The trap parameters of electrons in intermediate energy levels in quartz

The trap parameters (thermal activation energy E_t and frequency factor s) of the glow peaks of quartz, occurring in the temperature range 420–520 K and corresponding to intermediate energy levels, were evaluated using different and complementary methods of analysis: peak shift, isothermal decay and fractional glow curve. The values of E_t and of s derived with the isothermal decay method and with the peak shift technique agree quite well, within the error limits. The corresponding values obtained using the fractional glow curve analysis proved to be underestimated, probably as a consequence of the thermal quenching. Proper corrections were therefore applied to take into account this phenomenon.     

LiMgPO_4:Tm,Tb的热释光和光释光陷阱参数

采用高温固相法合成了LiMgPO_4:Tm,Tb粉末样品,测定了热释光陷阱参数激发能E和频率因子s.用脉冲退火和多次退火方法研究了其光释光陷阱参数E和s,并与用多速法得到的热释光的结果进行了比较.对不同β射线剂量照射的样品发光曲线的研究表明,300°C高温峰属于一级动力学发光峰.通过对热释光和光释光陷阱的相关性研究表明,经200°C预热的热释光信号(对应于300°C高温峰)和光释光信号很有可能来自于同一深度的陷阱.     

Apparent anomalous fading of thermoluminescence associated with competition with radiationless transitions

Anomalous fading of thermoluminescence (TL) is the effect of a fading which is significantly faster than what is warranted by the trapping parameters which are evaluated from the features of the TL peak in question. A previous work suggested that in certain cases, apparent anomalous fading may be a normal fading in disguise. The idea was that, at least in some cases, radiationless transitions into competing recombination centers may yield a very narrow peak which, while using either the curve fit technique or the different peak shape method will result in very high values of effective activation energy E and frequency factor s which, in turn, will yield an apparent life-time orders of magnitude higher than the real one. The question has been raised whether this anomaly is observable only when the peak shape methods are utilized and in particular, can the same effect occur when the broadly used initial-rise method is applied. It is demonstrated in this work that under similar circumstances of competition, very high effective values of E and s are evaluated which result in very high life-times when the activation energy is evaluated by the initial-rise method. Thus, the explanation of apparent anomalous fading as being a normal decay in disguise, is extended to cases in which the initial-rise method is utilized for the parameter evaluation.     

Die Bestimmung des Frequenzfaktors und der Haftstellentiefe aus der Temperaturabhängigkeit der Elektrolumineszenz von ZnS-Phosphoren

The temperature dependence of the a.c. electroluminescence of ZnS-phosphors shows characteristic features which are closely related to the energetic distribution of traps. Measurements over a wide range of exciting field frequencies are used to determine frequency factors and trap depths with high accuracy. The order of magnitude of the obtained frequency factors agrees with theoretical values and results of other authors, who investigated CdS single crystals by different methods. The trap depths resulting from electroluminescence measurements are lower than those estimated from glow curves. This deviation can be explained by considering multiple retrapping and a low quantum efficiency of the thermoluminescence. An expression for the trap depth in dependence of the temperature of a glow maximum is derived, which is valid for all kinetics of thermoluminescence.     

Diffusion of W on A W(211) plane

The diffusion of W on a (211) plane of a W field emitter has been re-examined by means of the fluctuation autocorrelation method. Diffusion along channels yielded E = 16.8 ± 0.5 kcal, D₀ = (3 ± 1) × 10⁻⁵ cm² s⁻¹. For diffusion across channels E =6.6 kcal, D₀ = 4 × 10⁻⁹cm² s⁻¹ at T < 752 K, and E = 24 kcal, D₀ = 5 × 10⁻⁴ cm² s⁻¹ at T > 752 K. The results for diffusion along channels yield E and D₀ values intermediate between recent results by Wang and Ehrlich [Surf. Sci. 206 (1988) 451] using field ion microscopy (E = 19 kcal, D₀ = 7.7 × 10⁻³ cm² s⁻¹) and Tringides and Gomer [J. Chem. Phys. 84 (1986) 4049], using the same method as the present work but a larger slit (E = 13.3 kcal, D₀ = 7 × 10⁻⁷ cm² s⁻¹). The results for cross channel diffus good agreement with those of Tringides and Gomer below 752 K, where these authors stopped. The new high temperature results suggest that the channel wall exchange mechanism postulated by Tringides and Gomer for cross channel diffusion at low T gives way to diffusion by climbing over the channel walls with higher E but also higher D₀ above 752 K. Possible reasons for the discrepancies between these three sets of results and the absence of cross channel diffusion in the work of Wang and Ehrlich are briefly discussed.     

Thermoluminescence in gallium sulfide crystals: an unusual heating rate dependence

Trap centres in gallium sulfide single crystals have been investigated by thermoluminescence measurements in the temperature range of 10–230 K. A curve-fitting method was utilized to evaluate the activation energies (52, 200 and 304 meV) of the revealed three trap centres. The heating rate dependence and trap distribution of the peaks have been studied using experimental techniques based on various heating rates and various illumination temperatures, respectively. An anomalous heating rate dependence of the high-temperature peak was found by carrying out TL measurements with various heating rates between 0.2 and 1.0 K/s. This behaviour was explained on the basis of a semi-localized transition model. Whereas normal heating rate dependence was established for low-temperature peak, that is, the TL intensity of the glow curve decreases and the peak maximum temperature shifts to higher values with increasing the heating rate. Moreover, a quasi-continuous trap distribution with the increase of activation energies from 52 to 90 meV, from 200 to 268 meV and from 304 to 469 meV for the observed three different traps was established employing the various illumination temperatures method.     

Comparative study on the effect of annealing treatments on RTL mechanism in natural quartz from different origins

The behaviour of trap centres and luminescence centres has been investigated for fired and unfired natural quartz from bricks and sediments irradiated at 100 Gy and annealed at different temperatures in the range 350-700 °C. The annealing treatment affects thermoluminescence (TL) glow curve as various changes were observed. The higher sensitization occurred for an annealing in the region 550-600 °C. At this annealing temperature, it has been observed the emergence of two peaks arising at 96 and 180 °C. At lower annealing temperatures, these peaks are overlapped by the peaks localized at 90 and 195 °C, respectively. Concerning the fired quartz, the higher sensitization occurred for an annealing in the region 500-550 °C for peak temperature around 200 °C and an unusual desensitization for the peak temperature around 100 °C. The behaviour of the two types of quartz is analyzed regarding to their kinetic parameters and luminescence emission and compared to literature data.     

Excitation of thermoluminescence in Eu doped Ba0.12Sr0.88SO4 nanophosphor by low energy argon ions

In the present paper thermoluminescence properties of argon ions irradiated barium strontium mixed sulphate phosphor are reported. The Ba_0.12Sr_0.88SO₄ phosphor was prepared by chemical co-precipitation method. The X-ray diffraction study of prepared sample suggests orthorhombic structure with average grain size of 37 nm. The samples were irradiated with 1.2 MeV Argon ions at fluences varying between 10¹¹-10¹⁵ ions/cm². The argon ions penetrate to the depth of 1.89 μm and lose their energy mainly via electronic stopping. Due to ion irradiation, a large number of defects in the sample are formed. Thermoluminescence (TL) glow curves were recorded for each of the ion fluence. These curves exhibit one broad peak with maximum intensity at 498 K composed of three overlapping peaks. This indicates that different sets of traps are being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The peaks were observed due to formation of trap levels by ion irradiation and subsequently activation of traps on thermal stimulation. The TL response of the nanophosphor is linear in the dose range 59 kGy-590 MGy. Kinetic parameters associated with the prominent peaks were calculated using glow curve deconvolution (GCD) and verified by different glow curve shape and sample heating rate methods.     

Study of the glow curve structure of the minerals separated from black pepper (Piper nigrum L.)

The inorganic mineral fraction extracted from black pepper (Piper nigrum L.) has been analysed using a thermoluminescence (TL) method, investigating the glow curve structure, including an evaluation of the kinetic parameters. Different grain sizes, i.e. 10, 74, and 149 μm, were selected from commercial black pepper. The X-ray diffraction of the inorganic fraction shows that quartz is the main mineral present in it. The samples were exposed to 1–25 kGy doses by gamma rays of ⁶⁰Co in order to analyse the thermally stimulated luminescence response as a function of the delivered dose. The glow curves show a complex structure for different grain sizes of the pepper mineral samples. The fading of the TL signal at room temperature was obtained after irradiation, and it was observed that the maximum peaks of the glow curves shift towards higher values of the temperature when the elapsed time from irradiation increases. It seems that the fading characteristic may be related to a continuous trap distribution responsible for the complex structure of the glow curve. Similar glow curves structure behaviour was found under ultraviolet irradiation of the samples. The activation energy and the frequency factor were determined from the glow curves of different grain sizes using a deconvolution programme because of the evident complexity of the structure.     

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.     

Effect on thermoluminescence parameters of biotite mineral due to thermal quenching

The Thermally Stimulated Luminescence (TSL) at room temperature X-ray irradiated natural biotite in form of micro-grain powder was studied under various heating rates. TSL peaks showed at temperatures 393 K, 399.6 K, 403.5 K, 404.5 K, 406.9 K at their respective heating rates 2 K/s, 4 K/s, 6 K/s, 8 K/s and 10 K/s. The effect of thermal quenching on thermoluminescence parameters such as peak maximum temperature, peak area, FWHM, geometrical symmetry factor, the activation energy were investigated. From the symmetry factor it is clear that the TL glow curve follows the first order kinetics for the lowest heating rate, but as the heating rate increases it defers from the first order. The activation energies for each heating rates were calculated by using Chen peak shape methods for general order kinetics and found to be decreased for higher heating rates. When activation energy is calculated by variable heating rate method it is observed that the method overestimated the value of activation energy and pre-exponential frequency factor significantly due to thermal quenching.     

Two-point method for kinetic analysis of a thermoluminescence glow peak

We present a method for the estimation of defect (trap) physical parameters from thermoluminescence (TL) glow peaks. In this method, the order of kinetics b is determined using two values of TL intensity each of which corresponds to the same temperature (T ₁) on two separate glow peaks of a phosphor. The two glow peaks are obtained from two aliquots of the phosphor irradiated to same dose but read out at different heating rates. The proposed method requires a minimum of only two data points in contrast to standard peak shape (PS) methods that require three points corresponding to three different temperatures on the same glow peak. Once the order of kinetics b is determined, the activation energy E is calculated by taking a second point (T ₂) on any one of the two glow peaks. The values of b and E thus obtained are used to evaluate the frequency factor S ^′′ and the number of trapped electrons before the heating begins n _o. The validity of the method was checked using two numerically generated glow peaks. For the two cases, the method reproduced the input values reasonably well. The method was also used to analyse two experimental glow peaks. The results obtained provide a reasonably good fit to the experimental data. The kinetic parameters calculated using the present technique are comparable to those calculated using PS and initial rise methods. Initial guesses can easily be obtained for E and S ^′′ using the present technique when a glow curve is to be deconvoluted with a model consisting of many unknown parameters with E and S″ inclusive.     

Thermoluminescence Kinetic Parameters of TLD-600 and TLD-700 after ~(252)Cf Neutron+Gamma and ~(90)Sr-~(90)Y Beta Radiations

The thermoluminescent(TL) properties such as glow curve structure, relative thermoluminescence sensitivity,dose response linearity of lithium fluoride thermoluminescent dosimeters 6 LiF:Ti,Mg(TLD-600) and 7 LiF:Ti,Mg(TLD-700) are investigated after irradiation ~(252)Cf neutron+gamma and ~(90)Sr-~(90)Y beta sources at room temperature and then the obtained results are compared. The kinetic parameters, namely the order of kinetics b,activation energy Ea and the frequency factor s,are calculated using the computerized glow curve deconvolution(CGCD) program. The effect of heating rate on the glow curves of dosimeters is also investigated. The maximum TL peak intensities and the total area under the glow curves decrease with the increasing heating rate. There is no agreement with the kinetic parameters calculated by the CGCD program for both radiation sources.     

The ‘110°C’ TL peak in synthetic quartz

The thermoluminescence (TL) of synthetic quartz has been investigated in the temperature region 275–475 K. These measurements have revealed a more complicated structure of the 110°C TL peak and thermal activation energies and frequency factors have been estimated for a number of peaks within the glow curve. The results obtained after annealing samples in different atmospheres indicate that oxygen-related defects play an important role in the luminescence process, involving both the charge traps and recombination centres.     

Concerning infrared-stimulated luminescence from K-feldspars: evidence from heating before stimulating

Repeated heating and stimulation by infrared of feldspar samples causes a reduction in the luminescence signal. Two feldspars were investigated, one microcline and one orthoclase. Empirically the fraction of luminescence signal f(n) remaining after the nth cycle of heating and stimulation is given by f(n)=1−a ln(n) for laboratory dosed samples of both microcline and orthoclase feldspars, for heating temperatures of 150°C, 180°C and 220°C, for heating durations per cycle ranging from 20 s to 2400 s and with the study covering 10 cycles of heating and stimulation. Logarithmic decay of luminescence with time has been explained previously, in other contexts, as due either to quantum tunnelling or to a continuous distribution of states being involved but it is shown that these explanations do not fit the present data. The measured data on f(n) were corrected for the loss of luminescence due to infrared stimulation to ensure that this did not account for the differences between the data and the expectations from models; the functional form f(n)=1−a ln(n) remains valid, although with changed values of a. Numerical simulations of systems involving a limited number of trap depths, from 21 down to 3, were investigated and those with 5 or more trap depths were found to be capable of resembling the data. The simulations could not define a unique pattern of trap depths to match the data, but of the patterns investigated the data were best reproduced by a distribution of at least 5 traps in the energy range from 1.18–1.66 eV. These conclusions augment, and are consistent with, existing information on luminescence mechanisms in potassium-feldspars.     

Thermo-stimulated luminescence of x-ray- and alpha-irradiated yttria-stabilized zirconia

Yttria-stabilized zirconia (ZrO2 : Y3+) single crystals (with 9.5 mol% Y2O3) were irradiated with x-rays and α particles. Thermally stimulated luminescence (TSL) data show a main broad peak centred at ～500-550 K in the glow curves of all irradiated samples. The TSL peak maximum temperature is consistent with the characteristic recovery temperature (～450 K) of colour centres (T centres) deduced from isochronal annealing curves measured by electron paramagnetic resonance (EPR) spectroscopy. However, the trap-depth energies (ranging between 0.8 and 1.2 eV) deduced from the initial rise of partially cleaned TSL peaks (and from a rough approximation using Urbach's formula) are much larger than the activation energies for defect recovery of 0.3 eV deduced from the EPR data. A second TSL peak centred at ～350-450 K found in freshly irradiated samples is seen to decay substantially in aged samples. The processes involved in TSL are discussed in relation to the defect annealing processes, and available defect-level energy and TSL data.     

The analysis of thermoluminescence glow curves

Information about the behavior of traps in a luminescent material is usually derived by fitting the glow curves in the thermoluminescence spectrum of the material to a general formula. From the fit one seeks to obtain values for the depth of the traps, the frequency factors governing the release of electrons from the traps, and some indication of the rates of trapping and retrapping. This study investigates how successful this fitting process is in providing reliable values for the trap parameters. The relevant rate equations are used to numerically generate simulated glow curves for specific values of trap parameters. These glow curves are then analyzed by the usual fitting process, and values for the trap parameters are derived from the fitting process. We comment on the comparison between the derived parameter values and the correct values. From these comparisons we attempt to obtain some useful insights to assist in the interpretation of experimentally observed thermoluminescence spectra.     

Trap levels in Y-aluminum garnet scintillating crystals

Point defects acting as trap levels were investigated on undoped, Ce- and (Ce, Si)-doped Y₃Al₅O₁₂ (YAG) crystals by TSL measurements performed over a wide temperature range (10–800 K). Below room temperature, a composite glow curve was observed, whose intensity strongly increased after Ce doping. Moreover, Ce doping introduced new trap levels giving rise to glow peaks in the 100–200 K range. On the other hand, Si co-doping did not influence the low T glow curve in a significant way. The spectral emission of the TSL was found to be governed by the Ce³⁺ 5d–4f radiative transition, while defect related higher energy emission bands were detected only in the undoped crystal. Above RT, the glow curve was found to be much more influenced by Si co-doping since a strong increase of a glow peak at about 250°C was noticed. Scintillation time decays of Ce- and Ce,Si-doped samples are also reported and compared with TSL data. The significance of the results and the potential impact of defect states on the scintillation properties are discussed.