microparticles with ZnO-T grown by the flame transport synthesis (FTS) in different weight ratios (ZnO-T:Me, e.g., 20:1) followed by subsequent thermal annealing in air. The gas sensing studies reveal the possibility to control and change/tune the selectivity of the materials, depending on the elemental content ratio and the type of added metal oxide in the 3-D ZnO-T hybrid networks. While pristine ZnO-T networks showed a good response to H2 gas, a change/tune in selectivity to ethanol vapor with a decrease in optimal operating temperature was observed in the networks hybridized with Fe-oxide and Cu-oxide. In the case of hybridization with ZnAl2O4, an improvement of H2 gas response (to ∼7.5) was reached at lower doping concentrations (20:1), whereas the increase in concentration of ZnAl2O4 (ZnO-T:Al, 10:1), the selectivity changes to methane CH4 gas (response is about 28). Selectivity tuning to different gases is attributed to the catalytic properties of the metal oxides after hybridization, while the gas sensitivity improvement is mainly associated with additional modulation of the electrical resistance by the built-in potential barriers between n-n and n-p heterojunctions, during adsorption and desorption of gaseous species. Density functional theory based calculations provided the mechanistic insights into the interactions between different hybrid networks and gas molecules to support the experimentally observed results. The studied networked materials and sensor structures performances would provide particular advantages in the field of fundamental research, applied physics studies, and industrial and ecological applications.

Making metal surfaces strong, resistant, and multifunctional by nanoscale-sculpturing.

Surfaces are the crucial and limiting factor in nearly all metal applications, especially when technologically relevant alloys are employed. Insufficient surface properties on the nano- and microscale of metals determine, e.g. metal-polymer composite stability, implant biocompatibility, or corrosion resistance. Conventional surface preparation is just like an arbitrary cut through the metal body optimized for bulk behavior so that such surfaces contain various element mixtures and complex microstructures in which grains and lattice planes vary in their chemical stability from weak to strong. In contrast, the here described novel nanoscale-surface sculpturing based on semiconductor etching knowledge turns surfaces of everyday metals into their most stable configuration, but leaves the bulk properties unaffected. Thus, nanoscale-sculpturing ensures stronger, reliable joints to nearly all materials, reduces corrosion vastly, and generates a multitude of multifunctional surface properties not limited to those shown below.

Self-assembled monolayers of benzylmercaptan and p-cyanobenzylmercaptan on Au(111) surfaces: structural and spectroscopic characterization.

The formation of self-assembled monolayers of benzylmercaptan (BM) and p-cyanobenzylmercaptan (pCBM) on Au(111) surfaces is investigated by a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and scanning tunneling microscopy (STM). The NEXAFS results of pCBM are supported by ab initio calculations. It is found that BM as well as pCBM form well-ordered monolayers with the molecules oriented almost perpendicular to the surface. BM forms a ( radical 3 x radical 3)R30 degrees structure whereas pCBM forms a slightly different c(7 x 7) hexagonal structure. No phase separation is detected for the adsorption of a 1:1 mixture of the two molecules. The implications of the results for the covalent attachment of transition-metal complexes to thiol-functionalized surfaces are discussed.

Influence of saliva contamination on zirconia ceramic bonding.

OBJECTIVES: The purpose of this study was to investigate the influence of saliva contamination and cleaning methods on adhesive bonding to dental zirconia ceramic with a phosphate-monomer-containing luting resin. METHODS: After saliva immersion, airborne-particle abraded ceramic specimens were cleaned with water rinsing, with isopropanol, with phosphoric acid gel, or with additional airborne-particle abrasion. Airborne-particle abraded specimens without contamination were used as the control group. Chemical analysis of the ceramic surfaces of all groups was done using X-ray photoelectron spectroscopy (XPS). The influence of contamination and cleaning methods on ceramic bond durability was examined by tensile bond strength (TBS) testing after 3 days or 150 days water storage with 37,500 thermal cycles. RESULTS: After saliva contamination XPS revealed an organic coating which was not removed completely with water rinsing, with isopropanol, or with phosphoric acid. Using TBS testing a strong influence of contamination and cleaning methods on resin bond strength and its durability was found. SIGNIFICANCE: Saliva contamination significantly affected resin bonds to zirconia ceramic and its durability. Airborne-particle abrasion was the most effective cleaning method.

Influence of contamination on zirconia ceramic bonding.

The removal of contaminants prior to the bonding of ceramics is critical for the clinical success of a long-term durable resin bond. This study tested the null hypotheses that there are no contaminants on the zirconia ceramic surface left after try-in simulation, and there are no influences of contamination and cleaning methods on zirconia ceramic bonding durability with 10-methacryloyloxy-decyl dihydrogenphosphate-containing composite resins. After saliva immersion and the use of a silicone disclosing agent, airborne-particle-abraded ceramic specimens were cleaned with acetone, 36% phosphoric acid, additional airborne-particle abrasion, or only water spray. Chemical analyses of specimen surfaces were performed by x-ray photoelectron spectroscopy. The influences of contamination and cleaning methods on ceramic bond durability were examined by tensile testing after 3 or 150 days' water storage with 37,500 thermal cycles. Contamination, existing after try-in simulation as confirmed by chemical analysis, significantly reduced zirconia ceramic-resin bonds. Airborne-particle abrasion may be the most effective cleaning method.

Direct comparison between potential landscape and local density of states in a disordered two-dimensional electron system.

The local density of states (LDOS) of the adsorbate-induced two-dimensional electron system (2DES) on n-InAs(110) is studied by scanning tunneling spectroscopy. In contrast to a similar 3DES, the 2DES LDOS exhibits 20 times stronger corrugations and rather irregular structures. Both results are interpreted as consequences of weak localization. Fourier transforms of the LDOS reveal that the k values of the unperturbed 2DES still dominate the 2DES, but additional lower k values contribute. To clarify the origin of the LDOS patterns, we measure the potential landscape of the 2DES area. We use it to calculate the expected LDOS and find reasonable agreement between calculation and experiment.

Sharper images by focusing soft X-rays with photon sieves.

Fresnel zone plates consisting of alternating transmissive and opaque circular rings can be used to focus X-rays. The spatial resolution that can be achieved with these devices is of the order of the width of the outermost zone and is therefore limited by the smallest structure (20-40 nm) that can be fabricated by lithography today. Here we show that a large number of pinholes distributed appropriately over the Fresnel zones make it possible to focus soft X-rays to spot sizes smaller than the diameter of the smallest pinhole. In addition, higher orders of diffraction and secondary maxima can be suppressed by several orders of magnitude. In combination with the next generation of synchrotron light sources (free-electron lasers) these 'photon sieves' offer new opportunities for high-resolution X-ray microscopy and spectroscopy in physical and life sciences.

Tuning dimensionality by nanowire adsorption on layered materials.

The dimensionality of electronic states determines a number of physical phenomena such as phase transitions, transport, or superconductivity. Employing scanning tunneling microscopy combined with angle-resolved photoemission spectroscopy we demonstrate how the dimensionality of electronic states can be continuously tuned from three to two dimensions. This is achieved by adsorption of nanowires on surfaces of layered crystals without changing the chemical composition of the material. Exemplary results for Rb nanowires on TiTe2 are discussed with the help of electronic structure calculations.