No Arabic abstract
An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid state nanopores.
Two-dimensional crystals with angstrom-scale pores are widely considered as candidates for a next generation of molecular separation technologies aiming to provide extreme selectivity combined with high flow rates. Here we study gas transport through individual graphene pores with an effective diameter of about 2 angstroms, or about one missing carbon ring, which are created reproducibly by a short-time exposure to a low-kV electron beam. Helium and hydrogen permeate easily through these pores whereas larger molecules such as xenon and methane are blocked. Permeating gases experience activation barriers that increase quadratically with the kinetic diameter, and the transport process crucially involves surface adsorption. Our results reveal underlying mechanisms for the long sought-after exponential selectivity and suggest the bounds on possible performance of porous two-dimensional membranes.
We present a study of the effects of inelastic scattering on the transport properties of various nanoscale devices, namely H$_2$ molecules sandwiched between Pt contacts, and a spin-valve made by an organic molecule attached to model half-metal ferromagnetic current/voltage probes. In both cases we use a tight-binding Su-Schrieffer-Heeger Hamiltonian and the inelastic effects are treated with a multi-channel method, including Pauli exclusion principle. In the case of the H$_2$ molecule, we find that inelastic backscattering is responsible for the drop of the differential conductance at biases larger than the excitation energy of the lower of the molecular phonon modes. In the case of the spin-valve, we investigate the different spin-currents and the magnetoresistance as a function of the position of the Fermi level with respect to the spin-polarized band edges. In general inelastic scattering reduces the spin-polarization of the current and consequently the magnetoresistance.
The role of the growth conditions in the spin transport properties of silver (Ag) have been studied by using lateral spin valve structures. By changing the deposition conditions of Ag from polycrystalline to epitaxial growth, we have observed a considerable enhancement of the spin diffusion length, from $lambda_{Ag}$ = 449 $pm$ 30 to 823 $pm$ 59 nm. This study shows that diminishing the grain boundary contribution to the spin relaxation mechanism is an effective way to improve the spin diffusion length in metallic nanostructures.
We study the electronic contribution to the main thermoelectric properties of a molecular junction consisting of a single quantum dot coupled to graphene external leads. The system electrical conductivity (G), Seebeck coefficient ($S$), and the thermal conductivity ($kappa$), are numerically calculated based on a Greens function formalism that includes contributions up to the Hartree-Fock level. We consider the system leads to be made either of pure or gapped-graphene. To describe the free electrons in the gapped-graphene electrodes we used two possible scenarios, the massive gap scenario, and the massless gap scenario, respectively. In all cases, the Fano effect is responsible for a strong violation of the Wiedemann-Franz law and we found a substantial increase of the system figure of merit $ZT$ due to a drastic reduction of the system thermal coefficient. In the case of gapped-graphene electrodes, the system figure of merit presents a maximum at an optimal value of the energy gap of the order of $Delta/Dsim$ 0.002 (massive gap scenario) and $Delta/Dsim$ 0.0026 (massless gap scenario). Additionally, for all cases, the system figure of merit is temperature dependent.
It has been an ultimate but seemingly distant goal of nanofluidics to controllably fabricate capillaries with dimensions approaching the size of small ions and water molecules. We report ion transport through ultimately narrow slits that are fabricated by effectively removing a single atomic plane from a bulk crystal. The atomically flat angstrom-scale slits exhibit little surface charge, allowing elucidation of the role of steric effects. We find that ions with hydrated diameters larger than the slit size can still permeate through, albeit with reduced mobility. The confinement also leads to a notable asymmetry between anions and cations of the same diameter. Our results provide a platform for studying effects of angstrom-scale confinement, which is important for development of nanofluidics, molecular separation and other nanoscale technologies.