Abstract
The phase behavior of organically passivated 20−75 A diameter Ag and Au nanocrystals is investigated by examining surface−area isotherms of Langmuir monolayers and transmission electron micrographs of Langmuir−Blodgett (LB) films. The effects of temperature, organic passivant chain length, and nanocrystal size and composition are studied. Three distinct types of phase behavior are observed and may be classified in terms of the extra (conical) volume (Ve) available to the alkyl capping group as it extends from a nearly spherical metal core. For Ve > 350 A3, the phase diagram is dominated by extended, low-dimensional structures that, at high pressures, compress into a two-dimensional foamlike phase. This behavior is rationalized as originating from the interpenetration of the ligand shells of adjacent particles. For Ve Ve > 150 A3, the particles condense to form closest packed structures, which, for suffici...
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