RECENT DEVELOPMENTS IN COMPUTERISED ANALYSIS OF THERMOLUMINESCENCE GLOW CURVES: SOFTWARE CODES, MECHANISMS AND DOSIMETRIC APPLICATIONS.

The computerised deconvolution of thermoluminescence glow curves into component glow peaks is discussed in detail with special emphasis on advances of the subject post 2013. A plethora of computer codes have been developed using models based on first-order kinetics, second-orders kinetics, interactive traps and continuous distributions of activation energies. The glow curves of several materials are displayed and discussed along with new and improved dosimetric applications:precision effects of heating rate, heavy charged particles, mixed field α/ϒ dosimetry, fading and dose-response linearity. Finally recommendations are made for future efforts.

DOSE DEPENDENCE OF RADIATION INDUCED DAMAGE IN THE THERMOLUMINESCENT RESPONSE OF LIF:Mg,Ti (TLD-100).

The effect of previous irradiation on the sensitivity of the glow peaks of LiF:Mg,Ti (TLD-100) is investigated up to levels of dose of 400 Gy in both slow-cooled and naturally cooled materials following the 400°C/1 hour pre-irradiation anneal. It is demonstrated that the naturally cooled samples can be re-used up to accumulated levels of dose of 50 Gy without recalibration. At 400 Gy a significant decrease in sensitivity of approximately 25% is observed for all the glow peaks (excluding peak 3). In slow-cooled materials even 100 Gy does not alter the sensitivity of the material.

MANIPULATION OF THE DOSE-RESPONSE OF COMPOSITE GLOW PEAK 5 IN THE THERMOLUMINESCENCE OF LiF:Mg,Ti (TLD-100) VIA OPTICAL EXCITATION POST-IRRADIATION: POTENTIAL FOR IMPROVED DOSE-RESPONSE LINEARITY BEYOND 1 Gy.

Many dosimetric applications and especially those involved in clinical dosimetry are hampered by the supralinearity of TLD-100 which begins at a level of dose of 1 Gy. This research investigates the effect of optical excitation following irradiation on the dose-response. It is expected that this will lead to a more linear dose-response, however, irrespective of the hoped-for linearity, the theoretical/kinetic simulations of the effect of optical excitation will further enhance our understanding of the thermoluminescence mechanisms, especially the role of spatially correlated trapping and luminescent centers. In the following, the various stages carried out in these investigations are discussed and preliminary results presented.

Theoretical and experimental investigation of the f(D)max-(S/S0)max anomaly in LiF:Mg,Ti.

Previous investigations in the framework of the Unified Interaction Model (UNIM) have demonstrated the difficulty in theoretically predicting both f(D)max and [S(Ds)/S(0)]max with the same set of UNIM parameters. This anomaly is re-investigated and an alternative explanation, based on experimental measurements combined with UNIM analysis, is given. This explanation is based on the assumption that N(LC), the total number of available luminescent centres is changed by the sensitisation dose or anneal or both. Allowing N(LC) to increase as the sensitisation dose is increased, a good fit to both f(D) and S(Ds)/S0 is obtained.

Modelling the dose response of peaks 4, 5 and 5b, in TLD-100, as a function of recombination temperature.

This investigation focuses on whether the experimentally observed changes, in supralinearity f(D) as a function of recombination temperature, can be, successfully, predicted by the Unified Interaction Model (UNIM). To resolve this question, the measurement of f(D) has been carried out for glow peaks 4, 5 and 5b in LiF:Mg,Ti (TLD-100) at two different heating rates and UNIM analysis is used in an attempt to arrive at a consistent/physically reasonable explanation of all the f(D)/heating rate data for the three glow peaks. It is demonstrated that in addition to the variation in the luminescence and competitive centre capture cross section with temperature changes in the ks (the geminate recombination coefficient) parameter as a function of temperature is also required in order to predict the changes in f(D).

Properties of the 4.45 eV optical absorption band in LiF:Mg,Ti.

The optical absorption (OA) and thermoluminescence (TL) of dosimetric LiF:Mg,Ti (TLD-100) as well as nominally pure LiF single crystal have been studied as a function of irradiation dose, thermal and optical bleaching in order to investigate the role of the 4.45 eV OA band in low temperature TL. Computerised deconvolution was used to resolve the absorption spectrum into individual gaussian bands and the TL glow curve into glow peaks. Although the 4.45 eV OA band shows thermal decay characteristics similar to the 4.0 eV band its dose filling constant and optical bleaching properties suggest that it cannot be associated with the TL of composite peaks 4 or 5. Its presence in optical grade single crystal LiF further suggests that it is an intrinsic defect or possibly associated with chance impurities other than Mg, Ti.

New evidence for spatially correlated TC-LC mechanisms in thermoluminescence of LiF:Mg,Ti.

New experimental investigations, consistent with the spatial coupling/perturbation between the trapping centres (TC) and luminescent centres (LC) giving rise to the peaks 5 and 4 thermoluminescence (TL) of LiF:Mg,Ti are discussed: (1) The glow peak widths of peaks 2 and 3 are constant as a function of Ti concentration, while the width of peak 4 decreases with a correlated increase in the width of peak 5. The dependence of glow peak shape on Ti concentration indicates that peaks 4 and 5 arise from a TC/LC spatially correlated extended defect. (2) The increased TL intensity of peak 5a following high ionisation density HCP irradiation compared to low ionisation density gamma irradiation strongly suggests that peak 5a arises from the geminate recombination of a locally trapped e-h pair. (3) The observation that the optical bleaching conversion efficiency (CE) of peak 5a to peak 4 is measured to be 3+/-0.5 and is three orders of magnitude greater than the CE of peak 5 to peak 4, is strong evidence for the unique structure of peak 5a--trap, i.e. peak 5a is due to a TC/LC structure which has captured an e-h pair, optical ionisation of the electron leads directly to the peak 4 TC.

Investigation of the emission spectra of LiF:Mg,Ti (TLD-100) during thermoluminescence.

The thermoluminescence (TL) of LiF:Mg,Ti has been studied using a high resolution CCD spectrophotometer, which simultaneously measures the emission intensity and the emission spectrum as a function of sample temperature. Computerised deconvolution was used to resolve the emission spectrum into individual Gaussian bands and the TL glow curve into glow peaks. Correction for spectral response and non-linear changes in dispersion were taken into account in the evaluation of the emission spectra. The emission spectra of all TL glow peaks following 200 Gy beta irradiation were found to consist of a common set of five emission bands at 2.49 eV, 2.64 eV, 2.84 eV, 3.1 eV and 3.59 eV, of which the 2.95 eV and 3.59 eV bands have not been previously observed at these dose levels. The band characteristics (E, deltaE) are not sample temperature or dose dependent indicating that the same LCs or the same single centre with several excited states are common to all the glow peaks. The relative intensities of the emission bands do. however, change as a function of readout temperature and dose, a behaviour that could be connected to a temperature and dose dependent perturbation between spatially coupled TCs and LCs.

Glow curve analysis of composite peak 5 in LiF:Mg,Ti (TLD-100) using optical bleaching, thermal annealing and computerised glow curve deconvolution.

The relative intensity of glow peak 5a in the composite glow peak 5 of LiF:Mg,Ti (TLD-100) is very weak following gamma irradiation, and has been estimated at approximately 0.1 of the intensity of peak 5. Typical glow curve analysis using computerised glow curve deconvolution with unconstrained variation of the peak shape parameters, yields values of the relative intensity of glow peak 5a varying from 0 to 15%. Due to the potential of peak 5a to fulfil the criteria of a quasi-tissue-equivalent nanodosemeter which estimates quality factor, considerable efforts have been invested in ancilliary techniques to improve the reliability of the estimation of the intensity of peak 5a. Optical bleaching and thermal annealing techniques were used to obtain single-peak glow curves consisting of peak 4 only and peak 5 only. A multi-stage CGCD protocol was then constructed using these peak shape parameters for peaks 4 and 5, which allows more accurate estimation of the relative intensity of peak 5a. Following 60Co irradiation of ten chips to a dose level of 1 Gy, the technique yields a relative intensity of 0.08 +/- 0.008 (1 SD).

The composite structure of peak 5 in the glow curve of LiF:Mg,Ti (TLD-100): confirmation of peak 5a arising from a locally trapped electron-hole configuration.

The hypothesis that glow peak 5a arises from localised e-h capture is confirmed by the following experimental observations: (i) The high conversion efficiency (CE) (CE5a-->4 = 3 +/- 0.5) of peak 5a to peak 4 (a hole-only trap) deduced from detailed Im-Tstop optical bleaching studies at 310 nm compared to the much lower CE of peak 5 (an electron-only trap) (CE5-->4 = 0.0026+/-0.012). (ii) The lack of an increase in the sensitivity of glow peak 5a following 2.6 MeV and 6.8 MeV He ion irradiation in 'sensitised' material compared to the factor two increase in the sensitivity of peak 5; (S/S0)5a = 0.86+/-0.12, compared to (S/S0)5 = 2.0+/-0.2. (iii) The late entry into saturation of the 2.6 MeV and 6.8 MeV He ion TL-fluence response curves for peak 5a compared to peak 5 in sensitised and normal material resulting in the following values for the track radial saturation parameter: (r50)5a = 100+/-20) Angstroms compared to (r50)5 = 380+/-30 Angstroms. (iv) The low value of 0.1 for the 'track-escape' parameter of peak 5a deduced from the Extended Track Interaction Model analysis of He ion TL fluence response compared to order of magnitude greater values for peaks 5 and 5b.

Localised and delocalised optically induced conversion of composite glow peak 5 in LiF:Mg,Ti (TLD-100) to glow peak 4 as a function of postirradiation annealing temperature.

The composite structure of glow peak 5 in LiF:Mg,Ti (TLD-100) has been investigated using optical bleaching by 310 nm (4 eV) light. The glow peak conversion efficiency of peak 5a (Tm = 187 degrees C) to peak 4 traps is very high at a value of 3+/-0.5 (1 SD) whereas the glow peak conversion efficiency of peak 5 (Tm = 205 degrees C) to peak 4 traps is 0.0026+/-0.0012 (1 SD). The high conversion efficiency of peak 5a to peak 4 arises from direct optical ionisation of the electron in the electron-hole pair. leaving behind a singly-trapped hole (peak 4), a direct mechanism, relatively free of competitive mechanisms. Optical ionisation of the 'singly-trapped' electron (peak 5), however, can lead to peak 4 only via multi-stage mechanisms involving charge carrier transport in the valence and conduction bands, a mechanism subject to competitive processes. The conduction/valence band competitive processes lead to the factor of one thousand decrease in the conversion efficiency of peak 5 compared to peak 5a.

The unified interaction model applied to LiF:Mg,Ti (TLD-100): properties of the luminescent and competitive centres during sensitisation.

An attempt is made to predict/interpret theoretically the experimentally measured values of f(D) and S(Ds)/So for composite peak 5 in TLD-100. using the Unified Interaction Model (UNIM) with identical values of the UNIM parameters for both sets of experimental data. Although an excellent fit can be obtained to the experimental f(D) data over the entire dose region where f(D) is greater than unity. i.e. from 5 Gy to several thousand Gy, a satisfactory fit to both sets of data is found to require different values for at least one of the parameters. The lack of success in fining f(D) and S(Ds)/So with the same values of all the parameters, suggests that the sensitisation anneal (particularly the duration of the anneal) may somehow change the structure (S(LC)) and/or the total number of available LCs in an unknown manner.

The concept of quasi-tissue-equivalent nanodosimeter based on the glow peak 5a/5 in LiF:Mg,Ti (TLD-100).

We demonstrate the viability of the concept of using existing molecular nanostructures in thermoluminescent solid-state materials as solid-state nanodosimeters. The concept is based on mimicking radiobiology (specifically the ionization density dependence of double strand breaks in DNA) by using the similar ionization density dependence of simultaneous electron-hole capture in spatially correlated trapping and luminescent centres pairs in the thermoluminescence of LiF:Mg,Ti. This simultaneous electron-hole capture has been shown to lead to ionization density dependence in the relative intensity of peak 5a to peak 5 similar to the ratio of double-strand breaks to single-strand breaks for low energy He ions.