The extinction coefficient per mole of nanocrystals at the first exitonic absorption peak, ε, for high-quality CdTe, CdSe, and CdS nanocrystals was found to be strongly dependent on the size of the nanocrystals, between a square and a cubic dependence. The measurements were carried out using either nanocrystals purified with monitored purification procedures or nanocrystals prepared through controlled etching methods. The nature of the surface ligands, the refractive index of the solvents, the PL quantum yield of the nanocrystals, the methods used for the synthesis of the nanocrystals, and the temperature for the measurements all did not show detectable influence on the extinction coefficient for a given sized nanocrystal within experimental error.
Nanometre-size inorganic dots, tubes and wires exhibit a wide range of electrical and optical properties that depend sensitively on both size and shape, and are of both fundamental and technological interest. In contrast to the syntheses of zero-dimensional systems, existing preparations of one-dimensional systems often yield networks of tubes or rods which are difficult to separate. And, in the case of optically active II-VI and III-V semiconductors, the resulting rod diameters are too large to exhibit quantum confinement effects. Thus, except for some metal nanocrystals, there are no methods of preparation that yield soluble and monodisperse particles that are quantum-confined in two of their dimensions. For semiconductors, a benchmark preparation is the growth of nearly spherical II-VI and III-V nanocrystals by injection of precursor molecules into a hot surfactant. Here we demonstrate that control of the growth kinetics of the II-VI semiconductor cadmium selenide can be used to vary the shapes of the resulting particles from a nearly spherical morphology to a rod-like one, with aspect ratios as large as ten to one. This method should be useful, not only for testing theories of quantum confinement, but also for obtaining particles with spectroscopic properties that could prove advantageous in biological labelling experiments and as chromophores in light-emitting diodes.
The synthesis of epitaxially grown, wurtzite CdSe/CdS core/shell nanocrystals is reported. Shells of up to three monolayers in thickness were grown on cores ranging in diameter from 23 to 39 Å. Shell growth was controllable to within a tenth of a monolayer and was consistently accompanied by a red shift of the absorption spectrum, an increase of the room temperature photoluminescence quantum yield (up to at least 50%), and an increase in the photostability. Shell growth was shown to be uniform and epitaxial by the use of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and optical spectroscopy. The experimental results indicate that in the excited state the hole is confined to the core and the electron is delocalized throughout the entire structure. The photostability can be explained by the confinement of the hole, while the delocalization of the electron results in a degree of electronic accessibility that makes these nanocrystals attractive for use in optoelectronic devices.
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