Published online by Cambridge University Press: 14 March 2011
Micropatterned self-assembled monolayers (SAMs) that serve as substrates for nucleation provide a way of controlling various aspects of the crystallization process with a previously unreachable precision. We focus on crystallization of calcite (CaCO3) on SAMs of HS(CH2)nX (X = CO2H, CH3, SO3H, OH, N(CH3)3Cl) supported on Ag and Au. Fine-tuning of the crystallographic orientation of the forming crystals has been achieved by using different functional groups and metal substrates. By patterning SAMs with microregions having different nucleating activities and proper geometry, it is possible to confine crystallization to well defined, spatially delineated sites. This method provides means to fabricate arbitrarily patterned calcitic arrays with controlled density of nucleation, crystallographic orientation, and crystal sizes. The experimental conditions and the mechanisms discussed can be applied to the templated nucleation of a wide range of inorganic materials.