 Solution

The competition between crystallization, exposed surfaces, adhesion and elastic strain can be summarized byHere $\Delta g>0$ measures the bulk driving force from supersaturation, and the $\gamma$ values are interfacial free energies. For a free spherical nucleus, $\Delta G=4\pi r^2\gamma -4\pi r^3\Delta g/3$ gives $r_{\ast }=2\gamma /\Delta g$. A support changes the heterogeneous nucleation barrier through adhesion and geometry.

Precursor activities and supply rate, temperature, time, solvent and ligands control nucleation, attachment, detachment and surface diffusion. Many nuclei divide a fixed solute inventory into smaller particles; continued growth or Ostwald ripening can enlarge them. Substrate defects determine preferred nucleation sites; lattice mismatch and interface bonding constrain orientation and elastic relaxation. Facet-selective adsorption can change both surface energies and growth rates.

Near equilibrium, a free nanocrystal follows a Wulff construction; a supported particle can follow a Winterbottom construction. Under kinetic control, slowly advancing facets remain visible while rapidly growing ones disappear. Equilibrium facet energy and kinetic growth rate are different controls, so a crystal structure does not uniquely determine particle shape.