Transport in single-molecule transistors: Kondo physics and negative differential resistance

We report two examples of transport phenomena based on sharp features in the effective density of states of molecular-scale transistors: Kondo physics in C$_{60}$-based devices, and gate-modulated negative differential resistance (NDR) in ``control'' devices that we ascribe to adsorbed contamination. We discuss the need for a statistical approach to device characterization, and the criteria that must be satisfied to infer that transport is based on single molecules. We describe apparent Kondo physics in C$_{60}$-based single-molecule transistors (SMTs), including signatures of molecular vibrations in the Kondo regime. Finally, we report gate-modulated NDR in devices made without intentional molecular components, and discuss possible origins of this property.Comment: 15 pages, 8 figures. To appear in Oct. 2004 issue of Nanotechnology, proceedings of International Conference on Nanoscale Devices and Systems Integratio

Slow fluctuations in enhanced Raman scattering and surface roughness relaxation

We propose an explanation for the recently measured slow fluctuations and ``blinking'' in the surface enhanced Raman scattering (SERS) spectrum of single molecules adsorbed on a silver colloidal particle. We suggest that these fluctuations may be related to the dynamic relaxation of the surface roughness on the nanometer scale and show that there are two classes of roughness with qualitatively different dynamics. The predictions agree with measurements of surface roughness relaxation. Using a theoretical model for the kinetics of surface roughness relaxation in the presence of charges and optical electrical fields, we predict that the high-frequency electromagnetic field increases both the effective surface tension and the surface diffusion constant and thus accelerates the surface smoothing kinetics and time scale of the Raman fluctuations in manner that is linear with the laser power intensity, while the addition of salt retards the surface relaxation kinetics and increases the time scale of the fluctuations. These predictions are in qualitative agreement with the Raman experiments

Photoelectric Emission from Interstellar Dust: Grain Charging and Gas Heating

We model the photoelectric emission from and charging of interstellar dust and obtain photoelectric gas heating efficiencies as a function of grain size and the relevant ambient conditions. Using realistic grain size distributions, we evaluate the net gas heating rate for various interstellar environments, and find less heating for dense regions characterized by R_V=5.5 than for diffuse regions with R_V=3.1. We provide fitting functions which reproduce our numerical results for photoelectric heating and recombination cooling for a wide range of interstellar conditions. In a separate paper we will examine the implications of these results for the thermal structure of the interstellar medium. Finally, we investigate the potential importance of photoelectric heating in H II regions, including the warm ionized medium. We find that photoelectric heating could be comparable to or exceed heating due to photoionization of H for high ratios of the radiation intensity to the gas density. We also find that photoelectric heating by dust can account for the observed variation of temperature with distance from the galactic midplane in the warm ionized medium.Comment: 50 pages, including 18 figures; corrected title and abstract field

Light emission from a scanning tunneling microscope: Fully retarded calculation

The light emission rate from a scanning tunneling microscope (STM) scanning a noble metal surface is calculated taking retardation effects into account. As in our previous, non-retarded theory [Johansson, Monreal, and Apell, Phys. Rev. B 42, 9210 (1990)], the STM tip is modeled by a sphere, and the dielectric properties of tip and sample are described by experimentally measured dielectric functions. The calculations are based on exact diffraction theory through the vector equivalent of the Kirchoff integral. The present results are qualitatively similar to those of the non-retarded calculations. The light emission spectra have pronounced resonance peaks due to the formation of a tip-induced plasmon mode localized to the cavity between the tip and the sample. At a quantitative level, the effects of retardation are rather small as long as the sample material is Au or Cu, and the tip consists of W or Ir. However, for Ag samples, in which the resistive losses are smaller, the inclusion of retardation effects in the calculation leads to larger changes: the resonance energy decreases by 0.2-0.3 eV, and the resonance broadens. These changes improve the agreement with experiment. For a Ag sample and an Ir tip, the quantum efficiency is $\approx$ 10$^{-4}$ emitted photons in the visible frequency range per tunneling electron. A study of the energy dissipation into the tip and sample shows that in total about 1 % of the electrons undergo inelastic processes while tunneling.Comment: 16 pages, 10 figures (1 ps, 9 tex, automatically included); To appear in Phys. Rev. B (15 October 1998

Resolving the electromagnetic mechanism of surface-enhanced light scattering at single hot spots

Light scattering at nanoparticles and molecules can be dramatically enhanced in the 'hot spots' of optical antennas, where the incident light is highly concentrated. Although this effect is widely applied in surface-enhanced optical sensing, spectroscopy and microscopy, the underlying electromagnetic mechanism of the signal enhancement is challenging to trace experimentally. Here we study elastically scattered light from an individual object located in the well-defined hot spot of single antennas, as a new approach to resolve the role of the antenna in the scattering process. We provide experimental evidence that the intensity elastically scattered off the object scales with the fourth power of the local field enhancement provided by the antenna, and that the underlying electromagnetic mechanism is identical to the one commonly accepted in surface-enhanced Raman scattering. We also measure the phase shift of the scattered light, which provides a novel and unambiguous fingerprint of surface-enhanced light scattering

Surface Plasmon Resonance from Bimetallic Interface in Au–Ag Core–Shell Structure Nanowires

Transverse surface plasmon resonances (SPR) in Au–Ag and Ag–Au core–shell structure nanowires have been investigated by means of quasi-static theory. There are two kinds of SPR bands resulting from the outer surface of wall metal and the interface between core and wall metals, respectively. The SPR corresponding to the interface, which is similar to that of alloy particle, decreases and shifts obviously with increasing the wall thickness. However, the SPR corresponding to the outer surface, which is similar to that of pure metal particle, increases and shifts slightly with increasing the wall thickness. A mechanism based on oscillatory surface electrons under coulombic attraction is developed to illuminate the shift fashion of SPR from bimetallic core–shell interface. The net charges and extra coulombic force in metallic wall affect the SPR energy and the shift fashion

Rhodium nanoparticles for ultraviolet plasmonics

The nonoxidizing catalytic noble metal rhodium is introduced for ultraviolet plasmonics. Planar tripods of 8 nm Rh nanoparticles, synthesized by a modified polyol reduction method, have a calculated local surface plasmon resonance near 330 nm. By attaching p-aminothiophenol, local field-enhanced Raman spectra and accelerated photodamage were observed under near-resonant ultraviolet illumination, while charge transfer simultaneously increased fluorescence for up to 13 min. The combined local field enhancement and charge transfer demonstrate essential steps toward plasmonically enhanced ultraviolet photocatalysis.This work has been supported by NSF-ECCS-12-32239. This work was partially supported by the Army’s In-house Laboratory Innovative Research program. Financial support from USAITCA (project no. W911NF-13-1-0245) and MICINN (Spanish Ministry of Science and Innovation, project no. FIS2013- 45854-P) is also acknowledged

Determining molecular orientation via single molecule SERS in a plasmonic nano-gap

In this work, plasmonic nano-gaps consisting of a silver nanoparticle coupled to an extended silver film have been fully optimized for single molecule Surface-Enhanced Raman Scattering (SERS) spectroscopy. The SERS signal was found to be strongly dependent on the particle size and the molecule orientation with respect to the field inside the nano-gap. Using Finite Difference Time Domain (FDTD) simulations to complement the experimental measurements, the complex interplay between the excitation enhancement and the emission enhancement of the system as a function of particle size were highlighted. Additionally, in conjunction with Density Functional Theory (DFT), the well-defined field direction in the nano-gap enables to recover the orientation of individual molecules

Water-Driven Assembly of Laser Ablation-Induced Au Condensates as Mesomorphic Nano- and Micro-Tubes

Reddish Au condensates, predominant atom clusters and minor amount of multiply twinned particles and fcc nanoparticles with internal compressive stress, were produced by pulsed laser ablation on gold target in de-ionized water under a very high power density. Such condensates were self-assembled as lamellae and then nano- to micro-diameter tubes with multiple walls when aged at room temperature in water for up to 40 days. The nano- and micro-tubes have a lamellar- and relaxed fcc-type wall, respectively, both following partial epitaxial relationship with the co-existing multiply twinned nanoparticles. The entangled tubes, being mesomorphic with a large extent of bifurcation, flexibility, opaqueness, and surface-enhanced Raman scattering, may have potential encapsulated and catalytic/label applications in biomedical systems