Tunable assembly of heterogeneously charged colloids.

The self-assembly of colloidal particles is a route to designed materials production that combines high flexibility, cost effectiveness, and the opportunity to create ordered structures at length scales ranging from nano- to micrometers. For many practical applications in electronics, photovoltaics, and biomimetic material synthesis, ordered mono- and bilayers are often needed. Here we present a novel and simple way to tune via external parameters the ordering of heterogeneously charged colloids into quasi two-dimensional structures. Depending on the charges of the underlying substrate and of the particles, a rich and versatile assembly scenario takes place, resulting from the complex interplay between directional attractive and repulsive particle-particle and particle-substrate interactions. Upon subtle variations of the relative charge of the system components, emerging via pH modification, reversible changes either from extended aggregates to a monomeric phase or from triangular to square domains are observed.