Section 1.8.4.6. Anharmonic interactions

In crystals that are relatively pure, i.e. those that lack large numbers of impurities, the important limitation on thermal conductivity at high temperature is from anharmonic interactions (Ziman, 1962). The vibrational potential between neighbouring atoms is not perfectly harmonic. Besides the quadratic dependence on vibrational distance, there is usually a term that depends upon the third and perhaps fourth powers of the relative displacements of the ions. These latter terms are the anharmonic part of the vibrational potential energy. They cause the crystal to expand with temperature and also contribute to the thermal resistance.

For most crystals, the cubic term is important. Its contribution is best explained using the language of phonons. The cubic term means that three phonons are involved. This usually means that one phonon decays into two others, or two phonons combine into one. Both processes contribute to the lifetime of the phonons. On rare occasions, the phase space of the phonons does not permit these events. For example, silicon has a very high frequency optical phonon branch (62 meV at the zone centre) while the acoustic phonons have rather low frequencies. The optical phonons are unable to decay into two of lower frequency, since the two do not have enough energy. This explains, in part, why silicon has a high thermal conductivity. However, this case is unusual. In most crystals, the phonons have similar energy and one can decay into two of lower energy.

The three-phonon events have a simple dependence upon temperature. When one phonon goes to two, or vice versa, the rate depends upon the density of phonons as given by the Bose–Einstein occupation number. At high temperature, i.e. about half of the Debye temperature, this function can be expanded to and the thermal resistance is proportional to temperature. Thus a plot of the inverse thermal conductivity versus temperature usually shows a linear behaviour at high temperature. This linear term is from the anharmonic interactions. There are two main reasons for deviations from linear behaviour: the thermal expansion of the crystal and the contribution of the anharmonic quartic terms, which tend to go as .