The role that applied potential has in controlling the properties of porous silicon formed on highly conductive p-type silicon in diluted HF has been investigated by studying the photoluminescence characteristics along the current-voltage curve and using high resolution transmission electron microscopy (HRTEM) evidence to support the conclusions drawn. A dramatic decrease in the average nanocrystal size was found to take place after the etching current density switched from an exponential dependence on the applied potential to a linear relationship. Importantly this event occurred prior to reaching the U-ps potential (usually consider the onset of electropolishing). This rapid decrease in particle sizes has been explained in terms of the partial formation of an oxide film. The presence of oxygen terminated porous silicon allows a trapped exciton states model to be invoked, which removes the quantum confinement restrictions on the minimum particle size. Support for the presence of a partial oxide prior to U-ps comes from both FTIR measurements and previous literature related to the location of the flat-band potential. (c) 2008 Elsevier Ltd. All rights reserved.