Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2022 / Paper 2 / Section A(i) / 13 / ii / Solution

Symmetry breaking in nanocrystal growth makes growth rates along initially equivalent crystallographic directions unequal, so the final shape has lower symmetry than an unperturbed seed. It need not change the underlying face-centered cubic lattice. A cubic lattice does not require a cubic external shape.

Anisotropy can originate in a twin or stacking fault, unequal ligand coverage of nominally equivalent sites, selective adsorption or etching, a substrate or external field, or a local fluctuation amplified because newly deposited material changes subsequent growth. Facet-selective binding suppresses some normal growth rates; concentration and reduction kinetics determine whether atoms can redistribute towards a near-equilibrium shape or remain in a kinetically selected one. A facet with slow normal growth tends to remain exposed, while a fast-growing facet can disappear.

For a one-dimensional silver example, begin with a small seed with multiple regions related by crystal twinning containing five sectors around a common axis. Ligand-protected lateral faces and more active ends favour axial addition, producing an elongated pentagonal rod and then a wire. The defect geometry and surface kinetics jointly distinguish the axial direction. Fivefold twinning is a composite structure with strain accommodation, not a perfect single fcc crystal with forbidden fivefold lattice symmetry.

For a two-dimensional example, begin with a seed containing a planar twin or stacking fault. Basal-face protection and enhanced incorporation at suitable edges favour lateral extension over thickening, producing a thin triangular or hexagonal plate. The accompanying schematic emphasizes seed, symmetry-breaking event and anisotropic growth stages. These are representative routes, not universal requirements for every rod or plate. Experimentally, silver-seed growth can also be redirected into lower-symmetry forms by controlling reduction kinetics.^[ref]