Physical Trace Gas Identification with the Photo Electron Ionization Spectrometer (PEIS).

Chemosensor technology for trace gases in the air always aims to identify these compounds and then measure their concentrations. For identification, traceable methods are sparse and relate to large appliances such as mass spectrometers. We present a new method that uses the alternative traceable measurement of the ionization energies of trace gases in a way that can be miniaturized and energetically tuned. We investigate the achievable performance. Since tunable UV sources are not available for photoionization, we take a detour via impact ionization with electrons, which we generate using the photoelectric effect and bring to sharp, defined energies on a nanoscale in the air. Electron impact ionization is thus possible at air pressures of up to 900 hPa. The sensitivity of the process reaches 1 ppm and is equivalent to that of classic PID. With sharpened energy settings, substance identification is currently possible with an accuracy of 30 meV. We can largely explain the experimental observations with the known quantum mechanical models.

Overcoming intra-molecular repulsions in PEDTT by sulphate counter-ion.

We set out to demonstrate the development of a highly conductive polymer based on poly-(3,4-ethylenedithia thiophene) (PEDTT), PEDOTs structural analogue historically notorious for structural disorder and limited conductivities. The caveat therein was previously described to lie in intra-molecular repulsions. We demonstrate how a tremendous >2600-fold improvement in conductivity and metallic features, such as magnetoconductivity can be achieved. This is achieved through a careful choice of the counter-ion (sulphate) and the use of oxidative chemical vapour deposition (oCVD). It is shown that high structural order on the molecular level was established and the formation of crystallites tens of nanometres in size was achieved. We infer that the sulphate ions therein intercalate between the polymer chains, thus forming densely packed crystals of planar molecules with extended π-systems. Consequently, room-temperature conductivities of above 1000 S cm-1 are achieved, challenging those of conventional PEDOT:PSS. The material is in the critical regime of the metal-insulator transition.

Enhanced Bio-Electrochemical Reduction of Carbon Dioxide by Using Neutral Red as a Redox Mediator.

Microbial electrosynthetic cells containing Methylobacterium extorquens were studied for the reduction of CO2 to formate by direct electron injection and redox mediator-assisted approaches, with CO2 as the sole carbon source. The formation of a biofilm on a carbon felt (CF) electrode was achieved while applying a constant potential of -0.75 V versus Ag/AgCl under CO2 -saturated conditions. During the biofilm growth period, continuous H2 evolution was observed. The long-term performance for CO2 reduction of the biofilm with and without neutral red as a redox mediator was studied by an applied potential of -0.75 V versus Ag/AgCl. The neutral red was introduced into the systems in two different ways: homogeneous (dissolved in solution) and heterogeneous (electropolymerized onto the working electrode). The heterogeneous approach was investigated in the microbial system, for the first time, where the CF working electrode was coated with poly(neutral red) by the oxidative electropolymerization thereof. The formation of poly(neutral red) was characterized by spectroscopic techniques. During long-term electrolysis up to 17 weeks, the formation of formate was observed continuously with an average Faradaic efficiency of 4 %. With the contribution of neutral red, higher formate accumulation was observed. Moreover, the microbial electrosynthetic cell was characterized by means of electrochemical impedance spectroscopy to obtain more information on the CO2 reduction mechanism.

Basic properties mapping of anodic oxides in the hafnium-niobium-tantalum ternary system.

A thin film combinatorial library deposited by co-sputtering of Hf, Nb and Ta was employed to characterise fundamental properties of the Hf-Nb-Ta system. Compositional mappings of microstructure and crystallography revealed similarities in alloy evolution. Distinct lattice distortion was observed upon addition of hexagonal Hf, leading to amorphisation of alloys containing more than 32 at.% Hf and less than 27 and 41 at.% Nb and Ta, respectively. Volta potential and open circuit potential mappings indicated minimal values for the highest Hf concentration. Localised anodisation of the library by scanning droplet cell microscopy revealed valve metal behaviour. Oxide formation factors above 2 nm V-1 were identified in compositional zones with high amounts of Nb and Ta. Fitting of electrochemical impedance spectroscopy data allowed electrical permittivity and resistivity of mixed oxides to be mapped. Their compositional behaviours were attributed to characteristics of the parent metal alloys and particularities of the pure oxides. Mott-Schottky analysis suggested n-type semiconductor properties for all Hf-Nb-Ta oxides studied. Donor density and flat-band potential were mapped compositionally, and their variations were found to be related mainly to the Nb amount. Synergetic effects were identified in mappings of Hf-Nb-Ta parent metals and their anodic oxides.

Anodic oxide formation on aluminium-terbium alloys.

Aluminium terbium alloys were prepared by simultaneous thermal evaporation resulting in a thin film library covering a 5 to 25 at.% Tb compositional spread. Synchrotron x-ray diffraction (XRD) proves all of the alloys to be amorphous. Scanning electron microscopy (SEM) measurements reveal the structural changes upon increase in Tb content with the formation of small, Tb-rich segregations right before a drastic change in morphology around 25 at.% Tb. Anodic oxides were formed systematically in cyclic voltammograms using scanning droplet cell microscopy. Coulometric analysis revealed a linear thickness over formation potential behaviour with film formation factors ranging from 1.2 nm V-1 (5 at.% Tb) to 1.6 nm V-1 (25 % Tb). Electrochemical impedance spectroscopy was performed for each incremental oxidation step resulting in a linear relation between inverse capacity and formation potential with dielectric constants ranging from 8 (5 at.% Tb) to 16 (25 at.% Tb).

Rhodium-coordinated poly(arylene-ethynylene)-alt-poly(arylene-vinylene) copolymer acting as photocatalyst for visible-light-powered NAD⁺/NADH reduction.

A 2,2'-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD(+)/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390-650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD(+). With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled.

Photoelectrochemical scanning droplet cell microscopy for localized photovoltaic investigations on organic semiconductors.

Photoelectrochemical characterization of the regioregular poly(3-hexylthiophene) (P3HT) was performed using an adapted version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM). The real and imaginary parts of the dielectric function were determined using spectroscopic ellipsometry in order to identify the absorption region of the polymer. Detailed photoelectrochemical experiments were performed for the thin polymer layer contacted with 0.1 M tetrabutylammonium hexafluorophosphate dissolved in propylene carbonate as well as with an electrolyte containing a 5.4 mM ferrocene/ferrocenium redox couple. The effect of the illumination on the P3HT covered WE in contact with both the pure electrolyte and an electrolyte containing a ferrocene/ferrocenium redox couple was studied using dark/illumination sequences. The stability of the photovoltaic effect was characterized using long term current transients. Finally, the photoelectrochemical impedance spectroscopy was applied to determine the electrical properties of the P3HT in the dark and under illumination.

Properties of anodic oxides grown on a hafnium-tantalum-titanium thin film library.

A ternary thin film combinatorial materials library of the valve metal system Hf-Ta-Ti obtained by co-sputtering was studied. The microstructural and crystallographic analysis of the obtained compositions revealed a crystalline and textured surface, with the exception of compositions with Ta concentration above 48 at.% which are amorphous and show a flat surface. Electrochemical anodization of the composition spread thin films was used for analysing the growth of the mixed surface oxides. Oxide formation factors, obtained from the potentiodynamic anodization curves, as well as the dielectric constants and electrical resistances, obtained from electrochemical impedance spectroscopy, were mapped along two dimensions of the library using a scanning droplet cell microscope. The semiconducting properties of the anodic oxides were mapped using Mott-Schottky analysis. The degree of oxide mixing was analysed qualitatively using x-ray photoelectron spectroscopy depth profiling. A quantitative analysis of the surface oxides was performed and correlated to the as-deposited metal thin film compositions. In the concurrent transport of the three metal cations during oxide growth a clear speed order of Ti > Hf > Ta was proven.

Localized photovoltaic investigations on organic semiconductors and bulk heterojunction solar cells.

Newly synthesized organic electronics materials are often available in submicrogram amounts only. Photoelectrochemical scanning droplet cell microscopy is a powerful method that allows a comprehensive characterisation of such small amounts including oxidation, reduction potentials, doping, determination of charge carriers, band gap, charge capacity, over-oxidation sensitivity and many more. Localized photoelectrochemical characterization of the poly[4,8-bis-substituted-benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl-alt-4-substituted-thieno [3,4-b] thiophene-2,6-diyl] (PBDTTT-c) and PBDTTT-c:PCBM bulk heterojunction was performed using photoelectrochemical scanning droplet cell microscopy (PE-SDCM). The optical properties and the real and imaginary part of the dielectric function, of the polymer were determined using spectroscopic ellipsometry. The photoelectrochemical characterizations were performed in a three and two electrode configuration of PE-SDCM under laser and white light illumination. The effect of illumination was characterized using dark/illumination sequences. The stability of the photocurrent was studied using longer term (600 s) illumination. Finally the effect of cell configuration and illumination conditions on the photovoltage was studied.

Tuning the magnetic properties of metal oxide nanocrystal heterostructures by cation exchange.

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal's magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe(2+) to Co(2+) cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co(2+) is demonstrated. By applying the cation exchange to FeO/CoFe(2)O(4) core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system.

Interfacial Resistive Switching of Niobium-Titanium Anodic Memristors with Self-Rectifying Capabilities.

A broad compositional range of Nb-Ti anodic memristors with volatile and self-rectifying behaviour was studied using a combinatorial screening approach. A Nb-Ti thin-film combinatorial library was co-deposited by sputtering, serving as the bottom electrode for the memristive devices. The library, with a compositional spread ranging between 22 and 64 at.% Ti was anodically oxidised, the mixed oxide being the active layer in MIM-type structures completed by Pt discreet top electrode patterning. By studying I-U sweeps, memristors with self-rectifying and volatile behaviour were identified. Moreover, all the analysed memristors demonstrated multilevel properties. The best-performing memristors showed HRS/LRS (high resistive state/low resistive state) ratios between 4 and 6 × 105 and very good retention up to 106 successive readings. The anodic memristors grown along the compositional spread showed very good endurance up to 106 switching cycles, excluding those grown from alloys containing between 31 and 39 at.% Ti, which withstood only 10 switching cycles. Taking into consideration all the parameters studied, the Nb-46 at.% Ti composition was screened as the parent metal alloy composition, leading to the best-performing anodic memristor in this alloy system. The results obtained suggest that memristive behaviour is based on an interfacial non-filamentary type of resistive switching, which is consistent with the performed cross-sectional TEM structural and chemical characterisation.

Revisiting Electronic Topological Transitions in the Silver-Palladium (AgcPd1-c) Solid Solution: An Experimental and Theoretical Investigation.

Multiple thick film samples of the AgcPd1-c solid solution were prepared using physical vapour deposition over a borosilicate glass substrate. This synthesis technique allows continuous variation in stoichiometry, while the distribution of silver or palladium atoms retains the arrangement into an on-average periodic lattice with smoothly varying unit cell parameters. The alloy concentration and geometry were measured over a set of sample points, respectively, via energy-dispersive X-ray spectroscopy and via X-ray diffraction. These results are compared with ab initio total energy and electronic structure calculations based on density functional theory, and using the coherent potential approximation for an effective medium description of disorder. The theoretically acquired lattice parameters appear in qualitative agreement with the measured trends. The numerical study of the Fermi surface also shows a variation in its topological features, which follow the change in silver concentration. These were related to the electrical resistivity of the AgcPd1-c alloy. The theoretically obtained variation exhibits a significant correlation with nonlinear changes in the resistivity as a function of composition. This combined experimental and theoretical study suggests the possibility of using resistivity measurements along concentration gradients as a way to gain some microscopic insight into the electronic structure of an alloy.

Photoelectrochemical scanning droplet cell microscopy (PE-SDCM).

Principles of localised photoelectrochemistry are summarised and an experimental approach is described that allows the performance of the most important photoelectrochemical experiments within a diameter of 100 µm. Various light sources, such as a continuum emitter with a monochromator, LEDs, and lasers are coupled into a multi-mode fibre to illuminate a small spot that is wetted by the electrolyte from a capillary. Reference electrode, counter electrode, and optical fibre are installed in the capillary system. The performance of this system is demonstrated by photocurrent measurements on n-doped Si and p-doped Si as model substrates. A thickness-graded aluminium thin film for partial shadowing on Si proves the applicability for material library investigations in combinatorial materials science. Further experiments demonstrate the possibility of electrical light chopping as well as impedance spectroscopy with subsequent Mott-Schottky analysis for the determination of charge-carrier concentration and type, flat-band potential, and inversion layer formation. Photoelectrochemical scanning droplet cell microscopy (PE-SDCM) is an extremely versatile tool for the screening of water splitting photoelectrodes, the characterisation of photocatalysts, and high throughput characterisation of microgram amounts of new solar cell materials.

Characterization of local electrochemical doping of high performance conjugated polymer for photovoltaics using scanning droplet cell microscopy.

The electrochemical oxidation of a next generation low bandgap high performance photovoltaic material namely poly[4,8-bis-substituted-benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl-alt-4-substituted-thieno[3,4-b] thiophene-2,6-diyl] (PBDTTT-c) thin film was investigated using a scanning droplet cell microscope. Cyclic voltammetry was used for the basic characterization of the oxidation/doping of PBDTTT-c. Application of the different final potentials during the electrochemical study provides a close look to the oxidation kinetics. The electrical properties of both doped and undoped PBDTTT-c were analyzed in situ by electrochemical impedance spectroscopy giving the possibility to correlate the changes in the doping level with the subsequent changes in the resistance and capacitance. As a result one oxidation peak was found during the cyclic voltammetry and in potentiostatic measurements. From Mott-Schottky analysis a donor concentration of 2.3 × 1020 cm-3 and a flat band potential of 1.00 V vs. SHE were found. The oxidation process resulted in an increase of the conductivity by two orders of magnitude reaching a maximum for the oxidized form of 1.4 S cm-1.

Evolution of Microstructure, Mechanical Properties, and Corrosion Resistance of Mg-2.2Gd-2.2Zn-0.2Ca (wt%) Alloy by Extrusion at Various Temperatures.

The current investigation involved casting the Mg-2.2Gd-2.2Zn-0.2Ca (wt%) alloy (GZX220) through permanent mold casting, followed by homogenization at 400 °C for 24 h and extrusion at 250 °C, 300 °C, 350 °C, and 400 °C. Microstructure investigations revealed that α-Mg, Mg-Gd, and Mg-Gd-Zn intermetallic phases were present in the as-cast alloy. Following the homogenization treatment, a majority of these intermetallic particles underwent partial dissolution into the matrix phase. α-Mg grains exhibited a considerable refinement by extrusion due to dynamic recrystallization (DRX). At low extrusion temperatures, higher basal texture intensities were observed. The mechanical properties were remarkably enhanced after the extrusion process. However, a consistent decline in strength was observed with the rise in extrusion temperature. The corrosion performance of the as-cast GZX220 alloy was reduced by homogenization because of the lack of corrosion barrier effect of secondary phases. A significant enhancement of corrosion resistance was achieved by the extrusion process.

Threshold Switching in Forming-Free Anodic Memristors Grown on Hf-Nb Combinatorial Thin-Film Alloys.

The development of novel materials with coexisting volatile threshold and non-volatile memristive switching is crucial for neuromorphic applications. Hence, the aim of this work was to investigate the memristive properties of oxides in a Hf-Nb thin-film combinatorial system deposited by sputtering on Si substrates. The active layer was grown anodically on each Hf-Nb alloy from the library, whereas Pt electrodes were deposited as the top electrodes. The devices grown on Hf-45 at.% Nb alloys showed improved memristive performances reaching resistive state ratios up to a few orders of magnitude and achieving multi-level switching behavior while consuming low power in comparison with memristors grown on pure metals. The coexistence of threshold and resistive switching is dependent upon the current compliance regime applied during memristive studies. Such behaviors were explained by the structure of the mixed oxides investigated by TEM and XPS. The mixed oxides, with HfO2 crystallites embedded in quasi amorphous and stoichiometrically non-uniform Nb oxide regions, were found to be favorable for the formation of conductive filaments as a necessary step toward memristive behavior. Finally, metal-insulator-metal structures grown on the respective alloys can be considered as relevant candidates for the future fabrication of anodic high-density in-memory computing systems for neuromorphic applications.

Comparative Behavior of Viscose-Based Supercapacitor Electrodes Activated by KOH, H2O, and CO2.

Activated carbons derived from viscose fibers were prepared using potassium hydroxide, carbon dioxide, or water vapor as activation agents. The produced activated carbon fibers were analyzed via scanning electron microscopy and energy dispersive X-ray spectroscopy, and their porosity (specific surface area, total pore volume, and pore size distribution) was calculated employing physisorption experiments. Activated carbon fibers with a specific surface area of more than 2500 m2 g-1 were obtained by each of the three methods. Afterwards, the suitability of these materials as electrodes for electrochemical double-layer capacitors (supercapacitors) was investigated using cyclic voltammetry, galvanostatic measurements, and electrochemical impedance spectroscopy. By combining CO2 and H2O activation, activated carbon fibers of high purity and excellent electrochemical performance could be obtained. A specific capacitance per electrode of up to 180 F g-1 was found. In addition, an energy density per double-layer capacitor of 42 W h kg-1 was achieved. These results demonstrate the outstanding electrochemical properties of viscose-based activated carbon fibers for use as electrode materials in energy storage devices such as supercapacitors.

Impact of Electrolyte Incorporation in Anodized Niobium on Its Resistive Switching.

The aim of this study was to develop memristors based on Nb2O5 grown by a simple and inexpensive electrochemical anodization process. It was confirmed that the electrolyte selection plays a crucial role in resistive switching due to electrolyte species incorporation in oxide, thus influencing the formation of conductive filaments. Anodic memristors grown in phosphate buffer showed improved electrical characteristics, while those formed in citrated buffer exhibited excellent memory capabilities. The chemical composition of oxides was successfully determined using HAXPES, while their phase composition and crystal structure with conductive filaments was assessed by TEM at the nanoscale. Overall, understanding the switching mechanism leads towards a wide range of possible applications for Nb memristors either as selector devices or nonvolatile memories.

Composite Memristors by Nanoscale Modification of Hf/Ta Anodic Oxides.

Composite memristors based on anodic oxidation of Hf superimposed on Ta thin films are studied. A layered structure is obtained by successive sputtering of Ta and Hf thin films. The deposition geometry ensured components' thickness gradient profiles (wedges) aligned in opposite directions. Anodization in citrate buffer electrolyte leads to a nanoscale columnar structuring of Ta2O5 in HfO2 due to the higher electrical resistance of the latter. Following the less resistive path, the ionic current forces Ta oxide to locally grow toward the electrolyte interface according to the Rayleigh-Taylor principle. The obtained composite oxide memristive properties are studied as a function of the Hf/Ta thickness ratio. One pronounced zone prominent for memristive applications is found for ratios between 4 and 5. Here, unipolar and bipolar memristors are found, with remarkable endurance and retention capabilities. This is discussed in the frame of conductive filament formation preferentially along the interfaces between oxides.

Femtosecond Laser-Processing of Pre-Anodized Ti-Based Bone Implants for Cell-Repellent Functionalization.

Microstructures and nanostructures can be used to reduce the adhesion of the cells on the auxiliary material. Therefore, the aim of our work was to fabricate laser-induced hierarchical microstructures and nanostructures by femtosecond laser-treatment (wavelength 1040 nm, pulse length 350 fs, repetition rates in the kHz range) to reduce the cell adhesion. Additionally, surface chemistry modification by optimized electrochemical anodization was used to further reduce the cell adhesion. For testing, flat plates and bone screws made of Ti-6Al-4V were used. Bone-forming cells (human osteoblasts from the cell line SAOS-2) were grown on the bone implants and additional test samples for two to three weeks. After the growth period, the cells were characterized by scanning electron microscopy (SEM). While earlier experiments with fibroblasts had shown that femtosecond laser-processing followed by electrochemical anodization had a significant impact on cell adhesion reduction, for osteoblasts the same conditions resulted in an activation of the cells with increased production of extracellular matrix material. Significant reduction of cell adhesion for osteoblasts was only obtained at pre-anodized surfaces. It could be demonstrated that this functionalization by means of femtosecond laser-processing can result in bone screws that hinder the adhesion of osteoblasts.