Interface Studies with Nonlinear Optics

Abstract

The importance of interfaces for material science and electronic devices has stimulated great interest in the development of surface analytical tools. Among them, modern optical techniques using lasers have attracted the most attention in recent years. They have the advantage of being applicable to all interfaces accessible by light, and the high temporal, spatial, and spectral resolutions offer unique opportunities for studying ultrafast molecular dynamics and other transient phenomena at interfaces. Optical second harmonic generation (SHG) and sum-frequency generation (SFG) are particularly being noticed because of the many recent successful demonstrations of their versatility. This article briefly introduces these newly developed surface probes, first outlining the basic principles behind surface SHG and SFG, and then illustrating the power of the techniques with selected examples. A more complete treatment of the theory can be found in References 4–6. An overview of the earlier applications can be found in Reference 3.SHG arises from the nonlinear polarization P(2)(2ω) induced in a medium by an incident laser field E(ω). In the electric dipole approximation, P is given by:where is a second-order nonlinear susceptibility. For a medium with inversion symmetry, it follows directly from Eq. 1 that = 0. However, at an interface the surface nonlinear susceptibility is nonvanishing because there the inversion symmetry is necessarily broken.