11,453 research outputs found
Inorganic–organic nanocomposites of CdSe nanocrystals surface-modified with oligo- and poly(fluorene) moieties
We report a facile grafting-from strategy towards the synthesis of inorganic–organic composites of semiconductor nanocrystals and wide-bandgap polymers. Amino-functional fluorenes have been used as co-ligands for CdSe nanocrystals, thus enabling us to design their surface directly during the synthesis. Highly monodisperse, strongly emitting CdSe nanocrystals have been obtained. Subsequently, a straightforward Yamamoto C–C coupling protocol was used to carry out surface polymerisation, hence modifying CdSe nanocrystals with oligo- and poly(fluorene) moieties. Both amino-fluorene capped CdSe nanocrystals and the resulting nanocrystal–polymer composites were characterized in detail by optical and FT-IR spectroscopy, TEM, AFM, and gel permeation chromatography, showing their potential as novel functional inorganic–organic hybrid materials
Insights into the Structure of Dot@Rod and Dot@Octapod CdSe@CdS Heterostructures
CdSe@CdS dot@rods with diameter around 6 nm and length of either
20, 27, or 30 nm and dot@octapods with pod diameters of ?15 nm and lengths of ?50
nm were investigated by X-ray absorption spectroscopy. These heterostructures are
prepared by seed-mediated routes, where the structure, composition, and morphology of
the CdSe nanocrystals used as a seed play key roles in directing the growth of the second
semiconducting domain. The local structural environment of all the elements in the
CdSe@CdS heterostructures was investigated at the Cd, S, and Se K-edges by taking
advantage of the selectivity of X-ray absorption spectroscopy, and was compared to pure
reference compounds. We found that the structural features of dot@rods are
independent of the size of the rods. These structures can be described as made of a
CdSe dot and a CdS rod, both in the wurtzite phase with a high crystallinity of both the
core and the rod. This result supports the effectiveness of high temperature colloidal
synthesis in promoting the formation of core@shell nanocrystals with very low
defectivity. On the other hand, data on the CdSe@CdS with octapod morphology suggest the occurrence of a core composed of
a CdSe cubic sphalerite phase with eight pods made of CdS wurtzite phase. Our findings are compared to current models
proposed for the design of functional heterostructures with controlled nanoarchitecture
Electron and Phonon Confinement and New Surface Phonon Modes in CdSe-CdS Core-Shell Nanocrystals
Optical and vibrational properties of bare and CdS shelled CdSe
nanocrystalline particles are investigated. To confirm the formation of such
nanocrystals in our samples we estimate their average particle sizes and size
distributions using TEM measurements. From the line profile analysis of the
images the core-shell structure in the particles has been confirmed. The blue
shift in optical absorption spectra, analyzed using theoretical estimates based
on the effective bond order model, establishes the electron confinement in the
nanoparticles. Unique characteristics of the nanocrystals (which are absent in
the corresponding bulk material), such as confinement of optical phonons and
the appearance of surface phonons, are then discussed. Making use of the
dielectric response function model we are able to match the experimental and
theoretical values of the frequencies of the surface phonons. We believe that
our studies using optical probes provide further evidence on the existence of
core-shell structures in CdSe-CdS type materials.Comment: 19 pages 8 figure
Dirac Cones, Topological Edge States, and Nontrivial Flat Bands in Two-Dimensional Semiconductors with a Honeycomb Nanogeometry
We study theoretically two-dimensional single-crystalline sheets of
semiconductors that form a honeycomb lattice with a period below 10 nm. These
systems could combine the usual semiconductor properties with Dirac bands.
Using atomistic tight-binding calculations, we show that both the atomic
lattice and the overall geometry influence the band structure, revealing
materials with unusual electronic properties. In rocksalt Pb chalcogenides, the
expected Dirac-type features are clouded by a complex band structure. However,
in the case of zinc-blende Cd-chalcogenide semiconductors, the honeycomb
nanogeometry leads to rich band structures, including, in the conduction band,
Dirac cones at two distinct energies and nontrivial flat bands and, in the
valence band, topological edge states. These edge states are present in several
electronic gaps opened in the valence band by the spin-orbit coupling and the
quantum confinement in the honeycomb geometry. The lowest Dirac conduction band
has S-orbital character and is equivalent to the pi-pi* band of graphene but
with renormalized couplings. The conduction bands higher in energy have no
counterpart in graphene; they combine a Dirac cone and flat bands because of
their P-orbital character. We show that the width of the Dirac bands varies
between tens and hundreds of meV. These systems emerge as remarkable platforms
for studying complex electronic phases starting from conventional
semiconductors. Recent advancements in colloidal chemistry indicate that these
materials can be synthesized from semiconductor nanocrystals.Comment: 12 pages, 12 figure
3D characterization of CdSe nanoparticles attached to carbon nanotubes
The crystallographic structure of CdSe nanoparticles attached to carbon
nanotubes has been elucidated by means of high resolution transmission electron
microscopy and high angle annular dark field scanning transmission electron
microscopy tomography. CdSe rod-like nanoparticles, grown in solution together
with carbon nanotubes, undergo a morphological transformation and become
attached to the carbon surface. Electron tomography reveals that the
nanoparticles are hexagonal-based with the (001) planes epitaxially matched to
the outer graphene layer.Comment: 7 pages, 8 figure
Stereoelectronic effects on the binding of neutral Lewis bases to CdSe nanocrystals
Using P-31 nuclear magnetic resonance (NMR) spectroscopy, we monitor the competition between tri-nbutylphosphine (Bu3P) and various amine and phosphine ligands for the surface of chloride terminated CdSe nanocrystals. Distinct P-31 NMR signals for free and bound phosphine ligands allow the surface ligand coverage to be measured in phosphine solution. Ligands with a small steric profile achieve higher surface coverages (Bu3P = 0.5 nm(-2), Me2P-n-octyl = 2.0 nm(-2), NH2Bu = >3 nm(-2)) and have greater relative binding affinity for the nanocrystal (binding affinity: Me3P > Me2P -n-octyl similar to Me2P -n-octadecyl > Et3P > Bu3P). Among phosphines, only Bu 3 P and Me2P-n-octyl support a colloidal dispersion, allowing a relative surface binding affinity (K-rel) to be estimated in that case (K-rel = 3.1). The affinity of the amine ligands is measured by the extent to which they displace Bu3P from the nanocrystals (K-rel: H2NBu similar to N-n-butylimidazole > 4-ethylpyridine > Bu3P similar to HNBu2 > Me2NBu > Bu3N). The affinity for the CdSe surface is greatest among soft, basic donors and depends on the number of each ligand that bind. Sterically unencumbered ligands such as imidazole, pyridine, and n-alkylamines can therefore outcompete stronger donors such as alkylphosphines. The influence of repulsive interactions between ligands on the binding affinity is a consequence of the high atom density of binary semiconductor surfaces. The observed behavior is distinct from the self-assembly of straight-chain surfactants on gold and silver where the ligands are commensurate with the underlying lattice and attractive interactions between aliphatic chains strengthen the binding
Distance Dependence of the Energy Transfer Rate From a Single Semiconductor Nanostructure to Graphene
The near-field Coulomb interaction between a nano-emitter and a graphene
monolayer results in strong F\"orster-type resonant energy transfer and
subsequent fluorescence quenching. Here, we investigate the distance dependence
of the energy transfer rate from individual, i) zero-dimensional CdSe/CdS
nanocrystals and ii) two-dimensional CdSe/CdS/ZnS nanoplatelets to a graphene
monolayer. For increasing distances , the energy transfer rate from
individual nanocrystals to graphene decays as . In contrast, the
distance dependence of the energy transfer rate from a two-dimensional
nanoplatelet to graphene deviates from a simple power law, but is well
described by a theoretical model, which considers a thermal distribution of
free excitons in a two-dimensional quantum well. Our results show that accurate
distance measurements can be performed at the single particle level using
graphene-based molecular rulers and that energy transfer allows probing
dimensionality effects at the nanoscale.Comment: Main text (+ 5 figures) and Supporting Information (+ 7 figures
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