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222 result(s) for "Electronic structure of nanoscale materials : clusters, nanoparticles, nanotubes, and nanocrystals"
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Bright Infrared Emission from Electrically Induced Excitons in Carbon Nanotubes
We used the high local electric fields at the junction between the suspended and supported parts of a single carbon nanotube molecule to produce unusually bright infrared emission under unipolar operation. Carriers were accelerated by band-bending at the suspension interface, and they created excitons that radiatively recombined. This excitation mechanism is [approximately]1000 times more efficient than recombination of independently injected electrons and holes, and it results from weak electron-phonon scattering and strong electron-hole binding caused by one-dimensional confinement. The ensuing high excitation density allows us to observe emission from higher excited states not seen by photoexcitation. The excitation mechanism of these states was analyzed.
Direct observation of Tomonaga–Luttinger-liquid state in carbon nanotubes at low temperatures
The electronic transport properties of conventional three-dimensional metals are successfully described by Fermi-liquid theory. But when the dimensionality of such a system is reduced to one, the Fermi-liquid state becomes unstable to Coulomb interactions, and the conduction electrons should instead behave according to Tomonaga–Luttinger-liquid (TLL) theory. Such a state reveals itself through interaction-dependent anomalous exponents in the correlation functions, density of states and momentum distribution of the electrons 1 , 2 , 3 . Metallic single-walled carbon nanotubes (SWNTs) are considered to be ideal one-dimensional systems for realizing TLL states 4 , 5 , 6 . Indeed, the results of transport measurements on metal–SWNT and SWNT–SWNT junctions have been attributed 7 , 8 , 9 to the effects of tunnelling into or between TLLs, although there remains some ambiguity in these interpretations 10 . Direct observations of the electronic states in SWNTs are therefore needed to resolve these uncertainties. Here we report angle-integrated photoemission measurements of SWNTs. Our results reveal an oscillation in the π-electron density of states owing to one-dimensional van Hove singularities, confirming the one-dimensional nature of the valence band. The spectral function and intensities at the Fermi level both exhibit power-law behaviour (with almost identical exponents) in good agreement with theoretical predictions for the TLL state in SWNTs.
Ultrastable silver nanoparticles
Silver nanoparticles are susceptible to oxidation and have accordingly received less attention than gold nanoparticles; ultrastable silver nanoparticles are now reported, which can be produced in very large quantities as a single-sized molecular product, and the origins of their enhanced stability are elucidated using a single-crystal X-ray structure and first-principles calculations. Silver nanoparticles as good as gold Noble metals in nanoparticulate form find practical application as catalysts and in optoelectronics, energy conservation and many other fields. Gold nanoparticles, stable and easy to use, have proved much more useful and so have been studied more extensively than silver nanoparticles, which tend to be susceptible to oxidation. Anil Desireddy et al . describe a simple recipe for the large-scale production of single-sized silver nanoclusters, whose electronic structure gives them exceptional chemical stability. With the availability of stable silver nanoparticles, the metal's desirable electrical and physical properties, abundance and comparatively low cost could be harnessed in a wealth of new applications. Noble-metal nanoparticles have had a substantial impact across a diverse range of fields, including catalysis 1 , sensing 2 , photochemistry 3 , optoelectronics 4 , 5 , energy conversion 6 and medicine 7 . Although silver has very desirable physical properties, good relative abundance and low cost, gold nanoparticles have been widely favoured owing to their proved stability and ease of use. Unlike gold, silver is notorious for its susceptibility to oxidation (tarnishing), which has limited the development of important silver-based nanomaterials. Despite two decades of synthetic efforts, silver nanoparticles that are inert or have long-term stability remain unrealized. Here we report a simple synthetic protocol for producing ultrastable silver nanoparticles, yielding a single-sized molecular product in very large quantities with quantitative yield and without the need for size sorting. The stability, purity and yield are substantially better than those for other metal nanoparticles, including gold, owing to an effective stabilization mechanism. The particular size and stoichiometry of the product were found to be insensitive to variations in synthesis parameters. The chemical stability and structural, electronic and optical properties can be understood using first-principles electronic structure theory based on an experimental single-crystal X-ray structure. Although several structures have been determined for protected gold nanoclusters 8 , 9 , 10 , 11 , 12 , none has been reported so far for silver nanoparticles. The total structure of a thiolate-protected silver nanocluster reported here uncovers the unique structure of the silver thiolate protecting layer, consisting of Ag 2 S 5 capping structures. The outstanding stability of the nanoparticle is attributed to a closed-shell 18-electron configuration with a large energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, an ultrastable 32-silver-atom excavated-dodecahedral 13 core consisting of a hollow 12-silver-atom icosahedron encapsulated by a 20-silver-atom dodecahedron, and the choice of protective coordinating ligands. The straightforward synthesis of large quantities of pure molecular product promises to make this class of materials widely available for further research and technology development 14 , 15 , 16 , 17 , 18 .
Visualization and Spectroscopy of a Metal-Molecule-Metal Bridge
Artificial nanostructures, each composed of a copper(II) phthalocyanine (CuPc) molecule bonded to two gold atomic chains with a controlled gap, were assembled on a NiAl(110) surface by manipulation of individual gold atoms and CuPc molecules with a scanning tunneling microscope. The electronic densities of states of these hybrid structures were measured by spatially resolved electronic spectroscopy and systematically tuned by varying the number of gold atoms in the chains one by one. The present approach provides structural images and electronic characterization of the metal-molecule-metal junction, thereby elucidating the nature of the contacts between the molecule and metal in this junction.
Probing the Ultimate Limits of Plasmonic Enhancement
Metals support surface plasmons at optical wavelengths and have the ability to localize light to subwavelength regions. The field enhancements that occur in these regions set the ultimate limitations on a wide range of nonlinear and quantum optical phenomena. We found that the dominant limiting factor is not the resistive loss of the metal, but rather the intrinsic nonlocality of its dielectric response. A semiclassical model of the electronic response of a metal places strict bounds on the ultimate field enhancement. To demonstrate the accuracy of this model, we studied optical scattering from gold nanoparticles spaced a few angstroms from a gold film. The bounds derived from the models and experiments impose limitations on all nanophotonic systems.
Development of One-Dimensional Band Structure in Artificial Gold Chains
The ability of a scanning tunneling microscope to manipulate single atoms is used to build well-defined gold chains on NiAl(110). The electronic properties of the one-dimensional chains are dominated by an unoccupied electron band, gradually developing from a single atomic orbital present in a gold atom. Spatially resolved conductance measurements along a 20-atom chain provide the dispersion relation, effective mass, and density of states of the free electron-like band. These experiments demonstrate a strategy for probing the interrelation between geometric structure, elemental composition, and electronic properties in metallic nanostructures.
Determination of electron orbital magnetic moments in carbon nanotubes
The remarkable transport properties of carbon nanotubes (CNTs) are determined by their unusual electronic structure 1 . The electronic states of a carbon nanotube form one-dimensional electron and hole sub-bands, which, in general, are separated by an energy gap 2 , 3 . States near the energy gap are predicted 4 , 5 to have an orbital magnetic moment, µ orb , that is much larger than the Bohr magneton (the magnetic moment of an electron due to its spin). This large moment is due to the motion of electrons around the circumference of the nanotube, and is thought to play a role in the magnetic susceptibility of CNTs 6 , 7 , 8 , 9 and the magnetoresistance observed in large multiwalled CNTs 10 , 11 , 12 . But the coupling between magnetic field and the electronic states of individual nanotubes remains to be quantified experimentally. Here we report electrical measurements of relatively small diameter (2–5 nm) individual CNTs in the presence of an axial magnetic field. We observe field-induced energy shifts of electronic states and the associated changes in sub-band structure, which enable us to confirm quantitatively the predicted values for µ orb .
Fluorescence Enhancement at Docking Sites of DNA-Directed Self-Assembled Nanoantennas
We introduce self-assembled nanoantennas to enhance the fluorescence intensity in a plasmonic hotspot of zeptoliter volume. The nanoantennas are prepared by attaching one or two gold nanoparticles (NPs) to DNA origami structures, which also incorporated docking sites for a single fluorescent dye next to one NP or in the gap between two NPs. We measured the dependence of the fluorescence enhancement on NP size and number and compare it to numerical simulations. A maximum of 117-fold fluorescence enhancement was obtained for a dye molecule positioned in the 23-nanometer gap between 100-nanometer gold NPs. Direct visualization of the binding and unbinding of short DNA strands, as well as the conformational dynamics of a DNA Holliday junction in the hotspot of the nanoantenna, show the compatibility with single-molecule assays.
Gate-tuning of graphene plasmons revealed by infrared nano-imaging
Plasmons are directly launched in graphene, and their key parameters — propagation and attenuation — are studied with near-field infrared nano-imaging. Voltage-controlled graphene plasmonics Plasmonic devices, which exploit surface plasmons (electromagnetic waves that propagate along the surface of metals) offer the possibility of controlling and guiding light at subwavelength scales. All eyes are on graphene — atom-thick layers of carbon — as a promising platform for plasmonic applications because it can strongly interact with light and host surface plasmons in the infrared range. Two independent groups reporting in this issue of Nature show that plasmons can be directly launched in graphene, and observed with near-field optical microscopy. Moreover, the wavelengths and amplitudes of the plasmons can be tuned by a gate voltage, a promising capability for the development of on-chip graphene photonics for use in applications including telecommunications and information processing. Surface plasmons are collective oscillations of electrons in metals or semiconductors that enable confinement and control of electromagnetic energy at subwavelength scales 1 , 2 , 3 , 4 , 5 . Rapid progress in plasmonics has largely relied on advances in device nano-fabrication 5 , 6 , 7 , whereas less attention has been paid to the tunable properties of plasmonic media. One such medium—graphene—is amenable to convenient tuning of its electronic and optical properties by varying the applied voltage 8 , 9 , 10 , 11 . Here, using infrared nano-imaging, we show that common graphene/SiO 2 /Si back-gated structures support propagating surface plasmons. The wavelength of graphene plasmons is of the order of 200 nanometres at technologically relevant infrared frequencies, and they can propagate several times this distance. We have succeeded in altering both the amplitude and the wavelength of these plasmons by varying the gate voltage. Using plasmon interferometry, we investigated losses in graphene by exploring real-space profiles of plasmon standing waves formed between the tip of our nano-probe and the edges of the samples. Plasmon dissipation quantified through this analysis is linked to the exotic electrodynamics of graphene 10 . Standard plasmonic figures of merit of our tunable graphene devices surpass those of common metal-based structures.
Ultrafast Three-Dimensional Imaging of Lattice Dynamics in Individual Gold Nanocrystals
Key insights into the behavior of materials can be gained by observing their structure as they undergo lattice distortion. Laser pulses on the femtosecond time scale can be used to induce disorder in a \"pump-probe\" experiment with the ensuing transients being probed stroboscopically with femtosecond pulses of visible light, x-rays, or electrons. Here we report three-dimensional imaging of the generation and subsequent evolution of coherent acoustic phonons on the picosecond time scale within a single gold nanocrystal by means of an x-ray free-electron laser, providing insights into the physics of this phenomenon. Our results allow comparison and confirmation of predictive models based on continuum elasticity theory and molecular dynamics simulations.