high-work-function contact. For the same reason, electrons are extracted from C60 at the CalMEH-PPV:C,, interface. The result, then, is that separated carriers are not "wasted": thev are automaticallv collected by the prope; electrode so that external work can be done.The substantial enhancement in n ' C achieved with the bicontinuous D-A network material results from the large increase in the interfacial area over that in a D-A bilayer and from the relatively short distance from any point in the polymer to a charge-separating interface. Moreover, the internal D-A junctions inhibit carrier recombination and thereby improve the lifetime of the photoinduced carriers (6), so that the separated charge carriers can be efficiently collected by the built-in field from the asymmetric electrodes. Similar effects have been observed in MEH-PPV:Cyano-PPV polymer blends (10 , 1 1).The device efficiencies are not yet optimized. Because only -60% of the incident power was absorbed at 430 nm in the thinfilm devices used for obtaining the data in u Fig. 3, the internal carrier collection efficiency and energy conversion efficiency are approximately 1.7 times larger; that is, qc.= 90% e/ph and qr;-5.5% at 10 p,W/cm2. Although nearly 100% absorption can be achieved"by using thicker films, qc is currently limited in thick-film devices by internal resistive losses. Further imorovements in device efficiencies are expected when the blend com~ositionand the network morphology are optimized. SCIENCE VOL. 270 15 DECEMBER 1995
Here, we elucidate a double-lamellar-template pathway for the formation of CdSe quantum belts. The lamellar templates form initially by dissolution of the CdX(2) precursors in the n-octylamine solvent. Exposure of the precursor templates to selenourea at room temperature ultimately affords (CdSe)(13) nanoclusters entrained within the double-lamellar templates. Upon heating, the nanoclusters are transformed to CdSe quantum belts having widths, lengths, and thicknesses that are predetermined by the dimensions within the templates. This template synthesis is responsible for the excellent optical properties exhibited by the quantum belts. We propose that the templated-growth pathway is responsible for the formation of the various flat, colloidal nanocrystals recently discovered, including nanoribbons, nanoplatelets, nanosheets, and nanodisks.
Soluble CdSe quantum wires are prepared by the solution-liquid-solid mechanism, using monodisperse bismith nanoparticles to catalyze wire growth. The quantum wires have micrometer lengths, diameters in the range of 5-20 nm, and diameter distributions of +/-10-20%. Spectroscopically determined wire band gaps compare closely to those calculated by the semiemipirical pseudopotential method, confirming 2D quantum confinement. The diameter dependence of the quantum wire band gaps is compared to that of CdSe quantum dots and rods. Quantum rod band gaps are shown to be delimited by the band gaps of dots and wires of like diameter, for short and long rods, respectively. The experimental data suggest that a length of ca. 30 nm is required for the third dimension of quantum confinement to fully vanish in CdSe rods. That length is about six times the bulk CdSe exciton Bohr radius.
Multiwalled BN nanotubes are grown from nickel boride catalyst particles by chemical vapor deposition at 1000−1100 °C using borazine, B3N3H6, as the precursor. This precursor is generated in situ from molten salt that forms from mixtures of (NH4)2SO4, NaBH4, and Co3O4 at 300−400 °C. The BN nanotubes have concentric-tube structures, are free of internal closures, have crystalline walls, and exhibit lengths of up to ∼5 μm. The nanotubes often possess bulbous, flag-like, or club-like tip closures. A root-growth mechanism is proposed for the catalyzed process.
We report the results of isotopic, chemical, structural, and crystallographic microanalyses of graphitic spherules (0.3È9 km) extracted from the Murchison meteorite. The spherules have 12C/13C ratios ranging over 3 orders of magnitude (from 0.02 to 80 times solar), clearly establishing their presolar origin as stellar condensates. These and other isotopic constraints point to a variety of stellar types as sources of the carbon, including low-mass asymptotic giant branch (AGB) stars and supernovae. Transmission electron microscopy (TEM) of ultrathin sections of the spherules revealed that many have a composite structure consisting of a core of nanocrystalline carbon surrounded by a mantle of well-graphitized carbon. The nanocrystalline cores are compact masses consisting of randomly oriented graphene sheets, from PAH-sized units up to sheets 3È4 nm in diameter, with little graphitic layering order. These sheets probably condensed as isolated particles that subsequently coalesced to form the cores, after which the surrounding graphitic mantles were added by vapor deposition. We also detected internal crystals of metal carbides in one-third of the spherules. These crystals (5È200 nm) have compositions ranging from nearly pure TiC to nearly pure Zr-Mo carbide. Some of these carbides occur at the centers of the spherules and are surrounded by well-graphitized carbon, having evidently served as heterogeneous nucleation centers for condensation of carbon. Others were entrained by carbon as the spherules grew. The chemical and textural evidence indicates that these carbides formed prior to carbon condensation, which indicates that the C/O ratios in the stellar sources were very close to unity. Only one of the 67 spherules studied in the TEM contained SiC, from which we infer that carbon condensation nearly always preceded SiC formation. This observation places stringent limits on the possible delay of graphite formation and is consistent with the predictions of equilibrium thermodynamics in the inferred range of pressure and C/O ratios. We model the formation of the observed refractory carbides under equilibrium conditions, both with and without s-process enrichment of Zr and Mo, and show that the chemical variation among internal crystals is consistent with the predicted equilibrium condensation sequence. The compositions of most of the Zr-Mo-Ti carbides require an s-process enrichment of both Zr and Mo to at least 30 times their solar abundances relative to Ti. However, to account for crystals in which Mo is also enriched relative to Zr, it is necessary to suppose that Zr is removed by separation of the earliest formed ZrC crystals from their parent gas. We also explore the formation constraints imposed by kinetics, equilibrium thermodynamics, and the observation of clusters of carbide crystals in some spherules, and conclude that relatively high formation pressures dynes cm~2), and/or condensable carbon number densities cm~3) are required. (Z0.1 (Z108 The graphite spherules with 12C/13C ratios less than the solar valu...
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