From fullerenes to nanocrystals and nanocrystal arrays: Novel preparation and characterization methods.

摘要

The success of cluster physics and chemistry and the macroscopic isolation of fullerenes motivated the research of nanometer-size from assemblies based on other elements. In this work an alternative fullerene generation method, utilizing the annealing of an all-carbon precursor formed in the reaction of halocarbons with alkali metals, has been demonstrated. Furthermore, a novel method of nanocrystal processing has been achieved via a compact, well-controlled, multi-stage inert gas flow system operating at near atmospheric pressure. The versatility and adaptability of the nanocrystal flow processor allows for the preparation of various nanostructured materials. Nanocrystal processing in the context of this work means the controlled growth of nanocrystals in a vapor phase environment, their annealing to obtain preferred morphologies, and subsequent full surface stabilization to facilitate collection and handling. The nanocrystal flow processor is coupled in-line to a time-of-flight mass spectrometer for real-time nanocrystal size and composition determination. Continuous sampling and mass analyzing of nanocrystals in the nanometer-diameter size range (up to one million Daltons) at part per billion concentrations has been achieved. Sampling of helium flows bearing benzene, fullerenes, as well as sodium, magnesium, silver, and cesium-iodide nanocrystals has been demonstrated. Using the nanocrystal processing approach, stable silver and gold nanocrystals of uniform size and shape distribution, passivated by self-assembled monolayers of long-chain thiol molecules were successfully prepared. The post-analysis of noble metal nanocrystals included optical spectroscopy, electron microscopy imaging and diffraction, x-ray diffraction and mass spectrometry. Stable and intense cluster beams from gold and silver nanocrystals were produced by laser desorption of molecular films. The mass onset of the desorbed entities corresponds directly to the dimensions of the nanocrystal core. Photofragmentation, photoionization and photodetachment from large metal cluster beams generated this way have all been observed. These robust and uniform in size and shape noble metal nanocrystals self-assemble into highly oriented molecular solids, as observed by transmission electron microscopy imaging and diffraction.