High-dose characterization of different LiF phosphors

The dose response of three LiF TLDs: standard LiF:Mg,Ti (denoted MTS), high-sensitive LiF:Mg,Cu,P (MCP) and a recently developed in Kraków version of LiF:Mg,Ti with modified activator composition (MTT) and increased high-LET response was measured. The TLDs have been exposed to ⁶⁰Co gamma-rays, up to dose of 10 000 Gy, i.e. beyond saturation dose of the main dosimetric peaks, which corresponds to ca. 1000 Gy. The measured glow-curves were deconvolved into separate peaks with first order kinetic function (using self-developed GlowFit software). The dose response of the main peaks was found to be supralinear for MTS and sublinear for MCP detectors, as expected. The dose response of MTT was found to be even more supralinear than that of MTS. An interesting effect has been observed with regard to glow-curve shape of MCP detectors. Up to a dose of 1 kGy it remains practically unchanged, while for higher doses a strong growth of high-temperature peaks is observed. In the same dose region a decrease of the main peak of MCP with increasing dose is observed, unlike LiF:Mg,Ti detectors.     

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.     

Radio-photoluminescence of highly irradiated Lif:Mg,Ti and Lif:Mg,Cu,P detectors

The radio-photoluminescent (RPL) characteristics of LiF:Mg,Ti (MTS) and LiF:Mg,Cu,P (MCP) thermoluminescent detectors, routinely used in radiation protection dosimetry, were investigated after irradiation with ultra-high electron doses ranging up to 1 MGy. The photoluminescence of both types of LiF detectors was stimulated by a blue light (460 nm) and measured within a spectral window around 530 nm. The RPL dose response was found to be linear up to 50 kGy and sublinear in the range of 50 kGy to 1 MGy for MCP detectors and linear up to 3 kGy and next sublinear in the range from 5 kGy to 1 MGy for MTS detectors. For both type of LiF detectors RPL signal is saturated for doses higher than 100 kGy. The observed differences between MCP and MTS may suggest, that the RPL effect in LiF is not entirely governed by intrinsic defects (F₂ and F₃⁺ centers), but dopants may also have a significant influence. Due to the non-destructive character of the RPL measurement, it is suggested to apply combined RPL/TL readouts, what should improve accuracy of high-dose dosimetry.     

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.     

Spectrally resolved thermoluminescence of highly irradiated LiF:Mg,Cu,P detectors

Well known, widely applied high sensitive thermoluminescence (TL) detector LiF:Mg,Cu,P (MCP-N) was investigated. This paper analyses changes of the TL emission spectrum of MCP-N after irradiation with ultra high doses (up to 500 kGy). Spectral dependence of TL on dose is very complex especially in the region of very high doses (>1 kGy). As a general trend we found that the number of peaks increases with dose in the long-wavelength region indicating new types of recombination centres (RCs). Wavelength peak positions for increasing doses are quite stable. Only some of them show slight red-shift.     

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.     

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 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.     

Optimization of preparation procedure of LiF:Mg,Cu,Si TLD for improving the reusability

Several thermal treatments in the temperature range from 270 °C to 320 °C (each of 10 min) were tested as a final preparation procedure of LiF:Mg,Cu,Si to improve the protocol of TL readout with less residual signal for the LiF:Mg,Cu,Si TLD. This high sensitivity LiF:Mg,Cu,Si TLD exhibited thermal stability much better than that of the well known LiF:Mg,Cu,P. For LiF:Mg,Cu,Si, a readout temperature up to 300 °C did not affect the TL sensitivity and glow curve structure for 12 cycles of exposure and readout following an initial thermal treatment at 295 °C for 10 min. The residual TL signal also remained negligible.     

Environmental gamma-ray dose rate measurement by using ultra-high sensitive LiF:Mg,Cu,Si TLD

Environmental gamma-ray dose rates were measured by using ultra-high sensitive LiF:Mg,Cu,Si thermoluminescence dosimeters (TLDs) during short-term burial. The resultant gamma-ray dose rates were compared with those measured by using optically stimulated luminescence (OSL) of Al₂O₃:C and assessed by using HPGe spectrometer. Regardless of the short-term burial and the change of environmental conditions as well as the mismatch of the effective atomic number (Z_eff) with the soil (mainly SiO₂), good agreement was observed between the doses measured by TLDs and OSL dosimeters or the assessed doses. LiF:Mg,Cu,Si TLD has been found to be an effective alternative for the measurement of environmental gamma-ray annual dose rates for use in optical dating.     

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.     

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.     

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.     

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.     

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.     

Thermoluminescence of nanocrystalline LiF:Mg, Cu, P

Nanocrystalline LiF:Mg, Cu, P of rod shape (about 30-40 nm in diameter and 0.3-0.5 μm in length) has been prepared by the chemical co-precipitation method. Thermoluminescence (TL) and dosimetric characteristics of the nanocrystalline phosphor are studied and presented here. The formation of the material was confirmed by the X-ray diffraction (XRD). Its shape and size were also observed by transmission electron microscope (TEM). The TL glow curve of the nanocrystalline powder shows a single peak at 410 K along with four overlapping peaks of lesser intensities at around 570, 609, 638 and 663 K. The observed TL sensitivity of the prepared nanocrystalline powder is less than that of the commercially available “Harshaw TLD-700H hot-pressed chips” at low doses but it still around three times more than that of LiF:Mg, Ti (TLD-100) phosphor. The 410 K peak of the nanomaterial phosphor shows a very linear response with exposures increasing up to very high values (as high as 10 kGy), where all the other thermoluminesent dosimeters (TLD) phosphors show saturation. This linear response over a large span of exposures (0.1 Gy-10 kGy) along with negligible fading and its insensitivity to heating treatments makes the nanocrystalline phosphor useful for its application to estimate high exposures of γ-rays. The ‘tissue equivalence’ property of this material also makes it useful over a wide range of high-energy radiation.     

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.