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.
Nanoscale materials are currently being exploited as active components in a wide range of technological applications in various fields, such as composite materials, chemical sensing, biomedicine, optoelectronics and nanoelectronics. Colloidal nanocrystals are promising candidates in these fields, due to their ease of fabrication and processibility. Even more applications and new functional materials might emerge if nanocrystals could be synthesized in shapes of higher complexity than the ones produced by current methods (spheres, rods, discs). Here, we demonstrate that polytypism, or the existence of two or more crystal structures in different domains of the same crystal, coupled with the manipulation of surface energy at the nanoscale, can be exploited to produce branched inorganic nanostructures controllably. For the case of CdTe, we designed a high yield, reproducible synthesis of soluble, tetrapod-shaped nanocrystals through which we can independently control the width and length of the four arms.
We report the preparation and structural characterization of core/shell CdSe/CdS/ZnS nanorods. A graded shell of larger band gap is grown around CdSe rods using trioctylphosphine oxide as a surfactant. Interfacial segregation is used to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. The reported synthesis allows for variation of the shell thickness between one and six monolayers, on core nanorods ranging from aspect ratios of 2:1 to 10:1. After an irreversible photochemical annealing process, the core/shell nanorods have increased quantum efficiencies and are stable in air under visible or UV excitation. In addition to their robust optical properties, these samples provide an opportunity for the study of the evolution of epitaxial strain as the shape of the core varies from nearly spherical to nearly cylindrical.
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