Self-assembly of nanoparticles
Nanoparticles are classified as having at least one of its dimensions in the range of 1-100 nanometers (nm). The small size of nanoparticles allows them to have unique characteristics which may not be possible on the macro-scale. Self-assembly is the spontaneous organization of smaller subunits to form larger, well-organized patterns. For nanoparticles, this spontaneous assembly is a consequence of interactions between the particles aimed at achieving a thermodynamic equilibrium and reducing the system’s free energy. The thermodynamics definition of self-assembly was introduced by Professor Nicholas A. Kotov. He describes self-assembly as a process where components of the system acquire non-random spatial distribution with respect to each other and the boundaries of the system. This definition allows one to account for mass and energy fluxes taking place in the self-assembly processes.
Transmission electron microscopy image of an iron oxide nanoparticle. Regularly arranged dots within the dashed border are columns of Fe atoms. Left inset is the corresponding electron diffraction pattern. Scale bar: 10 nm.
Iron oxide nanoparticles can be dispersed in an organic solvent (toluene). Upon its evaporation, they may self-assemble (left and right panels) into micron-sized mesocrystals (center) or multilayers (right). Each dot in the left image is a traditional "atomic" crystal shown in the image above. Scale bars: 100 nm (left), 25 μm (center), 50 nm (right).
Self-assembly of solid nanoparticles at oil-water interface.
An icosahedral twin is a nanostructure appearing in atomic clusters and also nanoparticles with some thousands of atoms. These clusters are twenty-faced, with twenty interlinked tetrahedral crystals joined along triangular faces having three-fold symmetry. A related, more common structure has five units similarly arranged with twinning, which were known as "fivelings" in the 19th century, more recently as "decahedral multiply twinned particles", "pentagonal particles" or "star particles". A variety of different methods lead to the icosahedral form at size scales where surface energies are more important than those from the bulk.
Annular dark-field image of a 5-fold twinned Au nanoparticle with a shape similar to a pentagonal bipyramid.
Dark field analysis of dual-tetrahedron crystal pairs.