A critical look at the kinetic models of thermoluminescence: I. First-order kinetics

Using a generalized scheme of multiple traps, thermoluminescence (TL) glow curves are calculated for different sets of systems parameters. In particular, the conditions under which glow peaks of first-order kinetics are produced are highlighted. The major findings and conclusions are as follows. (1) In the generalized scheme the glow peaks always reduce to first order at low trap occupancies. It is therefore suggested that the peak analysis to determine the parameters should be carried out only at low doses. (2) Glow peaks which follow first-order kinetics can be obtained irrespective of whether the recombination rate is faster, equal to or slower than the retrapping rate (Rret). (3) Quasi-equilibrium (QE) of free carriers in the delocalized band, which is the essential condition for the derivation of the conventional analytical expressions of TL and thermally stimulated conductivity, can be realized irrespective of whether RrecRret. (4) The realization of the QE condition depends on the concentrations of the traps and the recombination centres (RCs) and their cross sections for free carrier capture. It is discussed and shown that, in doped insulating and semiconducting materials, the values of these parameters are sufficiently high for the QE condition to be comfortably held. It is thus concluded that the doubts raised by earlier workers regarding the validity of the QE assumption in the derivation of the analytical expressions are unnecessary as far as these materials are concerned. (5) It is shown that a system in which some of the untrapped charge carriers recombine within the germinate centres and some become delocalized may satisfactorily explain the mechanism of TL emission in most of the phosphors. The properties of first-order, supralinearity and pre-dose sensitization may be easily explained under the framework of this system. (6) Conclusions (2) and (3) above disprove those of earlier workers who had concluded that QE and fast retrapping together do not form a consistent set of conditions and that the apparent dominance of first-order kinetics in nature is due to slow retrapping.