Effectiveness of Ligand Denticity-Dependent Oxidation Protection in Copper MOD Inks.

The recent cost-driven transition from silver- to copper-based inks for printing on flexible substrates is connected with new key challenges. Given the high oxidation sensitivity of copper inks before, during, and after the curing process, the conductivity and thereby the device performance can be affected. Strategies to limit or even avoid this drawback include the development of metal organic decomposition (MOD) inks with selected "protective" ligands. In this study, the influence of the ligand on the oxide formation during the ink decomposition process is described using a wide variety of in situ characterization techniques. It is demonstrated that bidentate ligands provide an improved oxidation barrier, although the copper preservation mechanism has its limits: oxygen can interfere in every reduction pathway depending on the curing duration and atmospheric conditions. The generated insights can be applied in the further evolution toward ambient-curable copper MOD inks.

Screen-printing of flexible semi-transparent electrodes and devices based on silver nanowire networks.

Silver nanowire networks have demonstrated significant potential as semi-transparent electrodes for various applications. However, for their widespread utilisation in devices, upscaled coating technologies such as screen-printing need to be explored and related to this, the formulation of suitable inks is indispensable. This work contributes to this effort by the synthesis of Ag-NW based formulations. The rheological characteristics that are essential for screen-printing are obtained by the addition of hydrophobically modified cellulose. The electrical and optical characteristics of screen-printed features on PET are compared by a Van der Pauw method and UV-vis spectroscopy. Despite the presence of the cellulose additive, the screen-printed electrodes exhibit a transmittance from 92.8% to 57.3% and a sheet resistance down to 27 Ohm sq-1. Based on the percolation theory in composites, a mathematical expression is presented, which allows the in-depth analysis of the resulting opto-electrical properties. The application potential of the nanowire-containing formulations is finally demonstrated by screen-printing functional, flexible electroluminescent devices.

Ti surface doping of LiNi0.5Mn1.5O4-δ positive electrodes for lithium ion batteries.

The particle surface of LiNi0.5Mn1.5O4-δ (LNMO), a Li-ion battery cathode material, has been modified by Ti cation doping through a hydrolysis-condensation reaction followed by annealing in oxygen. The effect of different annealing temperatures (500-850 °C) on the Ti distribution and electrochemical performance of the surface modified LNMO was investigated. Ti cations diffuse from the preformed amorphous 'TiO x ' layer into the LNMO surface during annealing at 500 °C. This results in a 2-4 nm thick Ti-rich spinel surface having lower Mn and Ni content compared to the core of the LNMO particles, which was observed with scanning transmission electron microscopy coupled with compositional EDX mapping. An increase in the annealing temperature promotes the formation of a Ti bulk doped LiNi(0.5-w)Mn(1.5+w)-t Ti t O4 phase and Ti-rich LiNi0.5Mn1.5-y Ti y O4 segregates above 750 °C. Fourier-transform infrared spectrometry indicates increasing Ni-Mn ordering with annealing temperature, for both bare and surface modified LNMO. Ti surface modified LNMO annealed at 500 °C shows a superior cyclic stability, coulombic efficiency and rate performance compared to bare LNMO annealed at 500 °C when cycled at 3.4-4.9 V vs. Li/Li+. The improvements are probably due to suppressed Ni and Mn dissolution with Ti surface doping.

A novel explanation for the increased conductivity in annealed Al-doped ZnO: an insight into migration of aluminum and displacement of zinc.

A combined experimental and first-principles study is performed to study the origin of conductivity in ZnO:Al nanoparticles synthesized under controlled conditions via a reflux route using benzylamine as a solvent. The experimental characterization of the samples by Raman, nuclear magnetic resonance (NMR) and conductivity measurements indicates that upon annealing in nitrogen, the Al atoms at interstitial positions migrate to the substitutional positions, creating at the same time Zn interstitials. We provide evidence for the fact that the formed complex of AlZn and Zni corresponds to the origin of the Knight shifted peak (KS) we observe in 27Al NMR. As far as we know, the role of this complex has not been discussed in the literature to date. However, our first-principles calculations show that such a complex is indeed energetically favoured over the isolated Al interstitial positions. In our calculations we also address the charge state of the Al interstitials. Further, Zn interstitials can migrate from AlZn and possibly also form Zn clusters, leading to the observed increased conductivity.

Remarkable lowering in the synthesis temperature of LiMn2O4via citrate solution-gel synthesis facilitated by ethanol.

LiMn2O4 (LMO) is interesting from the viewpoint of its energy storage applications as it is a cathode in lithium ion batteries (LIB), which contains no rare, toxic or expansive elements, while it provides a high theoretical capacity (148 mA h g-1) at a reasonable voltage (4 V region) and a higher thermal stability compared to cobalt based cathodes and has a good rechargeability and cycling stability due to its spinel structure. Low temperature synthesis routes for cathode materials are currently gaining attention, in order to decrease the ecological footprint of the final LIB. Here, the crystallization temperature of LMO by a citrate based solution-gel synthesis was significantly lowered, to as low as 250 °C by the addition of ethanol to the precursor. The role of ethanol in this synthesis process was explored. It was found to lead to a considerable increase in the oxidation rate of the redox couple Mn2+/Mn3+, a lowering of the precursor decomposition temperature by 200 °C, besides a drastic decrease in the crystallization temperature (reaching 250 °C). Moreover, the main cause was identified to be an esterification reaction of ethanol with the carboxylic acid in the precursor complexes, taking place before the oxide formation. The insights obtained strengthen the knowledge regarding citrato-Mn2+/Mn3+ complexes present in aqueous solution-gel synthesis routes and are relevant for the preparation of various manganese containing oxides. Moreover, the precursor developed opens up a new possibility for the low temperature synthesis of LMO powders and thin films for application in LIB. In the case of thin film batteries, the low temperature processing provides compatibility with other materials in the thin film battery stack, avoiding undesired oxidations or interfacial reactions.

Ultrasonically spray coated silver layers from designed precursor inks for flexible electronics.

Integration of electronic circuit components onto flexible materials such as plastic foils, paper and textiles is a key challenge for the development of future smart applications. Therefore, conductive metal features need to be deposited on temperature sensitive substrates in a fast and straightforward way. The feasibility of these emerging (nano-) electronic technologies depends on the availability of well-designed deposition techniques and on novel functional metal inks. As ultrasonic spray coating (USSC) is one of the most promising techniques to meet the above requirements, innovative metal organic decomposition (MOD) inks are designed to deposit silver features on plastic foils. Various amine ligands were screened and their influence on the ink stability and the characteristics of the resulting metal depositions were evaluated to determine the optimal formulation. Eventually, silver layers with excellent performance in terms of conductivity (15% bulk silver conductivity), stability, morphology and adhesion could be obtained, while operating in a very low temperature window of 70 °C-120 °C. Moreover, the optimal deposition conditions were determined via an in-depth analysis of the ultrasonically sprayed silver layers. Applying these tailored MOD inks, the USSC technique enabled smooth, semi-transparent silver layers with a tunable thickness on large areas without time-consuming additional sintering steps after deposition. Therefore, this novel combination of nanoparticle-free Ag-inks and the USSC process holds promise for high throughput deposition of highly conductive silver features on heat sensitive substrates and even 3D objects.

The pressure sensitivity of wrinkled B-doped nanocrystalline diamond membranes.

Nanocrystalline diamond (NCD) membranes are promising candidates for use as sensitive pressure sensors. NCD membranes are able to withstand harsh conditions and are easily fabricated on glass. In this study the sensitivity of heavily boron doped NCD (B:NCD) pressure sensors is evaluated with respect to different types of supporting glass substrates, doping levels and membrane sizes. Higher pressure sensing sensitivities are obtained for membranes on Corning Eagle 2000 glass, which have a better match in thermal expansion coefficient with diamond compared to those on Schott AF45 glass. In addition, it is shown that larger and more heavily doped membranes are more sensitive. After fabrication of the membranes, the stress in the B:NCD films is released by the emergence of wrinkles. A better match between the thermal expansion coefficient of the NCD layer and the underlying substrate results in less stress and a smaller amount of wrinkles as confirmed by Raman spectroscopy and 3D surface imaging.

Relaxor ferroelectricity and magnetoelectric coupling in ZnO-Co nanocomposite thin films: beyond multiferroic composites.

ZnO-Co nanocomposite thin films are synthesized by combination of pulsed laser deposition of ZnO and Co ion implantation. Both superparamagnetism and relaxor ferroelectricity as well as magnetoelectric coupling in the nanocomposites have been demonstrated. The unexpected relaxor ferroelectricity is believed to be the result of the local lattice distortion induced by the incorporation of the Co nanoparticles. Magnetoelectric coupling can be attributed to the interaction between the electric dipole moments and the magnetic moments, which are both induced by the incorporation of Co. The introduced ZnO-Co nanocomposite thin films are different from conventional strain-mediated multiferroic composites.

Paramagnetism and antiferromagnetic interactions in single-phase Fe-implanted ZnO.

As the intrinsic origin of the high-temperature ferromagnetism often observed in wide-gap dilute magnetic semiconductors becomes increasingly debated, there is a growing need for comprehensive studies on the single-phase region of the phase diagram of these materials. Here we report on the magnetic and structural properties of Fe-doped ZnO prepared by ion implantation of ZnO single crystals. A detailed structural characterization shows that the Fe impurities substitute for Zn in ZnO in a wurtzite Zn(1-x)Fe(x)O phase which is coherent with the ZnO host. In addition, the density of beam-induced defects is progressively decreased by thermal annealing up to 900 ° C, from highly disordered after implantation to highly crystalline upon subsequent annealing. Based on a detailed analysis of the magnetometry data, we demonstrate that isolated Fe impurities occupying Zn-substitutional sites behave as localized paramagnetic moments down to 2 K, irrespective of the Fe concentration and the density of beam-induced defects. With increasing local concentration of Zn-substitutional Fe, strong nearest-cation-neighbor antiferromagnetic interactions favor the antiparallel alignment of the Fe moments.

Atomic scale dynamics of ultrasmall germanium clusters.

Starting from the gas phase, small clusters can be produced and deposited with huge flexibility with regard to composition, materials choice and cluster size. Despite many advances in experimental characterization, a detailed morphology of such clusters is still lacking. Here we present an atomic scale observation as well as the dynamical behaviour of ultrasmall germanium clusters. Using quantitative scanning transmission electron microscopy in combination with ab initio calculations, we are able to characterize the transition between different equilibrium geometries of a germanium cluster consisting of less than 25 atoms. Seven-membered rings, trigonal prisms and some smaller subunits are identified as possible building blocks that stabilize the structure.

Paramagnetism and antiferromagnetic interactions in Cr-doped GaN.

We report on the magnetic and structural properties of Cr-doped GaN prepared by ion implantation of epitaxial thin films. Based on a detailed analysis of the magnetometry data, we demonstrate that the magnetic interactions between Cr moments in GaN are antiferromagnetic (AFM). Increasing the Cr fractional concentration up to 0.35, we observe that strong nearest cation neighbor AFM coupling results in the reduction of the effective moment per Cr atom. The uncompensated Cr moments exhibit paramagnetic behavior and we discuss to what extent the effects of an anisotropic crystal field and AFM interactions can be inferred from the magnetization data. We discuss the observed changes in magnetic and structural properties induced by thermal annealing in terms of defect annealing and Cr aggregation.

Hydrogen-induced Ostwald ripening at room temperature in a Pd nanocluster film.

The structural and morphological changes occurring in an ensemble of vapor deposited palladium nanoclusters have been studied after several hydrogenation cycles with x-ray diffraction, extended x-ray-absorption fine structure spectroscopy, Rutherford backscattering spectrometry, and STM. Initial hydrogenation increased the cluster size, a result that is attributed to hydrogen-induced Ostwald ripening. This phenomenon originates from the higher mobility of palladium atoms resulting from the low sublimation energy of the palladium hydride as compared to that of the palladium metal. The universality of this phenomenon makes it important for the application of future nanostructured hydrogen storage materials.

Domain-wall guided nucleation of superconductivity in hybrid ferromagnet-superconductor-ferromagnet layered structures.

Domain-wall superconductivity is studied in a superconducting Nb film placed between two ferromagnetic Co/Pd multilayers with perpendicular magnetization. The parameters of top and bottom ferromagnetic films are chosen to provide different coercive fields, so that the magnetic domain structure of the ferromagnets can be selectively controlled. From the dependence of the critical temperature Tc on the applied magnetic field H, we have found evidence for domain-wall superconductivity in this three-layered F/S/F structure for different magnetic domain patterns. The phase boundary, calculated numerically for this structure from the linearized Ginzburg-Landau equation, is in good agreement with the experimental data.

Enhanced asymmetric magnetization reversal in nanoscale Co/CoO arrays: competition between exchange bias and magnetostatic coupling.

Magnetization reversal was studied in square arrays of square Co/CoO dots with lateral size varying between 200 and 900 nm. While reference nonpatterned Co/CoO films show the typical shift and increased width of the hysteresis loop due to exchange bias, the patterned samples reveal a pronounced size dependence. In particular, an anomaly appears in the upper branch of the magnetization cycle and becomes stronger as the dot size decreases. This anomaly, which is absent at room temperature in the patterned samples, can be understood in terms of a competition between magnetostatic interdot interaction and exchange anisotropy during the magnetic switching process.

Symmetry locking and commensurate vortex domain formation in periodic pinning arrays.

The spontaneous formation of domains of commensurate vortex patterns near rational fractional matching fields of a periodic pinning array has been investigated with high resolution scanning Hall probe microscopy. We show that domain formation is promoted due to the efficient incorporation of mismatched excess vortices and vacancies at the corners of domain walls, which outweighs the energetic cost of creating them. Molecular dynamics simulations with a generic pinning potential reveal that domains are formed only when vortex-vortex interactions are long range.

In vitro susceptibility of Enterococcus faecium isolated from food to growth-promoting and therapeutic antibiotics.

A total of 76 E. faecium strains, isolated at retail level from raw poultry meat, cheese, raw pork, and preparations of cheese and raw pork, were tested for their susceptibility and resistance to growth-promoting antibacterials used in animals and antibiotics used therapeutically in humans. All strains were uniformly susceptible to the growth promoters bambermycin and avilamycin. Resistance against bacitracin, virginiamycin and narasin was high among strains from poultry meat. With tylosin, a macrolide antibiotic used therapeutically and for growth promotion, resistance was mainly detected in strains originating from poultry meat, though also in some strains from pork and from pork and cheese preparations. The therapeutic antibiotic dalfopristin/quinupristin did not show full cross-resistance with the growth-promoting antibiotic virginiamycin. With dalfopristin/quinupristin two different levels of resistance were found. Only one E. faecium strain isolated from poultry was resistant to the glycopeptides avoparcin and vancomycin. Only one poultry meat strain was highly resistant to ampicillin. However, nearly all poultry meat strains showed decreased sensitivity. Only 3 out of 24 poultry strains were susceptible to minocycline, while all strains from other origins were susceptible to this tetracycline antibiotic. High-level streptomycin resistance was seen in strains of all origins, though infrequently. High-level gentamicin resistance was not found.

Heterozygosity for Tay-Sachs disease in non-Jewish Americans with ancestry from Ireland or Great Britain.

We performed a genetic epidemiological analysis of American non-Jewish people with ancestry from Ireland or Great Britain with regard to heterozgosity for Tay-Sachs disease (TSD). This study was prompted by a recent report that the frequency of heterozygosity for TSD among Irish Americans was 1 in 8, a frequency much higher than that recognised for any other population group. We identified 19 of 576 (3.3%) people of Irish background as TSD heterozygotes by the standard thermolability assay for beta-hexosaminidase A (Hex A) activity. Three of 289 people of non-Irish British Isles background (1%) were also identified as heterozygotes by biochemical testing. Specimens from the biochemically identified Irish heterozygotes were analysed for seven different Hex A alpha subunit gene mutations; three (15.8%) had a lethal +1 IVS-9 G to A mutation, previously noted to be a common mutation among TSD heterozygotes of Irish ancestry. Eight of 19 (42.1%) had one of two benign or pseudodeficiency mutations, and no mutation was found in 42.1% of the heterozygotes analysed. These data indicate that non-Jewish Americans with Irish background have a significantly increased frequency of heterozygosity at the Hex A alpha subunit gene locus, but that approximately 42% of the biochemically ascertained heterozygotes have clinically benign mutations. A pseudodeficiency mutation was identified in one of the three TSD heterozygotes of non-Irish British Isles background; no mutations were found in the other two. The data allow for a frequency estimate of deleterious alleles for TSD among Irish Americans of 1 in 192 to 1 in 52. Non-Jewish Americans with ancestry from Great Britain have a minimal, if any, increase in rate of heterozygosity at the TSD gene locus relative to the general population.