The authors demonstrate that the order of kinetics of the TL process can change with the dose received by a sample. In LiF the order of kinetics becomes constant only when the dose given to the sample is smaller than the saturation dose by at least an order of magnitude. The order of kinetics followed by glow peaks V (190 degrees C) and XII (385 degrees C) of LiF TLD-100 is determined using two methods: (i) peak shape, and (ii) isothermal decay. The former gives the values as 1.4 for peak V and 1.35 for peak XII and the latter 1.6 for peak V and 1.5 for peak XII. For the saturation exposure of 105 R when no empty traps are available, peak V decays exponentially in the beginning (first-order kinetics) and as the decay progresses the order of kinetics continuously increases. After 3 min of decay at 165 degrees C, when the intensity has fallen to less than 20% of initial value, the order of kinetics stabilises at 1.6. The activation energies E of the two peaks are determined using (i) peak shape, and (ii) initial rise methods. The initial rise method is found to give lower values of E than the peak shape method. This is explained on the basis of a thermal effect on luminescence efficiency.

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.

No abstract

Strong doubts havc been expressed about the validity of the quasi-equilibrium (QE) assumption used in the derivation of the analytical expressions of thermoluminescence (TL). So far there is no established method available to check if QE actually prevails during the emission of an experimental TL signal. The present study shows that the level of QE changes with a change in the heating rate beta. The change in the level of QE in its turn gets reflected in a change in peak shape when the system turns to a non-QE condition. This property is used as the first ever experimental method to test whether or not the emission of a given glow peak occurs under the QE condition. An essential condition for holding the QE condition is found to be T(R)/taum> or = 10(-3) where T(R) and taum are the glow peak recording duration and the maximum value of the free carrier lifetime, respectively. This relation between T(R) and taum is useful in finding the approximate value of taum. The value of taum being a function of the concentration and cross section of the TL related centres, one may be able to assess these basic parameters from the study of TL glow curves. The theoretical results are discussed in the perspective of LiF (TLD-100).

Non-first order (FO) kinetics models are of three types; second order (SO), general order (GO) and mixed order (MO). It is shown that all three of these have constraints in their energy level schemes and their applicable parameter values. In nature such restrictions are not expected to exist. The thermoluminescence (TL) glow peaks produced by these models shift their position and change their shape as the trap occupancies change. Such characteristics are very unlike those found in samples of real materials. In these models, in general, retrapping predominates over recombination. It is shown that the quasi-equilibrium (QE) assumption implied in the derivation of the TL equation of these models is quite valid, thus disproving earlier workers' conclusion that QE cannot be held under retrapping dominant conditions. However notwithstanding their validity, they suffer from the shortcomings as stated above and have certain lacunae. For example, the kinetic order (KO) parameter and the pre-exponential factor which are assumed to be the constant parameters of the GO kinetics expression turn out to be variables when this expression is applied to plausible physical models. Further, in glow peak characterization using the GO expression, the quality of fit is found to deteriorate when the best fitted value of KO parameter is different from 1 and 2. This means that the found value of the basic parameter, namely the activation energy, becomes subject to error. In the MO kinetics model, the value of the KO parameter α would change with dose, and thus in this model also, as in the GO model, no single value of KO can be assigned to a given glow peak. The paper discusses TL of real materials having characteristics typically like those of FO kinetics. Theoretically too, a plausible physical model of TL emission produces glow peaks which have characteristics of FO kinetics under a wide variety of parametric combinations. In the background of the above findings, it is suggested that the kinetics analysis of the TL glow curves should be carried out straightforwardly assuming FO kinetics.