Lithium fluoride: from LiF:Mg,Ti to LiF:Mg,Cu,P

Differences and similarities between LiF-based LiF:Mg,Ti and LiF:Mg,Cu,P are discussed, with respect to their dosimetric properties--sensitivity, non-linearity of dose response and heavy charged particle efficiency, as related to the concentration and the individual role of the Mg, Ti, Cu and P dopants. To study further the role of these dopants, the properties of some new, 'hybrid' phosphors: LiF:Mg,Cu,Ti and LiF:Mg,P, specially developed for this purpose, are also discussed. In the glow curve of LiF:Mg,Cu,P with a low concentration of Mg a new peak was found, which appears to be an analogue of peak 4 in LiF:Mg,Ti, Magnesium apparently controls most of the dosimetric properties of LiF-based phosphors. For instance, charged-particle efficiency appears to be anti-correlated with the concentration of Mg, being much less dependent on the content of other dopants. On the other hand, some properties of LiF-based systems seem to be correlated with changes in the emission spectra. It is suggested that Ti hampers the acceptance of any increased amount of Mg into more traps in LiF:MgTi. The absence of Ti, not the presence of P or Cu, is therefore a key to the high sensitivity of LiF:MgCuP.     

Thermoluminescence emission spectra for the LiF:Mg,Cu,Na,Si thermoluminescent materials with various concentrations of the dopants (3-D measurement)

The thermoluminescence (TL) emission spectra from LiF TL materials, called KLT-300 (LiF:Mg,Cu,Na,Si) with various dopant concentrations are measured and analysed. These KLT-300 materials were developed by the Korea Atomic Energy Research Institute (KAERI) to achieve an enhancement of the thermal stability in TL readings. Six types of samples are prepared with different dopant concentrations in the following ranges; Mg (0-0.20 mol%), Cu (0-0.05 mol%), Na and Si (0-0.9 mol%). The spectra measurements are carried out for the six types of samples using a TL emission spectra measurement device. The spectra measurement device consists of a monochromator, photomultiplier tube and temperature control unit to thermally stimulate the samples. The measured data shows the light emission during heating of the sample as a function of temperature and wavelength (three-dimensional TL spectra). The spectra were analysed using a method of deconvolution based on gaussian curve. The wavelength of a main peak of the emission spectra changes depending on the existence of the Cu dopant, while intensity of the spectra rapidly changes with the Cu dopant concentrations. The 385 nm emission is mainly observed in all the spectra from the samples with the Cu dopant, but in those from the samples without the Cu dopant a very weak 401 nm emission is mainly observed. However, any change in the wavelength at a main peak of the TL emission spectra from the sample materials with Na and Si dopants is not observed but that in the intensity at a peak of the spectra is observed.     

On the roles of the dopants in LiF: Mg,Cu,Na,Si thermoluminescent material

In this paper, some results of the study on the roles of the dopants in the LiF:Mg,Cu,Na,Si thermoluminescent (TL) material that was developed at the Korea Atomic Energy Research Institute for radiation protection are presented. Although there have been many studies to investigate the roles of the dopants in LiF:Mg,Cu,P TL material in the TL process, there are some discrepancies in the understanding of the roles of Cu and P between various researchers. In case of LiF:Mg,Cu,Na,Si TL material, there are a few studies on the roles of the dopants. Three kinds of samples in each of which one dopant is excluded, and the optimised sample, were prepared for this study. The measurements and analysis of the three-dimensional TL spectra, based on the temperature, wavelength and intensity, and the glow curves for those samples are used in this study. The results show that Mg plays a role in the trapping of the charge carriers and Cu plays a role in the luminescence recombination process; however, the effect of Na and Si on the glow curve structure and the TL emission spectra is much less than that of Mg and Cu. It is considered that Na and Si each plays a role in the improvement of the luminescence efficiency.     

Pre- and post-irradiation fading effect for LiF:Mg,Ti and LiF:Mg,Cu,P materials used in routine monitoring

LiF is a well-known thermoluminescent (TL) material used in individual monitoring, and its fading characteristics have been studied for years. In the present study, the fading characteristics (for a period of 150 d) of various commercial LiF materials with different dopants have been evaluated. The materials used in the study are those used in routine procedures by the Personal Dosimetry Department of Greek Atomic Energy Commission and in particular, LiF:Mg,Ti (MTS-N, TL Poland), LiF:Mg,Cu,P (MCP-N, TL Poland), LiF:Mg,Cu,P (MCP-Ns, thin active layer detector, TL Poland) and LiF:Mg,Cu,P (TLD100H, Harshaw). The study showed that there is a sensitivity loss in signal of up to 20 % for the MTS-N material for a 150-d period in the pre-irradiation fading phase. The MCP-N has a stable behaviour in the pre-irradiation fading phase, but this also depends on the readout system. As far as the post-irradiation fading effect is concerned, a decrease of up to 20 % for the MTS-N material is observed for the same time period. On the other hand, the LiF:Mg,Cu,P material presents a stable behaviour within ± 5 %. These results show that the fading effect is different for each material and should be taken into account when estimating doses from dosemeters that are in use for >2 months.     

Developments in the synthesis of LiF:Mg,Cu,Na,Si TL material

A procedure for synthesis of the highly sensitive pellet-type LiF:Mg,Cu,Na,Si thermoluminescent (TL) detector has been newly developed. It was found that the optimum concentrations of dopants for a pellet-type LiF:Mg,Cu,Na,Si TL detector were found to be Mg: 0.2 mol %, Cu: 0.05 mol %, Na: 0.9 mol%, and Si: 0.9 mol%. The TL sensitivity of this new detector was about 30 times higher than that of the TLD-100 by light integration measurements. Reusability study of the detector was carried out for 10 cycles. The results show that the coefficients of variation for each detector separately did not exceed 0.016, and that for all 10 detectors collectively was 0.0054.     

Evaluation of the performance of two LiF:Mg,Ti and LiF:Mg,Cu,P dosemeters for extremity monitoring

In this paper, the results aimed at assessing the performance of two varieties of LiF detectors (LiF:Mg,Ti and LiF:Mg,Cu,P) in photon fields relatively to reproducibility, detection threshold and angular dependence as defined in the ISO 12794 standard are presented. The fading properties and the limit of detection were also investigated for both materials. The results suggest that both LiF varieties are well suited for extremity monitoring. However, better fading properties of LiF:Mg,Cu,P when compared with LiF:Mg,Ti, combined with previous results relatively to energy dependence suggests that LiF:Mg,Cu,P dosemeters are better suited for extremity monitoring.     

Reproducibility of TL measurements in a mixed field of thermal neutrons and photons

The reproducibility of measurements performed with GR-100 (LiF:Mg,Ti) from the Solid Dosimetric Detector and Method Laboratory (DML) China, GR-107 (7LiF:Mg,Ti, DML), TLD-700H (7LiF:Mg.Cu,P, Harshaw) and Al2O3:Mg,Y (Hungary) in photon and mixed photon-neutron fields was investigated. Mixed-field irradiations were performed in a thermal neutron field generated at a nuclear reactor. GR-100 sensitivity decreased after mixed-field irradiations, while no significant change was found for the other materials. Using GR-100 for the dosimetry of mixed and high-intensity fields requires careful procedures.     

The application of LiF:Mg,Cu,P to large scale personnel dosimetry: current status and future directions

LiF:Mg,Cu,P is starting to replace LiF:Mg,Ti in a variety of personnel dosimetry applications. LiF:Mg,Cu,P has superior characteristics as compared to LiF:Mg,Ti including, higher sensitivity, improved energy response for photons, lack of supralinearity and insignificant fading. The use of LiF:Mg,Cu,P in large scale dosimetry programs is of particular interest due to the extreme sensitivity of this material to the maximum readout temperature, and the variety of different dosimetry aspects and details that must be considered for a successful implementation in routine dosimetry. Here we discuss and explain the various aspects of large scale LiF:Mg,Cu,P based dosimetry programs including the properties of the TL material, new generation of TLD readers, calibration methodologies, a new generation of dose calculation algorithms based on the use of artificial neural networks and the overall uncertainty of the dose measurement. The United States Navy (USN) will be the first US dosimetry processor who will use this new material for routine applications. Until June 2002, the Navy used two types of thermoluminescent materials for personnel dosimetry, CaF2:Mn and LiF:Mg,Ti. A program to upgrade the system and to implement LiF:Mg,Cu,P, started in the mid 1990s and was recently concluded. In 2002, the new system replaced the LiF:Mg,Ti and is scheduled to start replacing the CaF2:Mn system in 2006. A pilot study to determine the dosimetric performance of the new LiF:Mg,Cu,P based dosimetry system was recently completed, and the results show the new system to be as good or better than the current system in all areas tested. As a result, LiF:Mg,Cu,P is scheduled to become the primary personnel dosimeter for the entire US Navy in 2006.     

UV-induced bleaching of deep traps in Harshaw TLD LiF:Mg,Cu,P and LiF:Mg,Ti

The effects of UV-induced bleaching of deep traps on Harshaw thermoluminescent (TL) LiF:Mg,Cu,P and LiF:Mg,Ti materials were investigated. During a normal heating cycle, LiF:Mg,Cu,P is limited to a maximum temperature of 240 °C. LiF:Mg,Ti can be read to higher temperatures; however, encapsulation in polytetrafluoroethylene limits the maximum readout temperature to 300 °C. Generally, for both materials, these respective temperatures are sufficient for emptying traps corresponding to the main dosemetric peaks. However, when the dosemeters are subjected to a high dose level, such as 1 Gy (much higher than individual monitoring dose levels), higher temperature traps are filled that cannot be emptied without exceeding the above-mentioned maximum temperatures. These high temperature traps tend to be unstable during normal readout and can significantly increase the residual TL signal. The purpose of this study was to investigate the applicability of a UV-induced bleaching technique for emptying higher temperature traps following high-dose applications. In addition, in the case of LiF:Mg,Cu,P, where the maximum readout temperature is significantly lower, we investigated the possibility of reducing the residual signal using the application of repeated readout cycles. The optical bleaching approach was found to be effective in the case of LiF:Mg,Ti; however, for LiF:Mg,Cu,P, no reduction in the residual signal was observed. For this latter material, the application of repeatable readout cycles is very effective and residual signals equivalent to dose levels as low as 0.01 mGy were observed following an initial dose of 5 Gy. To the best of our knowledge, this work is the first attempt to apply an 'optical annealing' technique to the Harshaw thermoluminescent dosemeter (TLD) materials.     

Comparison of the effects of exposure to light in Harshaw LiF:Mg,Ti and LiF:Mg,Cu,P

The response of thermoluminescence dosemeters (TLDs) to light, in various conditions, has been studied. TLD cards containing both conventional lithium fluoride (LiF:Mg,Ti) and the high-sensitivity material LiF:Mg,Cu,P were available, so permitting a comparison between the two types. Also available for the tests were Harshaw(TM) extremity EXT-RAD (LiF:Mg,Cu,P) dosemeters. The LiF:Mg,Ti body TLD cards and the EXT-RAD extremity dosemeters both showed some response to fluorescent light, while the LiF:Mg,Cu,P cards showed no significant response. It is therefore concluded that LiF:Mg,Cu,P body cards need no special precautions to protect them from the effects of light. For LiF:Mg,Ti cards and extremity dosemeters, effects are small, but steps to avoid excessive light exposure should be considered.     

Thermoluminescence dosimetry of a thermal neutron field and comparison with Monte Carlo calculations

The characteristics of thermoluminescence dosemeters (TLDs) regarding the determination of photon and neutron absorbed doses were investigated in a thermal neutron beam. Harshaw TLD-100 (LiF:Mg,Ti) and TLD-700 (7LiF:Mg,Ti) were compared with similar materials from Solid Dosimetric Detector and Method Laboratory (People's Republic of China). Harshaw TLD-700H (7LiF:Mg,Cu,P) and aluminium oxide (Al2O3:Mg,Y) from Hungary were also considered for photon dose measurement. The neutron sensitivity of the investigated materials was measured and found to be consistent with values reported by other authors. A comparison was made between the TL dose measurements and results obtained via conventional methods. An agreement within 20% was obtained, which demonstrates the ability of TLD for measuring neutron and photon doses in a mixed field, using careful calibration procedures and determining the neutron sensitivity for the usage conditions.     

Comparative study of LiF:Mg,Cu,Na,Si and Li2B4O7:Cu,Ag,P TL detectors

Recently, two new types of 'tissue equivalent' thermoluminescent detectors (TLDs) have aroused attention: LiF:Mg,Cu,Na,Si and Li2B4O7:Cu,Ag,P. In this work the characteristics of both detectors were compared with the characteristics of the well-known type LiF:Mg,Ti detector, TLD-100. The following properties were investigated: the glow curve structures, relative sensitivity, batch homogeneity and uniformity, detection threshold, reproducibility of the response, linearity in the wide dose range and fading. Also, the energy dependence for medium and low energy X rays was determined in the range of mean energies between 33 and 116 keV. The results confirmed 'tissue equivalency' of both new types in the investigated range of photon energies. LiF:Mg,Cu,Na,Si detector has very high sensitivity (approximately 75 times higher than that of TLD-100) and is convenient for use in a very low range of doses. Li2B4O7:Cu,Ag,P detector shows some improvements in comparison with the previously prepared types of lithium borate. The most important is the five times higher sensitivity than that of TLD-100. This detector is also very promising, especially in medical dosimetry.     

A comparative study on the susceptibility of LiF:Mg,Ti (TLD-100) and LiF:Mg,Cu,P (TLD-100H) to spurious signals in thermoluminescence dosimetry

It is well known that spurious signals can occur in thermoluminescence dosimetry (TLD) whenever contaminants (i.e. dirt, oil, dust) are present on the surface of the TLD card or crystal during the read-out process. For TLD cards, the Teflon material can also contribute to the background noise and this contribution has been found to depend on the material's light absorption. These non-radiation-induced signals contribute to the total light output during TLD read-out and can lead to incorrect dosimetry especially for low-dose measurements such as personal dosimetry. However, these spurious signals are generally in the low-temperature channels and are mostly accompanied by abnormal glow curves. Most of the published reports dealing with this type of spurious TL signal are on the LiF:Mg,Ti (TLD-100) material. The relatively new TLD material, LiF:Mg,Cu,P, is more sensitive and has higher signal-to-noise ratio than the traditional LiF:Mg,Ti. In this study, the effects of disturbing signals to the LiF:Mg,Cu,P (TLD-100H) cards used in personal dosimetry are investigated and compared with those of LiF:Mg,Ti (TLD-100).     

Energy response of LiF and Mg2SiO4 TLDs to 10-150 keV monoenergetic photons

Energy response of LiF:Mg,Ti, LiF:Mg,Cu,P and Mg2SiO4:Tb thermoluminescence dosemeters (TLDs) was measured in the range 10-150 keV for monoenergetic photons at SPring-8 of an 8-GeV synchrotron radiation facility. The photon beam was monitored by a parallel-plate free-air ionisation chamber calibrated with an uncertainty of 3%. Owing to the small dimension of the beam, a rotating holder was designed in order to irradiate TLDs uniformly. The measured responses of LiF to energy were approximately in agreement with the calculated dose absorption dependence in the soft tissue. However, two types of LiF TLDs presented the different luminescent responses to the photon energy. The response of LiF:Mg,Ti had a smooth curve, and that of LiF:Mg,Cu,P presented a local maximum at 30 keV and a local minimum at 100 keV. The Mg2SiO4:Tb response was nearly bone equivalent. Linearity of dose responses was also confirmed up to 2 Gy on each TL material.     

Low temperature radioluminescence of LiF:Mg,Cu,P

Low temperature radioluminescence spectra of LiF, variously co-doped with Mg, Cu and P, show highly unusual temperature dependencies which resemble thermoluminescence data. The signals include intense peaks and a relatively weak continuous background. One peak occurs below 30 K, together with a major peak near 125 K. The signals are highly sensitive to the dopants and slightly sensitive to X-ray dose rate. The role of donor acceptor pairs and the perturbations from intrinsic defects formed by ionisation can be used to describe all the observations. The 290 nm emission band is linked to H center annealing.     

On the relationship between dose-, energy- and LET-response of thermoluminescent detectors

Measurements of the response of thermoluminescent (TL) detectors after gamma ray doses high enough to observe signal saturation provide input to microdosimetric models which relate this gamma-ray response with the energy response after low doses of photons (gamma rays and low-energy X rays) and after high-LET irradiation. To measure their gamma ray response up to saturation, LiF:Mg,Ti (MTS-7 and MTT), LiF:Mg,Cu,P (MCP-7), CaSO4:Dy (KCD) and Al2O3:C detectors were irradiated with 60Co gamma rays over the range 1-5000 Gy. The X-ray photon energy response and TL efficiency (relative to gamma rays) after doses of beta rays and alpha particles, were also measured, for CaSO4:Dy and for Al2O3:C. Microdosimetric and track structure modelling was then applied to the experimental data. In a manner similar to LiF:Mg,Cu,P, the experimentally observed under response of alpha-Al2O3:C to X rays <100 keV, compared with cross-section calculations, is explained as a microdosimetric effect caused by the saturation of response of this detector without prior supralinearity (saturation of traps along the tracks). The enhanced X-ray photon energy response of CaSO4:Dy is related to the supralinearity observed in this material after high gamma ray doses, similarly to that in LiF:Mg,Ti. The discussed model approaches support the general rule relating dose-, energy- and ionisation density-responses in TL detectors: if their gamma ray response is sublinear prior to saturation, the measured photon energy response is lower, and if it is supralinear, it may be higher than that expected from the calculation of the interaction cross sections alone. Since similar rules have been found to apply to other solid-state detector systems, microdosimetry may offer a valuable contribution to solid-state dosimetry even prior to mechanistic explanations of physical phenomena in different TL detectors.     

Development of LiF:Mg,Cu,Si TL material (new KLT-300) with a low-residual signal and high-thermal stability

LiF-based thermoluminescence (TL) materials have been widely used for radiation dosimetry due to their attractive features. LiF:Mg,Cu,P is one of the most sensitive tissue-equivalent TL materials, approximately 40 times more sensitive than LiF:Mg,Ti (TLD-100), but it has two main drawbacks: a thermal loss of the TL sensitivity when annealed at temperatures >240 degrees C, and a relatively high-residual signal. Recently, LiF:Mg,Cu,Na,Si TL material was developed to overcome these drawbacks at the Korea Atomic Energy Research Institute, but it provided only marginal improvements in reducing the residual signal. The newly developed LiF:Mg,Cu,Si TL material has a significantly lower residual signal and a better stability to thermal treatments. In this article, the preparation method and some dosimetric properties (sensitivity and residual signal) of the new LiF:Mg,Cu,Si TL material are presented. At the end of the preparation procedures, a dual-step annealing method is introduced and this has proved as a very efficient method to reduce the high-temperature peak and is the cause of residual signal. Therefore, the high-temperature peak in the glow curve was significantly reduced. The sensitivity is approximately 20 times higher than that of TLD-100 and the residual signal was estimated to be approximately 0.04%.     

Miniature thermoluminescent detectors for dosimetry in radiotherapy

At the Institute of Nuclear Physics in Kraków (INP), in collaboration with the Centre of Oncology in Kraków, several types of miniature thermoluminescent LiF:Mg,Ti and LiF:Mg,Cu,P detectors specially designed for clinical dosimetry in radiotherapy have been developed. The detectors are manufactured in the form of solid pellets of diameter down to 1 mm and typical thickness 0.5 mm, in the form of rods with a diameter of 0.5 mm and a length of a few mm, and as two-layer detectors with a thin (in the range of 0.065 mm) active layer of high-sensitive LiF:Mg,Cu,P. All three types of newly developed detectors have already been applied in proton beam dosimetry, surface dosimetry of eye-plaque brachytherapy applicators, phantom dosimetry for vascular brachytherapy and in vivo dosimetry in interstitial brachytherapy. These detectors were found to be very useful for dose measurements in high dose gradients, where spatial resolution better than 1 mm is required.     

TiO2 doped with nitrogen: synthesis and characterization

In this study, nitrogen-doped titanium dioxide (TiO2) powders were synthesized in two ways: by heating of titanium hydroxide with urea and by direct hydrolysis of titanium tetraisopropoxide (TTIP) with ammonium hydroxide. The samples were characterized by structural (XRD), analytical (XPS), optical (UV/Vis absorption/reflection and Raman spectroscopy) and morphological (SEM, TEM) techniques. The characterization suggested that the doped materials have anatase crystalline form without any detectable peaks that correspond to dopants. The absorption threshold of titanium dioxide was moved in the visible range of optical spectrum from 3.2 eV to 2.20 eV. Particle sizes of synthesized powders were obtained from XRD measurements and from TEM data ranging from 6-20 nm. XPS and Raman spectroscopy were used for detection of nitrogen in doped samples.