Normal state properties of high angle grain boundaries in (Y,Ca)Ba2Cu3O7-delta

By lithographically fabricating an optimised Wheatstone bridge geometry, we have been able to make accurate measurements of the resistance of grain boundaries in Y1-xCaxBa2Cu3O7-d between the superconducting transition temperature, Tc, and room temperature. Below Tc the normal state properties were assessed by applying sufficiently high currents. The behaviour of the grain boundary resistance versus temperature and of the conductance versus voltage are discussed in the framework charge transport through a tunnel barrier. The influence of misorientation angle, oxygen content, and calcium doping on the normal state properties is related to changes of the height and shape of the grain boundary potential barrier.Comment: 17 pages, 1 table, 5 figures, submitted to PR

Absolute Seebeck coefficient of thin platinum films

The influence of size effects on the thermoelectric properties of thin platinum films is investigated and compared to the bulk. Structural properties, like the film thickness and the grain size, are varied. We correlate the electron mean free path with the temperature dependence of the electrical conductivity and the absolute Seebeck coefficient $S_{\text{Pt}}$ of platinum. We use a measurement platform as a standardized method to determine $S_{\text{Pt}}$ and show that $S_{\text{Pt,film}}$ is reduced compared to $S_{\text{Pt,bulk}}$. Boundary and surface scattering reduce the thermodiffusion and the phonon drag contribution to $S_{\text{Pt,film}}$ by nearly the same factor. A detailed discussion and a model to describe the temperature dependence of the absolute Seebeck coefficient and the influence of size effects of electron-phonon and phonon-phonon interaction on $S_{\text{Pt}}$ is given

Characterizing thermal conduction in polycrystalline graphene

Thermal conduction was explored and discussed through a combined theoretical and simulation approach in this work. The thermal conductivity k of polycrystalline graphene was calculated by molecular dynamics simulations based on a hexagonal patch model in close consistence with microstructural characterization in experiments. The effects of grain size, alignment, and temperature were identified with discussion on the microscopic phonon scattering mechanisms. The effective thermal conductivity is found to increase with the grain size and decrease with the mismatch angle and dislocation density at the grain boundaries. The 1/T temperature dependence of k is significantly weakened in the polycrystals. The effect of grain boundaries in modifying thermal transport properties of graphene was characterized by their effective width and thermal conductivity as an individual phase, which was later included in a predictive effective medium model that showed degraded reduction in thermal conductivity for grain larger than a few microns

On the extraction of resistivity and area of nanoscale interconnect lines by temperature-dependent resistance measurements

Several issues concerning the applicability of the temperature coefficient of the resistivity (TCR) method to scaled interconnect lines are discussed. The central approximation of the TCR method, the substitution of the interconnect wire TCR by the bulk TCR becomes doubtful when the resistivity of the conductor metal is strongly increased by finite size effects. Semiclassical calculations for thin films show that the TCR deviates from bulk values when the surface roughness scattering contribution to the total resistivity becomes significant with respect to grain boundary scattering, an effect that might become even more important in nanowires due to their larger surface-to-volume ration. In addition, the TCR method is redeveloped to account for line width roughness. It is shown that for rough wires, the TCR method yields the harmonic average of the cross-sectional area as well as, to first order, the accurate value of the resistivity at the extracted area. Finally, the effect of a conductive barrier or liner layer on the TCR method is discussed. It is shown that the liner or barrier parallel conductance can only be neglected when it is lower than about 5 to 10% of the total conductance. It is furthermore shown that neglecting the liner/barrier parallel conductance leads mainly to an overestimation of the cross-sectional area of the center conductor whereas its resistivity is less affected.Comment: 28 pages, 5 figure

Near-field photocurrent nanoscopy on bare and encapsulated graphene

Opto-electronic devices utilizing graphene have already demonstrated unique capabilities, which are much more difficult to realize with conventional technologies. However, the requirements in terms of material quality and uniformity are very demanding. A major roadblock towards high-performance devices are the nanoscale variations of graphene properties, which strongly impact the macroscopic device behaviour. Here, we present and apply opto-electronic nanoscopy to measure locally both the optical and electronic properties of graphene devices. This is achieved by combining scanning near-field infrared nanoscopy with electrical device read-out, allowing infrared photocurrent mapping at length scales of tens of nanometers. We apply this technique to study the impact of edges and grain boundaries on spatial carrier density profiles and local thermoelectric properties. Moreover, we show that the technique can also be applied to encapsulated graphene/hexagonal boron nitride (h-BN) devices, where we observe strong charge build-up near the edges, and also address a device solution to this problem. The technique enables nanoscale characterization for a broad range of common graphene devices without the need of special device architectures or invasive graphene treatment

Thickness dependence of the resistivity of Platinum group metal thin films

We report on the thin film resistivity of several platinum-group metals (Ru, Pd, Ir, Pt). Platinum-group thin films show comparable or lower resistivities than Cu for film thicknesses below about 5\,nm due to a weaker thickness dependence of the resistivity. Based on experimentally determined mean linear distances between grain boundaries as well as ab initio calculations of the electron mean free path, the data for Ru, Ir, and Cu were modeled within the semiclassical Mayadas--Shatzkes model [Phys. Rev. B 1, 1382 (1970)] to assess the combined contributions of surface and grain boundary scattering to the resistivity. For Ru, the modeling results indicated that surface scattering was strongly dependent on the surrounding material with nearly specular scattering at interfaces with SiO2 or air but with diffuse scattering at interfaces with TaN. The dependence of the thin film resistivity on the mean free path is also discussed within the Mayadas--Shatzkes model in consideration of the experimental findings.Comment: 28 pages, 9 figure

On the transport of alkali ions through polymeric mold compounds and polyelectrolyte membranes.

The aim of this work is the attempt in understanding ion transport properties across structured materials such as polyelectrolyte multilayers (PEMs) and highly filled epoxy resins used as an encapsulant, i.e. mold compounds. The ion transport properties are studied by means of the technique of charge attachment induced transport (CAIT), which was recently developed and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The mold compounds studied in this work are of four types (MCP1, MCP2, MCP3, MCP4) with a composition of 80% - 88% of silica filler and the rest of raw materials such as epoxy resin, hardener and flame retardant. The samples are analyzed by means of the CAIT technique, leading to the evaluation of values of ionic conductivity and activation energy related to the process of transport of potassium ions. The ionic conductivity of the mold compounds is on the order of 10-12/10-13 S/cm, while activation energy values are in a range of 1.3 eV - 2.7 eV. For a better understanding of the potassium diffusion process into the mold compounds, the diffusion of potassium through MCP3 sample is investigated via a combination of CAIT method and an ex-situ ToF-SIMS analysis. The ToF-SIMS analysis reveals a depth diffusion profile of the potassium into the material. A mathematical theory is established in order to evaluate the diffusion coefficients for the transport of potassium. According to the numerical procedure, a good fit between experimental and theoretical data is achieved assuming the presence of two different transport pathways operative inside the material: diffusion along the boundaries of grains, i.e. zones of accumulation of the inorganic component of the mold compound and diffusion through the bulk. Diffusion coefficients of DB = 1.8 x 10-21 cm2s-1 and DBG = 5.4 x 10-20 cm2s-1 are found for bulk and grain boundary diffusion, respectively. The PEM films studied in this work are prepared from the layer-by-layer assembly of ionic p-sulfonato-calix[8]arene (calix8) and cationic poly(allylamine hydrochloride) (PAH) onto functionalized gold substrates. Samples with n = 1, 3, 6, 9, 12, 15, 20, 30 bilayers are analyzed by means of the CAIT technique. The data lend support to the conclusion that conductivity, as well as activation energy measurements for (PAH/calix8)n, cannot be acquired under the conditions of the CAIT method, due to the low resistivity shown from the specific PEMs analyzed. Studies on the transport of Li+, K+ and Rb+ through (PAH/calix8)30 are performed by means of CAIT and ToF-SIMS. For each ion beam (Li+, K+, Rb+) two kind of experiments are performed: (PAH/calix8)30 samples are bombarded with the three different alkali ions varying the time for the bombardment, i.e. 5 seconds in one case and 100 seconds in the other. The evaluation of the concentration profiles gives qualitative information regarding the transport properties, whereas numerical analysis of the lithium and rubidium concentration profiles for 5 seconds long bombardment provides quantitative information on the diffusion process. The numerical calculation reveals that the lithium and rubidium transport across the membrane results in a combination of two diffusion pathways accounting for diffusion of slow ions and fast ions. For the lithium case, a good fit is achieved using diffusion coefficients of Dslow,Li+ = 0.4 x 10-16 cm2/s and Dfast,Li+ = 1.2 x 10-15 cm2/s and assuming that 40% of the incoming ions enter the slow pathway, whereas the rest of the ions is transported via a fast pathway. For the rubidium case, the numerical calculation reveals that the fast diffusion pathway is predominant: only the 0.01% of the rubidium ions enter the slow pathway, whereas the rest is dominated from the faster one, with a Dfast,Rb+ = 7 x 10-15 (± 1.5 x 10-15) cm2/s. The study of ion transport of alkali ions Li+ and Rb+ across calixarenes-based PEMs leads thus to the conclusion that the presence of the calixarenes units may influence the type of transport. Lastly, studies of voltage offset measured on current-voltage curves in a typical CAIT experiment are presented. This study aims to give a better understanding of the process beyond the measured voltage offset. In order to do that, a basic CAIT experiment is performed, where a metal plate is bombarded with an ion beam from a potassium emitter of the composition KAlSi2O6 : Mo (1:9). The registered current–voltage curves show finite offsets in the order of 0.5 eV. In order to investigate the detection process of the specific KAlSi2O6 : Mo (1:9) emitter, values of ionic and electronic work function are evaluated. By means of a theoretical model, the recombination of K+ ions from Leucite KAlSi2O6 : Mo (1:9) onto the metal detector is traced to a combination of the ionic work function of the emitter material, the electronic work function of the emitter material and the recombination energy of the elemental potassium I.E.K

Helical magnetic structure and the anomalous and topological Hall effects in epitaxial B20 Fe1−y_{1-y}Coy_yGe films

Epitaxial films of the B20-structure alloy Fe$_{1-y}$Co$_y$Ge were grown by molecular beam epitaxy on Si (111) substrates. The magnetization varied smoothly from the bulk-like values of one Bohr magneton per Fe atom for FeGe to zero for non-magnetic CoGe. The chiral lattice structure leads to a Dzyaloshinskii-Moriya interaction (DMI), and the films' helical magnetic ground state was confirmed using polarized neutron reflectometry measurements. The pitch of the spin helix, measured by this method, varies with Co content $y$ and diverges at $y \sim 0.45$. This indicates a zero-crossing of the DMI, which we reproduced in calculations using first principle methods. We also measured the longitudinal and Hall resistivity of our films as a function of magnetic field, temperature, and Co content $y$. The Hall resistivity is expected to contain contributions from the ordinary, anomalous, and topological Hall effects. Both the anomalous and topological Hall resistivities show peaks around $y \sim 0.5$. Our first principles calculations show a peak in the topological Hall constant at this value of $y$, related to the strong spin-polarisation predicted for intermediate values of $y$. Half-metallicity is predicted for $y = 0.6$, consistent with the experimentally observed linear magnetoresistance at this composition. Whilst it is possible to reconcile theory with experiment for the various Hall effects for FeGe, the large topological Hall resistivities for $y \sim 0.5$ are much larger then expected when the very small emergent fields associated with the divergence in the DMI are taken into account

Processing of yttrium-doped barium zirconate for high proton conductivity

The factors governing the transport properties of yttrium-doped barium zirconate (BYZ) have been explored, with the aim of attaining reproducible proton conductivity in well-densified samples. It was found that a small initial particle size (50–100 nm) and high-temperature sintering (1600 °C) in the presence of excess barium were essential. By this procedure, BaZr0.8Y0.2O3-d with 93% to 99% theoretical density and total (bulk plus grain boundary) conductivity of 7.9 × 10^-3 S/cm at 600 °C [as measured by alternating current (ac) impedance spectroscopy under humidified nitrogen] could be reliably prepared. Samples sintered in the absence of excess barium displayed yttria-like precipitates and a bulk conductivity that was reduced by more than 2 orders of magnitude