Newly developed highly sensitive LiF:Mg,Cu,Si TL discs with good stability to heat treatment

The preparation method and some dosimetric properties of the new LiF:Mg,Cu,Si discs are presented. The effect of heat treatments on LiF:Mg,Cu,Si was investigated. The shape of the glow curve for LiF:Mg,Cu,Si is similar to that for standard LiF:Mg,Cu,P (GR-200A), and shows minimal differences when annealed in the range from 260 °C to 290 °C for 10 min. The TL sensitivity for LiF:Mg,Cu,Si is much lower than that for GR-200A, but is 35 times larger than that for TLD-100 and is slightly higher than that for HMCP. The height of the high-temperature peaks for LiF:Mg,Cu,Si is not only lower than that for GR-200A, but also lower than that for HMCP. The glow curve shape of LiF:Mg,Cu,Si annealed at 260 °C for different times shows minimal differences and TL response remains stable. These results indicate that the new LiF:Mg,Cu,Si disc has a good stability to thermal treatments and a lower residual TL signal.     

Investigations of thermoluminescence properties of multicrystalline LiF: Mg,Cu, Si phosphor prepared by edge defined film fed growth technique

Thermoluminescence (TL) properties of LiF: Mg, Cu, Si phosphor prepared in multicrystalline form using edge defined film fed growth (EFG) technique has been investigated. The effect of preparation route on TL properties and thermal stability has been studied. To improve the TL dosimetry properties, phosphor is subjected to different annealing temperatures ranging from 250 °C to 450 °C. The shape of the glow curve structure and peak temperature remains similar at different annealing temperatures, however peak intensities vary. The consistency in the glow curve structure with annealing temperature elucidate that TL trapping states are stable in nature. Thermal annealing at 300 °C for 10 min gives maximum TL intensity with main dosimetry peak at 209 °C. The TL intensity of the main dosimetry peak is increased by a factor of five as compared to as-grown crystal. The thermal stability of LiF: Mg, Cu, Si is found to be better than LiF: Mg, Cu, P. Trapping parameters are calculated to have an insight study of defect states. A simple glow curve structure, tissue equivalency, thermal stability, low residual signal, linear response and reusability makes LiF: Mg, Cu, Si a suitable phosphor for radiation therapy, radio diagnostics and personnel dosimetry applications.     

Influence of sintering temperatures on LiF:Mg,Cu,P with various magnesium concentrations

The dependence of LiF:Mg,Cu,P samples with various concentrations of Mg on sintering temperatures was investigated to find a new dosimeter. The influence of high sintering temperatures on LiF:Mg,Cu,P chips depends strongly on Mg concentrations. The height of the main peak versus the sintering temperatures exhibits a maximum, the position of which varies between 690 °C and 750 °C, depending on the Mg concentration in the range studied. The high temperature peaks of LiF:Mg,Cu,P for various Mg concentrations reduce basically when the sintering temperature is increased. LiF:Mg,Cu,P is much less sensitive than LiF:Mg,Cu,Si to sintering temperature. LiF:Mg,Cu,P with 0.6 mol% of Mg can be re-used at annealing temperature of 260 °C, regardless of the sintering temperature. It was found that the optimum concentration is Mg: 0.6 mol%, the optimum sintering temperature is 750 °C, considering that LiF:Mg,Cu,P with a low residual signal and good sensitivity can be re-used at annealing temperature of 260 °C and produced in a large scale. The new optimum LiF:Mg,Cu,P formation has 52 times higher than that of the TLD-100, and an extremely low residual signal of 0.07% without an initialization readout procedure.     

The dependence of thermoluminescence of LiF:Mg,Cu,Si on sintering temperatures and dopants concentrations

The dependence of thermoluminescence (TL) of LiF:Mg,Cu,Si on sintering temperatures and dopants concentrations were investigated. The dependency of the TL in LiF:Mg,Cu,Si on sintering temperature exhibits a very sharp maximum at 830 °C. LiF:Mg,Cu,Si is much too sensitive than LiF:Mg,Cu,P to sintering temperature. The glow curve and the TL sensitivity depend on the concentration of Mg, Cu and Si, showing a distinct maximum for certain concentrations of these impurities. Mg seems to be the most essential dopant, as very small changes of the Mg content strongly influence both the glow curve and the TL sensitivity. Si is the main activator responsible for TL emission. The stability to heat treatments in LiF:Mg,Cu,Si was influenced greatly by Mg concentrations. The thermal instability in LiF:Mg,Cu,Si is caused not by Cu and Si but Mg ion state change. It was found that the optimum concentrations are Mg:0.6 mol%, Cu:0.03 mol% and Si:0.9 mol% for this material, which showed the best stability to heat treatment.     

Study of a new Lif:Mg,Cu,P formulation with enhanced thermal stability and a lower residual TL signal

This paper presents results obtained for a new LiF:Mg,Cu,P (HMCP) preparation with modified Mg and Cu concentrations. The shape of the HMCP glow curve shows minimal differences for annealing in the range from 523 to 543 K for 10 min. The thermoluminescence (TL) readout value remained stable when annealed in the range from 513 to 543 K for 10 min. The new formula allows heating of the material to higher temperatures than that originally employed for the well-known GR-200A dosemeter, practically without losses in sensitivity. The TL sensitivity is approximately half of that for the GR-200A, and still 29-fold greater than that for the TLD-100 dosemeter, and the residual signal is approximately five-fold lower than for the GR-200A. These results indicate that the new TL material shows enhanced thermal stability and a lower residual TL signal at a small TL sensitivity cost. The heat treatment temperatures are related to concentrations of Mg and Cu in LiF:Mg,Cu,P.     

The reusability characteristics of LiF:Mg,Cu,P with a maximum intensity at 280 °C in an environment with elevated temperature

Efforts are aimed at finding a method that could serve TL dosimetric measurements in the range of low-dose but carried out in an environment with elevated temperature. The temperature at the position of the maximum intensity of LiF:Mg,Cu,P was about 280 °C when annealed at 460 °C. LiF:Mg,Cu,P with a maximum intensity at 280 °C should present good thermal stability. The TL intensity of LiF:Mg,Cu,P with a maximum intensity at 280 °C was about 54% of the standard LiF:Mg,Cu,P, it should have a minimum measurable dose in the range of micro-Gy. LiF:Mg,Cu,P with a maximum intensity at 280 °C could be re-used by the 660 °C/30 min annealing, followed by 270 °C/20 min, 240 °C/10 min and 460 °C/30 min. It's possible for LiF:Mg,Cu,P to be extended application for low dose test in an environment with elevated temperature.     

The effect of pre-irradiation annealing on the thermoluminescence of LiF:Mg,Cu, P phosphor grown by EFG technique

LiF crystal doped with magnesium (Mg), copper (Cu) and phosphorous (P) was grown in the form of multicrystalline sheet using Edge-defined film-fed growth (EFG) technique for dosimetry application. These crystals were grown in argon gas atmosphere using graphite crucible and stainless steel die. Dosimetry peak was observed at 210 °C for as-grown crystal. As reported earlier LiF:Mg, Cu, P is a highly sensitive material but losses its sensitivity if annealed at temperature above 240 °C. In this paper, the effect of annealing temperature on thermoluminescence glow-curve structure, maximum peak temperature, peak height and integrated area of the glow peak of EFG grown samples was investigated in detail. Annealing temperature range from 220 °C to 500 °C was considered for the study. Experimental results of the obtained glow curve show that with increase in annealing temperature, glow peak shift towards higher temperature region with substantial increase in TL intensity. Annealing at 500 °C for 10 min gave maximum TL intensity with main dosimetry peak positioned at 233 °C. Change in the defect structure with different pre-annealing temperature was analysed using trapping parameters.     

Comparison of commercial thermoluminescent readers regarding high-dose high-temperature measurements

Three different thermoluminescent measuring systems have been compared with respect to the differences in temperature profiles, spectral sensitivities, as well as characteristics for high intensities of TL light. The comparison was performed using the Harshaw 3500, Risø DA-20 and RA’94 TLD readers. The instruments were tested for the readouts of highly irradiated LiF:Mg,Cu,P (MCP) TL detectors, which require readout up to 550 °C, in case of doses exceeding 1 kGy. It was found that the Harshaw 3500 can be used, without any additional light attenuation, for the measurements of MCP detectors exposed to doses up to about 5 Gy. For the other two readers the upper dose limit is about 10 times lower. It was also found that the Harshaw 3500 shows the best thermal stability considering the peak maximum position. For the ultra-high doses the differences in the spectral characteristics of the applied optical filters and photomultipliers, in conjunction with an evolution of the MCP TL emission spectrum with increasing dose, significantly influence the shape of TL glow curves measured with the DA-20 reader. The detailed characteristic of the compared TLD readers at high-dose high-temperature range is discussed.     

Post-irradiation storage and thermal stability of thermoluminescence glow peaks in LiF:Mg,Cu,Si

Newly developed LiF:Mg,Cu,Si was found to exhibit no significant fading on room temperature post-irradiation storage up to several months. In view of the wide variation in the reported data of fading of LiF:Mg,Cu,P exhibiting glow curve structure similar to that of LiF:Mg,Cu,Si, a study of the effect of post-irradiation storage and thermal treatments on the deconvoluted glow peaks of LiF:Mg,Cu,Si was undertaken. The decay of inseparable peak-3 by post-irradiation storage or thermal treatments did not indicate any rearrangement in the trap occupation that would affect the response of the main peak (peak-4). A post-irradiation treatment at 125 °C for 10 min was found to be the optimum to eliminate the lower temperature peaks.     

A study on thermal degradation of LiF:Mg,Cu,P and LiF:Mg,Cu,Si

We investigated the thermal degradation of LiF:Mg,Cu,P (NTL-250) and LiF:Mg,Cu,Si (MCS) for the development of TL sheet. By thermogravimetry and differential scanning calorimetry (TG-DSC), the exothermic reaction was observed between 320 °C and 400 °C in MCS as well as NTL-250. The heat value of MCS was twice as large as that of NTL-250. This ratio corresponded with that of Mg amount in these TL materials measured by ICP-OES (inductively-coupled plasma optical emission spectrometry). X-ray diffraction (XRD) measurements were also carried out, and the peaks of MgF₂ phase were also observed in degraded MCS sample as well as NTL-250. Moreover, X-ray absorption near-edge structures (XANES) of Cu in these LiF TLDs were measured. The valences of Cu did not change before and after degradation. It indicates that the thermal degradation is caused by not Cu but Mg ion state change. The exothermic reaction is possible caused by the stabilization reactions, and then it was expected to correspond with MgF₂ precipitation. From these results, we concluded that the thermal degradations of these LiF TLDs are caused by the precipitation of MgF₂.     

Long term study of Harshaw TLD LiF – LLD and uncertainty

Long term study of Harshaw TLD LiF has been performed in this work. The study is carried out over a period of 24 months at storage temperatures of 0 °C, 20 °C and 40 °C using more than 3500 dosimeters. The length and variations of this study may be the most comprehensive study published to date. The dosimeters are HarshawTLD LiF based cards and extremity dosimeters, which include LiF:Mg,Ti and LiF:Mg,Cu,P materials in their different isotopes, sizes and forms. There are three parts in this study: material fade in sensitivity and in signal; lower limit of detection (LLD) and uncertainty; and glow curve peaks and sensitivity change over 24 months. Part I was presented at the SSD15 (15th International Conference on Solid State Dosimetry) in Delft. This paper is the continuous work focused on Part II – the lower limit of detection and uncertainty analysis. The detailed results of each case are provided.     

Further study on the influence of thermal treatments on the glow curve structure in LiF:Mg,Cu,P (GR-200A)

The influence of various annealing treatments with heating temperatures (T_A) from 240 to 700 °C, with re-annealing at 240 °C, and with a combined re-annealing procedure of 20 min at 270 °C followed by 10 min at 240 °C on LiF:Mg,Cu,P (GR-200A) was investigated. As the T_A increased, the intensity decreased rapidly to almost no signal at 340–380 °C then increased clearly and achieved a maximum at 540 °C. The position of the maximum intensity of the glow curve shifted basically in the direction of higher temperatures with an increase at T_A and achieved a maximum of 279 °C when annealed at 460 °C. The re-annealing influenced both the intensity and the glow curve structure at certain degree. The effect of re-annealing on the glow curve depended markedly on the T_A. With re-annealing at 240 °C, the intensity decreased as T_A increased up to 360 °C then increased and achieved a maximum at 540 °C. The intensity could be restored fully when annealed at above 500 °C, however, the glow curve couldn't be restored fully. With a combined annealing, the shape of glow curve of a sample annealed at above 540 °C or below 320 °C was similar to that of the standard glow curve of LiF:Mg,Cu,P and the intensity and glow curve could be restored completely when annealed in the range 620–660 °C. It seems that the main roles of the re-annealing at 240 °C are to restore partially the intensity of peak 4 and peak shape for LiF:Mg,Cu,P when annealed at above 260 °C, and restore fully the total TL intensity of LiF:Mg,Cu,P when annealed at above 500 °C and the main roles of the combined re-annealing are to reduce the intensity of peak 5 and the total TL intensity, increase the intensity of peak 4 and restore the glow curve shape.     

High-dose high-temperature emission of LiF:Mg,Cu,P: Thermally and radiation induced loss & recovery of its sensitivity

Highly sensitive LiF:Mg,Cu,P (MCP) detectors enable measurements of radiation doses from tens of nanograys up to a few kilograys, where the saturation of the signal of the main dosimetric peak occurs. Thanks to the recently observed high-dose high-temperature emission of MCP detectors heated to temperatures up to 600 °C after exposures to radiation doses ranging from 1 kGy to 1 MGy, a new method of thermoluminescent measurement of radiation doses has been recently developed at the Institute of Nuclear Physics (IFJ). This method can measure doses ranging from micrograys up to a megagray. So far, high dose measurements were performed on fresh MCP samples and each detector was used only once, because as a result of these measurements, the detectors lose their sensitivity to a large extent. In this study, a specific thermal treatment intended to fully restore the loss of MCPs TL sensitivity was sought. We have investigated several annealing procedures, applying different temperatures (from 400 °C up to 700 °C) for different periods of time (10–30 min) in argon atmosphere. In this way we were able to recover MCP sensitivity fully, allowing for reuse of the samples after high-dose irradiation and high-temperature measurement.     

The glow curve structure for the LiF:Mg,Cu,Na,Si TL detector with dopants concentrations and sintering temperatures

The glow curve structures for LiF:Mg,Cu,Na,Si TL detectors with various dopant concentrations and sintering temperatures were investigated for the improvement of the glow curve structure and sensitivity of the TL detector. The dopant concentrations were varied over the following ranges: Mg (0–0.25 mol%), Cu (0–0.07 mol%), Na and Si (0–1.5 mol%). With increasing Cu concentration, the intensity of the main peak was intensified and reached a maximum at a concentration of 0.05 mol%. The high-temperature peak was reduced. The dependency of the main peak intensity on the Mg concentration exhibits a sharp maximum at 0.2 mol%. The intensity of the high-temperature peak tends to rise slightly with increasing Mg concentration. It was found that the optimum concentrations of the dopants in the LiF:Mg,Cu,Na,Si TL material are Mg: 0.2 mol%, Cu: 0.05 mol%, Na and Si: 0.9 mol%. The dependency of the main peak intensity on sintering temperature exhibits a very sharp maximum at 830°C. The high-temperature peak was rapidly reduced after 825°C.     

Clinical tests of large area thermoluminescent detectors under radiotherapy beams

Two-dimensional (2D) thermoluminescence (TL) dosimetry systems based on LiF:Mg,Cu,P, together with the newly developed, based on CaSO4:Dy, were tested under radiotherapy beams. The detectors were irradiated in a water phantom with 6 MV X-ray beams from linac and read with a dedicated TLD reader. Dose distributions of differently shaped fields and of a full stereotactic plan were measured and compared with planned distributions.Maximum distance-to-agreement (DTA) in the penumbra region was 1 mm for both LiF:Mg,Cu,P and CaSO4:Dy TL sheets, for all the measured fields. Maximum percentage dose difference (DA%) between planned and measured dose value in low dose gradient regions was up to 11% for LiF:Mg,Cu,P TL sheets and 18% for CaSO4:Dy TL sheets. Concerning the full stereotactic plan, the percentage of points with γ-index below 1 is 54.9% for the LiF:Mg,Cu,P-based foil and 96.9% for the CaSO4:Dy TL sheets. Both 2D TL detector types can be considered to be a promising tool for bi-dimensional dose measurements in radiotherapy. Non-homogeneity, presumably due to the TL sheets manufacture, still affects dosimetric distribution and the agreement between planned and measured distributions may depend on the chosen sample.     

Photoluminescence measurements of LiF TL detectors

The properties of standard lithium fluoride (LiF) thermoluminescent (TL) detectors, which are routinely used in radiation protection systems, were investigated under light stimulation. The luminescence of different types of LiF detectors, which were irradiated with gamma rays of energy up to 300 Gy and alpha particles with a fluence up to 5*10⁹ cm⁻², were stimulated by a blue light and were heated up to temperature of 240 °C or 400 °C, depending on the type of detectors. The irradiated LiF detectors during the blue-light (460 nm) stimulation emit green photoluminescence (PL) with a wavelength of 530 nm. The LiF detectors showed a PL effect of much higher efficiency after they were irradiated with alpha particles than after they were irradiated with gamma rays. However, in contrast to PL, the TL readout showed a significantly lower efficiency of LiF detectors after alpha particle irradiation. These effects result from the different trap mechanisms that are responsible for TL and PL phenomena. The temperature stability of the traps responsible for the PL effect for both types of LiF detectors was studied.     

Application of phototransferred thermoluminescence (PTTL) for dose re-assessment in routine dosimetry using MTS-N (LiF:Mg,Ti) thermoluminescent detectors

Erasure of the thermoluminescence (TL) signal on detector readout is considered to be a disadvantage of TL dosimetry, as post-readout dose reassessment is then impossible in principle. A method of dose reassessment based on phototransferred thermoluminescence (PTTL) has been developed at the Institute of Nuclear Physics, Polish Academy of Sciences (IFJ PAN) and applied to MTS-N (LiF:Mg,Ti) detectors. We demonstrate the possibility of applying PTTL for dose reassessment in MTS-N TL detectors routinely applied in the dosimetric service at IFJ PAN. Readings of TL detectors exposed to relatively high doses by the customers of our dosimetry service can now be reassessed using our automatic readers. A major obstacle in applying the PTTL method at lower exposures is the presence of residual dose accumulated in LiF:Mg,Ti detectors after many field exposure and readout cycles. Since most of the TL detectors in our service have been already used for a long time (e.g. for over 10 years in the case of some detector batches), we find that our PTTL method of dose reassessment is possible only in detectors which had received doses exceeding 5 mSv.     

Relative efficiency of TL detectors to energetic ion beams

The relative TL efficiency of LiF:Mg, Ti and LiF:Mg, Cu, P was evaluated for several ion beams, ranging from helium to xenon ions. Irradiations were realized at the HIMAC accelerator in Chiba, Japan, partly within the ICCHIBAN intercomparison project. The covered LET range was extending from about 2 keV/μm to 1500 keV/μm.Both tested TLD types exhibited a decrease of relative response with increasing ionization density – stronger for LiF:Mg,Cu,P detectors. The relationship between efficiency and LET was found to follow unique trend lines, as nearly all data points lied within 5% around the fitted empirical functions. Values of TL efficiency measured for various batches of same type TLDs agree within a few percent. The measured relationships between relative TL efficiency and LET will be used in the analysis of data obtained from space dosimetric experiments.     

OSL signal of lithium fluoride and its relationship with TL glow-curves

The widely known LiF TL detectors: LiF:Mg,Ti (MTS-N) and LiF:Mg,Cu,P (MCP-N), were investigated with respect to their OSL properties. It was found that both materials exhibit quite substantial OSL sensitivity. In particular, in the case of LiF:Mg,Cu,P this sensitivity was very high, significantly exceeding that of BeO, the standard OSL dosimetric material. LiF:Mg,Cu,P could be a very promising candidate for application in dosimetry, if not for the fading, which was found to be quite high, reaching nearly 80% loss of the signal within 60 h. The OSL signal intensity shows a correlation with the peak 2 of the TL glow curves indicating that the same trapping sites are responsible for both processes. Peak 2 of LiF:Mg,Ti shows a peculiar property, that blue light stimulation removes only about half of its initial intensity, disregarding the duration of stimulation. This suggests, that this peak may have a composite structure and originates from both light-sensitive and light-insensitive trapping centres.     

Feasibility study of CaSO4:Eu,CaSO4:Eu,Ag and CaSO4:Eu,Ag(NP) as thermoluminescent dosimeters

This work evaluates the dosimetric properties of crystals of CaSO₄ doped with unusual elements, such as europium (Eu) and silver (Ag), including their nanoparticle forms, after the incorporation of glass or Teflon and compares them with well-known thermoluminescent dosimeters (TLD). X-ray diffraction analyses showed that samples of doped CaSO₄ exhibit only a single phase corresponding to the crystal structure of anhydrite. Optical spectroscopy confirmed the presence of Eu³⁺ in the crystal matrix and a luminescent gain due the presence of silver nanoparticles. The composites showed thermoluminescent emission glow curves, with a single peak centered at approximately 200 °C for pellets with Teflon and at 230 °C for pellets with glass. The dosimeters based on calcium sulfate doped with europium and silver nanoparticles provided the most intense thermoluminescent (TL) emission of the composites studied. In comparison with commercial TLD, such as LiF:Mg,Ti and CaSO₄:Dy, the CaSO₄:Eu,Ag(NP)+glass produced in this work presented similar low detection limits and higher sensitivity. The new methods for the preparation of dosimeters and the incorporation of glass are shown to be viable because all of the samples presented a linear, reproducible and first order kinetic TL emission.