Surface Diffusion - Regimes

Regimes

There are four different general schemes in which diffusion may take place. Tracer diffusion and chemical diffusion differ in the level of adsorbate coverage at the surface, while intrinsic diffusion and mass transfer diffusion differ in the nature of the diffusion environment. Tracer diffusion and intrinsic diffusion both refer to systems where adparticles experience a relatively homogeneous environment, whereas in chemical and mass transfer diffusion adparticles are more strongly affected by their surroundings.

• Tracer diffusion describes the motion of individual adparticles on a surface at relatively low coverage levels. At these low levels (< 0.01 monolayer), particle interaction is low and each particle can be considered to move independently of the others. The single atom diffusing in figure 1 is a nice example of tracer diffusion.
• Chemical diffusion describes the process at higher level of coverage where the effects of attraction or repulsion between adatoms becomes important. These interactions serve to alter the mobility of adatoms. In a crude way, figure 3 serves to show how adatoms may interact at higher coverage levels. The adatoms have no "choice" but to move to the right at first, and adjacent adatoms may block adsorption sites from one another.
• Intrinsic diffusion occurs on a uniform surface (e.g. lacking steps or vacancies) such as a single terrace, where no adatom traps or sources are present. This regime is often studied using field ion microscopy, wherein the terrace is a sharp sample tip on which an adparticle diffuses. Even in the case of a clean terrace the process may be influenced by non-uniformity near the edges of the terrace.
• Mass transfer diffusion takes place in the case where adparticle sources and traps such as kinks, steps, and vacancies are present. Instead of being dependent only on the jump potential barrier E_diff, diffusion in this regime is now also dependent on the formation energy of mobile adparticles. The exact nature of the diffusion environment therefore plays a role in dictating the diffusion rate, since the formation energy of an adparticle is different for each type of surface feature as is described in the terrace-step-kink model.