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Cu(2)S nanocrystals with disklike morphologies were synthesized by the solventless thermolysis of a copper alkylthiolate molecular precursor. The nanodisks ranged from circular to hexagonal prisms from 3 to 150 nm in diameter and 3 to 12 nm in thickness depending on the growth conditions. High resolution transmission electron microscopy (HRTEM) revealed the high chalcocite (hexagonal) crystal structure oriented with the c-axis (001 direction) orthogonal to the favored growth direction. This disk morphology is thermodynamically favored as it allows the extension of the higher energy 100 and 110 surfaces with respect to the 001 planes. The hexagonal prism morphology also appears to relate to increased C-S bond cleavage of adsorbed dodecanethiol along the more energetic 100 facets relative to 001 facets. Monodisperse Cu(2)S nanodisks self-assemble into ribbons of stacked platelets. This solventless approach provides a new technique to synthesize anisotropic metal chalcogenide nanostructures with shapes that depend on both the face-sensitive thermodynamic surface energy and the surface reactivity.
Sigman et al. (Thu,) studied this question.