Field electron and ion emission from charged surfaces: a strategic historical review of theoretical concepts

The field-electron (FE) and field-ion techniques directly observe and measure atomic-level surface processes that occur in very high electric fields. In theoretical terms, the high fields put large additional terms into Hamiltonians and free energies, and significantly modify many aspects of the surface physics and chemistry, as compared with the field-free situation. This paper presents a strategic review of the fundamental science of some of these high-field surface effects and processes, as developed in the context of the field electron and ion emission techniques. It outlines the main theoretical concepts developed, notes some twists of scientific history, and suggests useful contributions made to mainstream science. Topics covered are basic aspects of FE emission, surface field ionisation, localised field adsorption, charged surfaces theory, field-ion image contrast theory and associated imaging-gas kinetics, field evaporation, and aspects of the thermodynamics of charged surfaces. Despite many years of effort, important aspects of the theory remain incomplete. Some theoretical challenges are noted. (C) 2002 Elsevier Science B.V. All rights reserved.