Recent years have seen great progress in our understanding of the electronic properties of nanomaterials in which at least one dimension measures less than 100 nm. However, contacting true nanometer scale materials such as individual molecules or nanoparticles remains a challenge as even state-of-the-art nanofabrication techniques such as electron-beam lithography have a resolution of a few nm at best. Here we present a fabrication and measurement technique that allows high sensitivity and high bandwidth readout of discrete quantum states of metallic nanoparticles which does not require nm resolution or precision. This is achieved by coupling the nanoparticles to resonant electrical circuits and measurement of the phase of a reflected radio-frequency signal. This requires only a single tunnel contact to the nanoparticles thus simplifying device fabrication and improving yield and reliability. The technique is demonstrated by measurements on 2.7 nm thiol coated gold nanoparticles which are shown to be in excellent quantitative agreement with theory.
With a focus on platinum nanoparticles of different sizes (diameter of 1-9 nm) and shapes, we sequence their geometrical genome by recording the relative occurrence of all the non equivalent active site, classified according to the number of neighbours in their first and second coordination shell. The occurrence of sites is morphology and size dependent, with significant changes in the relative occurrence up to 9 nm. Our geometrical genome sequencing approach is immediately transferable to address the effects of the morphological polydispersivity in size-selected samples and the influence of temperature, including ionic vibrations and thermal activated processes. The proposed geometrical genome forecasts an enhancement of the catalytic reduction of molecular oxygen on stellated and anisotropic platinum twinned nanoparticles, with their shortest axes of ~2 nm, and an irreversible disruption of the Pt nanocatalysts structure above 1000 K.
We demonstrate experimentally that graphene quantum capacitance $C_{mathrm{q}}$ can have a strong impact on transport spectroscopy through the interplay with nearby charge reservoirs. The effect is elucidated in a field-effect-gated epitaxial graphene device, in which interface states serve as charge reservoirs. The Fermi-level dependence of $C_{mathrm{q}}$ is manifested as an unusual parabolic gate voltage ($V_{mathrm{g}}$) dependence of the carrier density, centered on the Dirac point. Consequently, in high magnetic fields $B$, the spectroscopy of longitudinal resistance ($R_{xx}$) vs. $V_{mathrm{g}}$ represents the structure of the unequally spaced relativistic graphene Landau levels (LLs). $R_{xx}$ mapping vs. $V_{mathrm{g}}$ and $B$ thus reveals the vital role of the zero-energy LL on the development of the anomalously wide $ u=2$ quantum Hall state.
Motivated by the recent development of quantitative structure-activity relationship (QSAR) methods in the area of nanotoxicology, we proposed an approach to develop additional descriptors based on results of first principles calculations. For evaluation of the biochemical activity of metallic nanoparticles, we consider two processes: ion extraction from the surface of a specimen to aqueous media and water dissociation on the surface. We performed calculations for a set of metals (Al, Fe, Cu, Ag, Au, Pt). Taking into account the diversity of atomic structures of real metallic nanoparticles, we performed calculations for different models such as (001) and (111) surfaces, nanorods, and two different cubic nanoparticles of 0.6 and 0.3 nm size. Significant energy dependence of the processes from the selected model of nanoparticle suggests that for the correct description we should combine the calculations for the several representative models. In addition to the descriptors of chemical activity of the metallic nanoparticles for the two studied processes, we propose descriptors for taking into account the dependence of chemical activity from the size and shape of nanoparticles. Routes to minimization of computational costs for these calculations are also discussed.
We characterize the terahertz detection mechanism in antenna-coupled metallic single-walled carbon nanotubes. At low temperature, 4.2 K, a peak in the low-frequency differential resistance is observed at zero bias current due to non-Ohmic contacts. This electrical contact nonlinearity gives rise to the measured terahertz response. By modeling each nanotube contact as a nonlinear resistor in parallel with a capacitor, we determine an upper bound for the value of the contact capacitance that is smaller than previous experimental estimates. The small magnitude of this contact capacitance has favorable implications for the use of carbon nanotubes in high-frequency device applications.
We present a theory of the low-energy excitations of a ferromagnetic metal nanoparticle. In addition to the particle-hole excitations, which occur in a paramagnetic metal nanoparticle, we predict a branch of excitations involving the magnetization-orientation collective coordinate. Tunneling matrix elements are in general sizable for several different collective states associated with the same band configuration. We point out that the average change in ground state spin per added electron differs from non-interacting quasiparticle expectations, and that the change in the spin-polarization, due to Zeeman coupling, is strongly influenced by Coulomb blockade physics.