Kinetic and thermodynamic processes of organic species at the solution-solid interface: the view through an STM

A focused review is presented on the evolution of our understanding of the kinetic and thermodynamic factors that play a critical role in the formation of well ordered organic adlayers at the solution-solid interface. While the current state of knowledge is in the very early stages, it is now clear that assumptions of kinetic or thermodynamic control are dangerous and require careful confirmation. Equilibrium processes at the solution-solid interface are being described by evolving thermodynamic models that utilize concepts from the thermodynamics of micelles. A surface adsorption version of the Born-Haber cycle is helping to extract the thermodynamic functions of state associated with equilibrium structures, but only a very few systems have been so analyzed. The kinetics of surface phase transformation, especially for polymorphic phases is in an early qualitative stage. Adsorption and desorption kinetics are just starting to be measured. The study of kinetics and thermodynamics for organic self-assembly at the solution-solid interface is experiencing very exciting and rapid growth.