All solution-processed organic photocathodes with increased efficiency and stability via the tuning of the hole-extracting layer †

International audiencePhotoelectrodes based on solution-processed organic semiconductors are emerging as low-cost alternatives to crystalline semiconductors and platinum. In this work, the performance and stability of P3HT:PCBM\MoS 3-based photocathodes are considerably improved by changing the hole-extracting layer (HEL). Oxides such as reduced graphene oxide, nickel oxide or molybdenum oxide are deposited via solution processes. With MoO x , a photocurrent density of 2 mA cm À2 during 1 h is obtained with the processing temperature lower than 150 C – thus compatible with flexible substrates. Furthermore, we show that the performances are directly correlated with the work function of the HEL material, and the comparison with solid-state solar cells shows that efficient HELs are not the same for the two types of devices

Equidistribution of Heegner Points and Ternary Quadratic Forms

We prove new equidistribution results for Galois orbits of Heegner points with respect to reduction maps at inert primes. The arguments are based on two different techniques: primitive representations of integers by quadratic forms and distribution relations for Heegner points. Our results generalize one of the equidistribution theorems established by Cornut and Vatsal in the sense that we allow both the fundamental discriminant and the conductor to grow. Moreover, for fixed fundamental discriminant and variable conductor, we deduce an effective surjectivity theorem for the reduction map from Heegner points to supersingular points at a fixed inert prime. Our results are applicable to the setting considered by Kolyvagin in the construction of the Heegner points Euler system

Magnetocrystalline Anisotropy in a Single Crystal of CeNiGe2

We report measurements on single crystals of orthorhombic CeNiGe2, which is found to exhibit highly anisotropic magnetic and transport properties. The magnetization ratio M(H//b)/M(H^b) at 2 K is observed to be about 18 at 4 T and the electrical resistivity ratio r//b/r^b is about 70 at room temperature. It is confirmed that CeNiGe2 undergoes two-step antiferromagnetic transition at 4 and 3 K, as reported for polycrystalline samples. The application of magnetic field along the b axis (the easy magnetization axis) stabilizes a ferromagnetic correlation between the Ce ions and enhances the hopping of carriers. This results in large negative magnetoresistance along the b axis.Comment: 24 pages, including 9 figure

Thermodynamic and Transport Properties of CeMg2Cu9 under Pressure

We report the transport and thermodynamic properties under hydrostatic pressure in the antiferromagnetic Kondo compound CeMg2Cu9 with a two-dimensional arrangement of Ce atoms. Magnetic specific heat Cmag(T) shows a Schottky-type anomaly around 30 K originating from the crystal electric field (CEF) splitting of the 4f state with the first excited level at \Delta_{1}/kB = 58 K and the second excited level at \Delta_{2}/kB = 136 K from the ground state. Electric resistivity shows a two-peaks structure due to the Kondo effect on each CEF level around T_{1}^{max} = 3 K and T_{2}^{max} = 40 K. These peaks merge around 1.9 GPa with compression. With increasing pressure, Neel temperature TN initially increases and then change to decrease. TN finally disappears at the quantum critical point Pc = 2.4 GPa.Comment: 10 pages, 6 figure

Signatures of valence fluctuations in CeCu2Si2 under high pressure

Simultaneous resistivity and a.c.-specific heat measurements have been performed under pressure on single crystalline CeCu2Si2 to over 6 GPa in a hydrostatic helium pressure medium. A series of anomalies were observed around the pressure coinciding with a maximum in the superconducting critical temperature, $T_c^{max}$. These anomalies can be linked with an abrupt change of the Ce valence, and suggest a second quantum critical point at a pressure $P_v \simeq 4.5$ GPa, where critical valence fluctuations provide the superconducting pairing mechanism, as opposed to spin fluctuations at ambient pressure. Such a valence instability, and associated superconductivity, is predicted by an extended Anderson lattice model with Coulomb repulsion between the conduction and f-electrons. We explain the T-linear resistivity found at $P_v$ in this picture, while other anomalies found around $P_v$ can be qualitatively understood using the same model.Comment: Submitted to Phys. Rev.

Kondo engineering : from single Kondo impurity to the Kondo lattice

In the first step, experiments on a single cerium or ytterbium Kondo impurity reveal the importance of the Kondo temperature by comparison to other type of couplings like the hyperfine interaction, the crystal field and the intersite coupling. The extension to a lattice is discussed. Emphasis is given on the fact that the occupation number $n_f$ of the trivalent configuration may be the implicit key variable even for the Kondo lattice. Three $(P, H, T)$ phase diagrams are discussed: CeRu$_2$Si$_2$, CeRhIn$_5$ and SmS

Specific heat of Ce_{0.8}La_{0.2}Al_{3} in magnetic fields: a test of the anisotropic Kondo picture

The specific heat C of Ce_{0.8}La_{0.2}Al_{3} has been measured as a function of temperature T in magnetic fields up to 14 T. A large peak in C at 2.3 K has recently been ascribed to an anisotropic Kondo effect in this compound. A 14-T field depresses the temperature of the peak by only 0.2 K, but strongly reduces its height. The corresponding peak in C/T shifts from 2.1 K at zero field to 1.7 K at 14 T. The extrapolated specific heat coefficient C/T(T->0) increases with field over the range studied. We show that these trends are inconsistent with the anisotropic Kondo model.Comment: 4 pages, 5 figures, ReVTeX + eps

Quantitative localized proton-promoted dissolution kinetics of calcite using scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) has been used to determine quantitatively the kinetics of proton-promoted dissolution of the calcite (101̅4) cleavage surface (from natural “Iceland Spar”) at the microscopic scale. By working under conditions where the probe size is much less than the characteristic dislocation spacing (as revealed from etching), it has been possible to measure kinetics mainly in regions of the surface which are free from dislocations, for the first time. To clearly reveal the locations of measurements, studies focused on cleaved “mirror” surfaces, where one of the two faces produced by cleavage was etched freely to reveal defects intersecting the surface, while the other (mirror) face was etched locally (and quantitatively) using SECM to generate high proton fluxes with a 25 μm diameter Pt disk ultramicroelectrode (UME) positioned at a defined (known) distance from a crystal surface. The etch pits formed at various etch times were measured using white light interferometry to ascertain pit dimensions. To determine quantitative dissolution kinetics, a moving boundary finite element model was formulated in which experimental time-dependent pit expansion data formed the input for simulations, from which solution and interfacial concentrations of key chemical species, and interfacial fluxes, could then be determined and visualized. This novel analysis allowed the rate constant for proton attack on calcite, and the order of the reaction with respect to the interfacial proton concentration, to be determined unambiguously. The process was found to be first order in terms of interfacial proton concentration with a rate constant k = 6.3 (± 1.3) × 10–4 m s–1. Significantly, this value is similar to previous macroscopic rate measurements of calcite dissolution which averaged over large areas and many dislocation sites, and where such sites provided a continuous source of steps for dissolution. Since the local measurements reported herein are mainly made in regions without dislocations, this study demonstrates that dislocations and steps that arise from such sites are not needed for fast proton-promoted calcite dissolution. Other sites, such as point defects, which are naturally abundant in calcite, are likely to be key reaction sites

Electrochemical Nanoprobes for Single-Cell Analysis

The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5–200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microscopy probes, which should allow high resolution electrochemical mapping of species on or in living cells

Unusual kondo behavior in the indium-rich heavy fermion antiferromagnet Ce3Pt4In13

We report the thermodynamic, magnetic, and electronic transport properties of the new ternary intermetallic system (Ce,La)3Pt4In13. Ce3Pt4In13 orders antiferromagnetically at 0.95 K while the non-magnetic compound La3Pt4In13 is a conventional 3.3 K superconductor. Kondo lattice effects appear to limit the entropy associated with the Neel transition to (1/4)Rln2 as an electronic contribution to the specific heat of gamma = 1 J/mole-Ce K2 is observed at TN; roughly 35% of this gamma survives the ordering transition. Hall effect, thermoelectric power, and ambient-pressure resistivity measurements confirm this interpretation. These results suggest that RKKY and Kondo interactions are closely balanced in this compound (TN = TK). Contrary to expectations based on the Doniach Kondo necklace model, applied hydrostatic pressure modestly enhances the magnetic ordering temperature with dTN/dP = +23 mK/kbar. As such Ce3Pt4In13 provides a counterexample to Kondo systems with similar Kondo and RKKY energy scales wherein applied pressure enhances TK at the expense of the ordered magnetic state.Comment: submitted to Physical Review