Luminescence de recombinaison consecutive a la photoionisation d'une solution organique vitreuse-nouvelle methode experimentale

In this paper, we describe a new experimental method which is used to determine the effect of temperature on the mechanisms related to the detrapping of electrons trapped in a glass. The studied samples are organic vitreous solutions of an aromatic molecule (TMPD) inside a non-polar glass (3-MP or MCH). The intensity of the isothermal luminescence (ITL) following the photoionization of the sample at 77K is increased when applying thermal jumps ΔT≲2K (the rise time is ⋍s).

A general kinetical theory is used to explain the shapes of the luminescence curves perturbed by thermal jumps. It is shown that the experimental observations can be explained in terms of a slow diffusion of the trapped electrons towards a tunneling detrapping zone. When applying a thermal jump ΔT, the intensity of luminescence is multiplied by X such as: $\text{X =}\text{exp}\text{ΔT}\text{T}\text{E}\text{kT}\text{+ Y}\text{1+Y}$.

This relationship is in good agreement with experience. The thermal detrapping activation energy E and the tunnelling effect ratio Y can be determined through this formula. The shapes of the kinetic curves at T = 77K and T = 77·50K are compared in the case of 3-MP glassy samples (near the glass transition, T_g = 77K). It is concluded that there is a slow diffusion of trapped electrons (as it was already shown); the diffusion activation energy (E_d = 0·65eV) is found to be very close to viscosity activation energy (E = 0·65eV) as given by Willard. This last result seems to support the hypothesis according to which the diffusion of trapped electrons is the consequence of the diffusion of the trapping cavities (at T_g).