3D equilibrium crystal shapes in the new light of STM and AFM

Abstract

A systematic study of 3D equilibrium crystal shapes (ECS) can yield important surface energetic quantities, such as step, kink, surface and step–step interaction free energies. Observations of the ECS, especially of flat facets and adjacent vicinal regions, will provide primarily relative step and surface free energies. An advanced goal is to determine absolute step free energies, kink formation and step interaction energies. Absolute values of these energies are important in governing crystal growth morphologies, high temperature phase changes and kinetic processes associated with shape changes. Furthermore, absolute step and kink energies are the key to absolute surface free energies of well defined low-index orientations. We review new experiments where sections of the ECS are monitored as a function of temperature to extract characteristic morphological parameters, yielding absolute surface energetic quantities. Attention will be paid to the question of attaining true 3D equilibrium of an ensemble of crystallites. The special role of scanning tunneling and atomic force microscopies will be stressed. New ways of overcoming the problem of the activation barrier for facet growth (or shrinkage) through the study of dislocated crystallites will be demonstrated. In the general context of 3D crystallites, the study of 2D nano-crystals, in the form of adatom or vacancy islands on extended flat surfaces, will be discussed. In particular, the connection between the temperature dependent shape of 2D islands and the absolute step and kink formation energies of the bounding steps, complementary to facet shape changes of 3D crystallites, has emerged as an important topic of recent research. Finally, high temperature phase changes, such as surface roughening and surface melting, as they have been observed by scanning electron microscopy on 3D crystallites, will be briefly reviewed.