No Arabic abstract
The vibrations of gold nanowires and nanorods are investigated numerically in the framework of continuum elasticity using the Rayleigh-Ritz variational method. Special attention is paid to identify the vibrations relevant in Raman scattering experiments. A comprehensive description of the vibrations of nanorods is proposed by determining their symmetry, comparing with standing waves in the corresponding nanowires and estimating their Raman intensity. The role of experimentally relevant parameters such as the anisotropic cubic lattice structure, the presence of faceted lateral surfaces and the shape of the ends of the nanorods is evaluated. Elastic anisotropy is shown to play a significant role contrarily to the presence of facets. Localized vibrations are found for nanorods with flat ends. Their evolution as the shape of the ends is changed to half-spheres is discussed.
A theory of the electronic structure and excitonic absorption spectra of PbS and PbSe nanowires and nanorods in the framework of a four-band effective mass model is presented. Calculations conducted for PbSe show that dielectric contrast dramatically strengthens the exciton binding in narrow nanowires and nanorods. However, the self-interaction energies of the electron and hole nearly cancel the Coulomb binding, and as a result the optical absorption spectra are practically unaffected by the strong dielectric contrast between PbSe and the surrounding medium. Measurements of the size-dependent absorption spectra of colloidal PbSe nanorods are also presented. Using room-temperature energy-band parameters extracted from the optical spectra of spherical PbSe nanocrystals, the theory provides good quantitative agreement with the measured spectra.
The two-photon luminescence (TPL) of small 10 nm x 40 nm colloidal gold nanorods (GNR) is investigated at the single object level, combining polarization resolved TPL and simultaneously acquired topography. A very high dependence of the TPL signal with both the nanorods longitudinal axis and the incident wavelength is observed confirming the plasmonic origin of the signal and pointing the limit of the analogy between GNRs and molecules. The spectral analysis of the TPL evidences two emission bands peaks: in the visible (in direct connection with the gold band structure), and in the infrared. Both bands are observed to vary quadradically with the incident excitation beam but exhibit different polarization properties. The maximum two-photon brightness of a single GNR is measured to be a few millions higher than the two-photon brightness of fluorescein molecules. We show that the important TPL observed in these small gold nanorods results from resonance effects both at the excitation and emission level : local field enhancement at the longitudinal surface plasmon resonances (LSPR) first results in an increase of the electron-hole generation. Further relaxation of electron-hole pairs then mostly leads to the excitation of the GNR transverse plasmon mode and its subsequent radiative relaxation.
Coherent acoustic radial oscillations of thin spherical gold shells of submicron diameter excited by an ultrashort optical pulse are observed in the form of pronounced modulations of the transient reflectivity on a subnanosecond time scale. Strong acousto-optical coupling in a photonic crystal enhances the modulation of the transient reflectivity up to 4%. The frequency of these oscillations is demonstrated to be in good agreement with Lamb theory of free gold shells.
We report the effects of variation in length on the electronic structure of CdSe nanorods derived from atomic clusters and passivated by fictitious hydrogen atoms. These nanorods are augmented by attaching gold clusters at both the ends to form a nanodumbbell. The goal is to assess the changes at nanolevel after formation of contacts with gold clusters serving as electrodes and compare the results with experimental observations [PRL, 95, 056805 (2005)]. Calculations involving nanorods of length 4.6 Angstrom to 116.6 Angstrom are performed using density functional theory implemented within plane-wave basis set. The binding energy per atom saturates for nanorod of length 116.6 Angstrom. It is interesting to note that upon attaching gold clusters, the nanorods shorter than 27 Angstrom develop metallicity by means of metal induced gap states (MIGS). Longer nanorods exhibit a nanoscale Schottky barrier emerging at the center. For these nanorods, interfacial region closest to the gold electrodes shows a finite density of states in the gap due to MIGS, which gradually decreases towards the center of the nanorod opening up a finite gap. Bader charge analysis indicates localized charge transfer from metal to semiconductor.
In this paper an experimental study of the interaction of hydrogen molecules with gold nanowires is presented. Our results show, that chains of Au atoms can also be pulled in hydrogen environment, however in this case the conductance of the chain is strongly reduced compared to the perfect transmission of pure Au chains. The comparison of our experiments with recent theoretical prediction for the hydrogen welding of Au nanowires implies that a hydrogen molecule can even be incorporated in the gold nanocontact, and this hydrogen clamp is strong enough to pull a chain of gold atoms.