Investigation of the optical absorption dose response of LiF:Mg,Ti (TLD-100) and the role of V centers in F center (5.08 eV) bleaching

The optical absorption (OA) dose response of irradiated LiF:Mg,Ti has been measured over the dose range from 100 Gy to 1.4 M Gy. Measurements at high dose indicate that the 4.0 eV band is actually a composite band at 3.84 eV and 4.3 eV. Bleaching experiments at 5.08 eV (F band) support the participation of V₃ centers in the relaxation mechanisms following the bleach. The results are interpreted in the framework of a spatially correlated trapping center/luminescent center giving rise to composite peak 5 in the glow curve.     

Investigation of the optical absorption characteristics of slow-cooled LiF:Mg,Ti (TLD-100)

The optical absorption (OA) spectrum of LiF:Mg,Ti has been studied as a function of dose at two different cooling rates following the 400 °C pre-irradiation anneal in order to further investigate the role of cooling rate in the thermoluminescence (TL) mechanisms of this material. “Slow-cooling” following the pre-irradiation 400 °C anneal substantially decreases the OA bands at 3.25 eV and 4.0 eV, in agreement with the overall loss in TL peaks 2–5 intensity using slow-cooling routines. Slow-cooling appears to shift the maximum intensity of peak 5 to lower temperatures (a behaviour which has been attributed to an enhanced intensity of peak 5a), however, no difference in the shape of the 4.0 eV OA band is detected following “slow-cooling”. Apparently the OA band related to peak 5a is too close in energy to the peak 5 OA band to be observed due to lack of sufficient resolution and spectral deconvolution process or it is not present at room temperature (RT) and formed during heating of the sample. The intensity of the 4.0 eV OA band does not change if the sample (prior to irradiation to a standard dose of 200 Gy) is irradiated to 4 kGy followed by a 500 °C/1 h post-irradiation anneal. This result demonstrates that the loss of intensity at high levels of dose (so-called radiation damage) of TL glow peak 5 results from alteration of the LCs or to the creation of additional competitive centers and is not correlated with the dose behaviour of the TCs.     

Kinetic simulation of charge transfer following 5.08 eV (F band) optical excitation of irradiated LiF:Mg,Ti (TLD-100): Participation of holes released via V3-VK transformation

Kinetic simulations of charge transfer in the framework of the conduction band/valence band model are described which investigate the effect of 5.08 eV photon bleaching on the optical absorption spectrum of irradiated LiF:Mg,Ti (TLD-100). The decrease in intensity of the 3.8 eV and 4.3 eV bands, newly discovered sub-entities of the 4.0 eV composite band, is interpreted as arising from the participation of holes released by capture of electrons at V₃ two-hole-centers. The simulations also require highly efficient electron transfer from the excited state of the F center to the V₃ center which is necessary to guarantee an adequate supply of released holes following the V₃-V_k transformation.     

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.     

Ion beam induced luminescence studies of LiAlO2 using negative ions

Lithium aluminate (LiAlO₂) is the candidate material for solid tritium breeder applied in the developing fusion reactors. The research of its defect behavior under ion irradiation was proceeded in the negative ions induced luminescence setup of the GIC4117 Tandem accelerator in Beijing Normal University. The ion beam induced luminescence (IBIL) measurement was performed by 20 keV H⁻ ions at room temperature. The luminescence spectra showed seven emission bands: the 4.55 eV may due to a self-trapped exciton (STE), the 4.06 eV and the 1.72 eV may due to impurity or intrinsic defect, the 3.54 eV due to F center, the 3.20 eV due to F⁺ center, the 2.93 eV due to F₂ center, the 2.30 eV due to F-center aggregates (F_n center), respectively. The intensity evolutions of each band with fluence were presented and the corresponding mechanisms were discussed.     

Nanodosimetric kinetic model incorporating localized and delocalized recombination: Application to the prediction of the electron dose response of the peak 5a/5 ratio in the glow curve of LiF:Mg,Ti (TLD-100)

A kinetic model combining both localized and delocalized recombination is described which is based on different filling rates as a function of irradiation electron energy of a spatially correlated trapping center/luminescent center (TC/LC) complex. Following irradiation and thermal de-trapping the locally trapped electron-hole configuration is assumed to give rise to peak 5a and the e-only configuration to peak 5 in the glow curve of LiF:Mg,Ti (TLD-100). The model is capable of simulating the linear/supralinear dose response of composite peak 5, the dependence of the supralinearity on photon energy and the ratio of the intensities of peak 5a to peak 5 as a function of dose. However, this is achieved only by invoking the presence of band-tail states which allow thermally induced hopping leading to semi-localized recombination in the recombination mechanism of the e-only configuration.     

Spectral characteristic of high-dose high-temperature emission from LiF:Mg,Cu,P (MCP-N) TL detectors

High-temperature emission spectra of LiF:Mg,Cu,P (MCP-N) TL detectors, irradiated above the nominal saturation level, up to the hundreds of kGy, have been measured. Emission spectra integrated over the whole temperature range, as well as the spectra recorded at the temperatures corresponding to the TL peaks maxima, were analyzed. With increasing dose of γ-radiation no significant changes were observed in the short wavelength emission range (220–450 nm) of the measured spectra. For doses of 4 kGy and higher the long wavelength emission (450–800 nm) started to be visible. All recorded spectra have been expressed in a form of the sum of several Gaussian-shape bands in the energy domain, which parameters remain in a general agreement with the measurements of Mandowska et al. (2010). Spectra of the low-temperature, main, high-temperature and “B” TL peaks were investigated. In the ranges of the low-temperature and the main dosimetric peaks, that is 100–125 and 210–230 °C, respectively, the short wavelength emission disappeared with increasing dose and for the highest doses the long wavelength emission became dominant. Both the high-temperature (290–320 °C) and the “B” (370–425 °C) peaks emission spectra exhibited somewhat different behavior with increasing dose. Initially, an even growth of the whole spectrum was observed and for doses higher than 16 kGy the intensity of the spectrum decreased, but the short wavelength emission band fell significantly faster, in case of the high-temperature TL peaks. In case of the “B” peak emission spectra the long wavelength emission did not play any role in the analyzed dose range. The spectra measured at the TL peaks maxima were also fitted with several Gaussian-shape bands. Dose-intensity dependences for all Gaussian-shape bands fitted to the measured spectra are also included in this paper.     

Ultraviolet photoemission study of LiF

Photoemission from evaporated films of LiF were measured at photon energies of 10-27 eV. The photoelectron spectra exhibit features that can be identified as density-of-states structures in the valence and conduction bands of LiF. Regions of high density of states can be seen at ca. 3.3 and 7.8 eV above the vacuum level. The valence-band spectrum shows a doublet structure similar to the calculated density of states for the F^?2p band of LiF. The base width of this structure is found to be 4.6 ± 0.3 eV. The photoelectron spectra for photon energies > 15 eV indicate that the highest occupied states of the F^?2p band are located at 11.8 ± 0.3 eV below the vacuum level. The photoelectron spectra in the exciton region, however, show photo-emission from higher occupied states.     

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.     

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.     

Radiation induced defects in SiO 2

The main luminescent centers in SiO 2 films are the red luminescence R (650 v nm; 1.85 v eV) of the non-bridging oxygen hole center (NBOHC) and the twofold-coordinated (divalent) silicon with a blue B (460 v nm; 2.7 v eV) and a UV band (285 v nm; 4.4 v eV). Especially the latter ones are produced under irradiation, but from existing precursors assumed as silicon related oxygen deficient centers (SiODC). Therefore, in order to prove these models we compare a direct oxygen implantation with a direct silicon implantation into SiO 2 layers. The main result is: implanting oxygen increases the red band R but does not affect the blue band B. Silicon surplus increases the amplitude of the blue (B) luminescence, but reduces the amplitude of the red (R) one. Studying the cathodoluminescence dose dependence of these blue and red bands we have established defect transformation kinetics in SiO 2 including six main defects and precursors as well as the mobile oxygen as the main transmitter between precursors and the radiation induced defects. The kinetics is described by eight rate equations which predict the dose dependence of the red (R) and blue (B) luminescence intensities and their temperature dependences very well.     

Photoluminescence studies of γ-irradiated CaF2:Dy:Pb:Na single crystals

The optical absorption (OA) and photoluminescence (hereafter referred to as luminescence) studies were made on CaF₂:Dy:Pb:Na single crystals (Dy—0.005 at%, Pb—0.188 at% and Na—0.007 at%) before and after γ-irradiation. The unirradiated crystal exhibited a strong OA band around 6.36 eV attributed to the ‘A’ band absorption of Pb²⁺ ions. The γ-irradiated crystal exhibited OA bands around 2.06, 3.28, 3.75 (broad shoulder) and 2.48 eV. The first three bands could be tentatively attributed to M_Na centre when compared with that of the coloured CaF₂:Na. The origin of 2.48 eV band was not explicitly known. Luminescence emission and excitation of Pb²⁺ and Dy³⁺ ions were negligible in the unirradiated crystal. Irradiated crystal exhibited a strong excitation spectrum with overlapping bands, due to different colour centres, in the UV-vis region for the 2.15 eV emission characteristic of Dy³⁺ ion. When excited, the absorbed energy (may be a part) was transferred from a colour centre to nearby Dy³⁺ ions and Dy³⁺ characteristic emission was observed. Exciting the irradiated crystal around 3.28 eV yielded emission at 2.56, 2.15 and 1.76 eV. The first two emission bands were due to Dy³⁺ ions. The excitation spectrum for the 1.76 eV emission showed two prominent bands around 2.02 and 3.08 eV and hence the emission was attributed to the M_Na centre. The luminescence mechanism was described.     

Dose response of thermoluminescence emission spectra of LiF:Mg,Ti with different Mg, Ti impurity concentrations

The dose response of the TL emission spectra of an LiF:Mg,Ti (TLD-100) sample and three LiF:Mg,Ti samples with different impurity concentrations (0–6 ppm Ti and 80–100 ppm Mg) have been measured. At a dose less than 22 Gy the emission spectrum of the TLD-100 sample comprises one emission band at 420 nm. The sample without Ti shows also one emission band but now at 620 nm. The spectra of the other two samples comprises two emission bands at 420 nm and 620 nm of which the intensity of the 420 nm band increases with increasing Ti concentration. The dose response of the glow peaks is different for peaks at different temperatures and emission bands. From these observations it can be concluded than in LiF:Mg,Ti at least some of the traps and luminescent centers are coupled.     

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.     

Behaviour of LiF:Mg,Cu,P and LiF:Mg,Ti thermoluminescent detectors for electron doses up to 1 MGy

The behaviour of LiF:Mg,Cu,P and LiF:Mg,Ti detectors at ultra-high doses up to 1 MGy, has been investigated. The presence of the ultra-high-temperature peak (450 °C) of reproducible properties was observed in various batches of LiF:Mg,Cu,P, confirming earlier findings. The results indicate that this peak is not an effect of random impurities nor intrinsic effects of LiF, but it is rather connected with the doping.A parameter called ultra-high temperature ratio (UHTR) was defined in order to quantify the observed changes of LiF:Mg,Cu,P glow-curve shape at very high doses and very high temperatures. The use of this parameter allows to determine an absorbed dose in the range from 1 kGy to 1 MGy. This new method of high-dose dosimetry makes LiF:Mg,Cu,P a unique dosimeter, which is capable to cover at least 12 orders of magnitude of dose range: from a microgray to a megagray.     

Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

Dosimetric application of green luminescence in irradiated TLD-500 detectors

The spectral and kinetic characteristics of thermoluminescence (TL) for anion-defective α-Al₂O₃ single crystals in the 4.4–2.2 eV range at 300–600 K were studied. Three-dimensional (3D) plots of the luminescence under research for a sample before and after UV irradiation at 623 K for 30 min were analyzed. The increase in the emission response in the 2.4 and 3.7 eV bands for the sample after the photothermal treatment was observed. The dominant contribution of a thermally stimulated process with first-order kinetics in the regularities of the 2.4 eV luminescence was shown. The linearity of the dose dependences for the 2.4 eV TL response in different samples at 10⁻⁵–1 Gy was demonstrated. The advantage of using the green thermoluminescence in the TLD-500 for solid state dosimetry was discussed.     

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.     

A new look at the linear-modulated optically stimulated luminescence (LM-OSL) as a tool for dating and dosimetry

Optically stimulated luminescence (OSL) has been in use for dosimetry and dating in the last two decades. Since the OSL dependence on time is a featureless decaying function, a linear-modulation of the stimulating-light intensity has been suggested [Bulur, E., 1996. An alternative technique for optically stimulated luminescence. Radiat. Meas. 26, 701–709.], which resulted in a peak-shaped curve. The properties of this curve have been studied, assuming first-, second- and general-order kinetics. In a recent paper we have shown [Chen, R., Pagonis, V., 2008. A unified presentation of thermoluminescence (TL), phosphorescence and linear-modulated OSL (LM-OSL). J. Phys. D: Appl. Phys. 41, 035102 (1–6).] that for general-order curves, the peak maximum cannot be expected to depend linearly on the dose of excitation. A new presentation of the LM-OSL has been suggested, in which the peak maximum is linear with the filling of trapping states, which, in turn, may be expected to be linear with the dose under appropriate conditions. In the present work, we report on results of numerical simulation of the LM-OSL using the one trap-one recombination center (OTOR) model, dealing with the traffic of carriers between one trapping state, one kind of recombination center and the conduction and valence bands during excitation and read-out, and without making any simplifying assumptions. The process during optical read-out has been followed in the simulation that consisted of the numerical solution of the relevant sets of coupled differential equations, and also by analytical treatment. Sets of parameters leading to approximately first- and second-order kinetics, and to intermediate cases, have been used and the results presented in the original and the new ways are shown. The consequences concerning dating and dosimetry are discussed.     

Radioluminescence of synthetic quartz related to alkali ions

The radioluminescence (RL) of synthetic quartzes (GEMMA Quartz & Crystal Company) has been measured at room temperature. Some samples were treated by electrodiffusion (“sweeping”) in order to change the concentrations of alkali ions, mainly Li⁺ and Na⁺, which in quartz are known to be linked to Al ions, substitutional for Si ions.The RL emission spectra show evidence of a role of alkali ions in affecting some specific emissions. All the spectra could be analysed as composed of four bands in the blue and UV region. Specifically, the well known blue emission at around 470 nm was seen to be composed by two bands at 430 nm (2.86 eV) and at 485 nm (2.53 eV). Effects of irradiation, during the RL measurements, were clearly seen only in the “Li swept in” sample, namely an increase in the 485 nm band intensity and a decrease in the 430 nm band one. The previously reported UV emission was detected at 355 nm (3.44 eV) in all the samples, being the most intense band in the “swept out” sample. A further UV emission was detected at 315 nm (3.94 eV), more intense in untreated samples.Possible assignments of the detected emission bands are discussed in relation to the defects of quartz, specifically focusing on the Al centres that are most affected by sweeping procedures.