The self-assembly of monodisperse gold and silver colloid particles into monolayers on polymer-coated substrates yields macroscopic surfaces that are highly active for surface-enhanced Raman scattering (SERS). Particles are bound to the substrate through multiple bonds between the colloidal metal and functional groups on the polymer such as cyanide (CN), amine (NH(2)), and thiol (SH). Surface evolution, which can be followed in real time by ultraviolet-visible spectroscopy and SERS, can be controlled to yield high reproducibility on both the nanometer and the centimeter scales. On conducting substrates, colloid monolayers are electrochemically addressable and behave like a collection of closely spaced microelectrodes. These favorable properties and the ease of monolayer construction suggest a widespread use for metal colloid-based substrates.

Covalent attachment of nanometer-scale colloidal Au particles to organosilane-coated substrates is a flexible and general approach to formation of macroscopic Au surfaces that have well-defined nanostructure. Variations in substrate (glass, metal, Al2O3), geometry (planar, cylindrical), functional group (−SH, −P(C6H5)2, −NH2, −CN), and particle diameter (2.5−120 nm) demonstrate that each component of these assemblies can be changed without adverse consequences. Information about particle coverage and interparticle spacing has been obtained using atomic force microscopy, field emission scanning electron microscopy, and quartz crystal microgravimetry. Bulk surface properties have been probed with UV−vis spectroscopy, cyclic voltammetry, and surface enhanced Raman scattering. Successful application of the latter two techniques indicates that these substrates may have value for Raman and electrochemical measurements. The assembly method described herein is compared with previous methods for controlling the nanoscale roughness of metal surfaces, and its potential applicability to the assembly of other colloidal materials is discussed.