Applications of the three points analysis method for obtaining the trap parameters and the separation of thermoluminescence glow curve into its components

Here, we apply a recently developed technique to separate a composite thermoluminescence (TL) glow curve into its individual components and to evaluate the trap parameters of the individual TL glow peaks. These parameters include the order of kinetics b, the activation energy E (eV) and the frequency factor S (s^?1) or the pre-exponential factor S″ (s^?1). Recently, a general equation was developed to estimate the order of kinetics b. The characteristic point of this equation is that any set of three data points in a TL glow curve can yield b. Using this characteristic, an improved procedure was suggested to separate a composite glow curve, which includes several overlapping peaks, into its individual components and to obtain the trap parameters of the individual glow peaks. The method was applied here to analyze and determine the trap parameters of the TL glow curve of the promising TL dosimetric material, double potassium yttrium fluoride (K₂YF₅) doped with praseodymium ions (Pr³⁺), in response to γ-irradiation.     

Determination of thermoluminescence kinetic parameters of thulium doped lithium calcium borate

For the first time kinetic parameters of thulium doped Lithium calcium borate (LCB) Thermoluminescence (TL) material are reported here. Irradiated LCB:Tm³⁺ powder has revealed two intense TL glow peaks one at 510 (peak 1) and the other at 660 K (peak 2). Activation energy (E), frequency factor (s) and order of kinetics (b) of these peaks were determined by various heating rate (VHR), initial rise (IR), and peak shape (PS) methods. The trap depth and frequency factor determined for peaks 1 and 2 of LCB:Tm phosphor using VHR and IR methods are in good agreement. The average activation energy of peaks 1 and 2 obtained by these methods is 1.62 and 1.91 eV respectively. The frequency factors of peaks 1 and 2 are in the range of 10^13–16 and 10^12–14 sec⁻¹ respectively. The E and s values estimated using the glow peak shape dependent parameters are relatively less compared to the values obtained from other methods. The large difference in these values is due to the complex nature of the glow curves. The order of the kinetics process for complex glow curve peaks could not be assigned on the basis of shape parameters alone but T_m response on absorbed dose is to be considered for final confirmation. Glow peaks 1 and 2 of LCB:Tm³⁺ obey first and general order kinetics respectively.     

The validity of the two heating rates method to obtain the trapping parameters from general-order thermoluminescence glow peaks

The two heating rates method, which is usually known as Booth-Bohun method, is currently employed for obtaining the activation energy E (eV) of first-order thermoluminescence (TL) glow peak. However, this method can be used for obtaining the activation energy for all types of TL glow peaks irrespective of their order of kinetics (b). The present work shows that the condition of maximum intensity of first-order kinetics can be safely used to obtain the pre-exponential factor S″ (s⁻¹) in the case of general-order glow peak when Booth-Bohun method was used to obtain E. Also, the present work suggests a numerical method for obtaining the order of kinetic (b) of general-order glow peak. This method depends on the activation energy E obtained by Booth-Bohun method and the suggested method mentioned above to obtain S″. An independent evaluation of the suggested methods is illustrated here by taken some numerically computed glow peaks by applying the one-trap and one-recombination-center (OTOR) model.     

Method of Hoogenstraaten as a tool for obtaining the trap parameters of general-order thermoluminescence glow peaks

The Hoogenstraaten method is a technique that uses various heating rates for obtaining the activation energy E (eV) in the case of first-order thermoluminescence glow peaks. This method can also be used for obtaining E (eV) for all types of glow peaks regardless of their kinetics order (b). The present work shows that the intercept of the Hoogenstraaten relation, which is usually used for obtaining the frequency factor S (s ^?1) of the first-order glow peak, can be used as a very good approximation to obtain the pre-exponential factor S ^{′ ′} (s ^?1) in the case of general-order glow peaks, when one uses Hoogenstraaten’s method to obtain E (eV). In addition, the present work suggests a numerical method for obtaining the kinetics order of the general-order glow peak. The method depends on the activation energy E (eV) obtained by the Hoogenstraaten method and the above-mentioned approximation for obtaining the pre-exponential factor S ^{′ ′} (s ^?1). An independent evaluation of the suggested methods for obtaining the trap parameters, the activation energy E (eV), the pre-exponential factor S ^{′ ′} (s ^?1) and the kinetics order (b) is illustrated here by taking a numerically computed glow peak and applying a one-trap and one-recombination-center model.     

Thermo-luminescence kinetic parameters of γ-irradiated Sr4Al14O25:Eu2+, Dy3+ phosphors

In this paper, we present a detailed investigation of the thermo-luminescence (TL) kinetics of the long afterglow phosphor, Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, synthesized by the combustion method. Kinetic parameters such as the activation energy (E_α), the frequency factor (s) and the order of kinetics (b) were calculated using Chen's formulism. The crystalline structure of the phosphor was examined using X-ray powder diffraction and transmission electron microscopy. The average particle size was found to be in the range of 45–52 nm. The optimum dopant concentrations were Eu (1 mol%) and that of Dy (2 mol%). The TL response of the phosphor was monitored after the samples were irradiated with a γ-dose using a ⁶⁰Co source in the 20-800 Gy range. A broad TL peak, (stretching from 328 to 410 K) with a maximum at 368 K was observed. With increasing irradiation dose, the main peak shifts toward higher temperatures. Symmetry factor calculations show that the main TL glow peak obeys second-order kinetics, which could be attributed to the creation of deep level traps. This means that γ-ray irradiation greatly affects the distribution of traps in the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor. The phosphor showed a linear response with γ-dose.     

Thermoluminescence kinetics analysis of α-Al2O3:C at different dose levels and populations of trapping states and a model for its dose response

Kinetic analysis of a α-Al₂O₃ (TLD-500) thermoluminescent (TL) dosimeter was performed following irradiating the samples with ⁶⁰Co gamma rays. The number of glow peaks contained in the complex glow curve of this phosphor was identified using the T_m ? T_stop method, which demonstrates three component glow peaks. A computerized glow curve deconvolution (CGCD) program was used to determine the trapping parameters of the three constituent glow peaks obtained at different dose levels and different populations of trapping states. To analyze the number of constituent glow peaks, we used a kinetic model to describe both the irradiation and heating stages. The predictions of the model for the TL response agreed well with the experimental data when three dosimetry traps were incorporated.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.     

Luminescence characteristics of Na21(SO4)7F6Cl:Cu+ phosphor

Copper-doped Na₂₁(SO₄)₇F₆Cl phosphor was synthesized via the conventional wet chemical method. The synthesis was carried using CuCl₂ and Cu (NO₃)₂·3H₂O as dopants in two different steps successively. The formation and phase purity of the compound were revealed by the X-ray diffraction pattern. Functional groups of the prepared phosphor were observed in the FT–IR spectrum. The emission along with excitation spectra were followed to explore the luminescence attributes. Photoluminescence (PL) emission spectrum of the material synthesized using CuCl₂ as the dopant was observed at 358?nm due to 3d^l0?3d⁹4s transitions when excited around 247?nm for various copper concentrations. Efficient blue emissions were obtained at peaks 423 and 469?nm for materials synthesized using Cu (NO₃)₂·3H₂O as the dopant, when monitored at 357?nm excitation. The Commission Internationale de I’Eclairage chromaticity coordinates for different copper concentrations were calculated for the emission around 423?nm. TL glow curves of Na₂₁(SO₄)₇F₆Cl:Cu phosphor for different dopant concentrations, irradiated with 100?Gy gamma dose, were studied and hence the trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peak of Na₂₁(SO₄)₇F₆Cl:Cu phosphor were determined by using Chen’s Peak shape method. The results indicate that Na₂₁(SO₄)₇F₆Cl:Cu⁺ is a potential novel blue-emitting lamp phosphor and may be quite suitable for use in dosimetry of ionizing radiations.     

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.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

On extending the applicability of the initial rise method for thermoluminescence glow peak analysis

We discuss an approach by which the initial rise (IR) method can be extended to evaluate the frequency factor (s) of a glow peak, in addition to activation energy (E) that is usually obtainable from it. The approach requires that the phosphor be irradiated to a dose near or equal to the saturation dose of the glow peak to be analyzed. By plotting ln(I) against 1/T for the thermoluminescence glow peak, one obtains a straight line whose gradient is ? E/k and intercept is ln(n ₀ s/β) from which E and s are determined respectively. The approach was used to analyze two numerically generated glow peaks and reproduce with reasonably good accuracy the E and s values used to generate the glow peaks. It is also shown that when it becomes necessary to include intensities above 10% of the maximum glow peak intensity, the error introduced into the calculated frequency factor by the assumption n? n ₀ is always negligible when the analysis is done by plotting ln(I/n) against 1/T. In this case the frequency factor is obtained from ln(s/β) which is now the intercept. Two experimental glow peaks were also analyzed using the new IR method approach and peak shape method. Good agreement, which again shows the validity and reliability of the present approach was observed between the values of E and s obtained by the two methods.     

Argon ions induced thermoluminescence properties of Ba0.12Sr0.88SO4 phosphor

Thermoluminescence properties of barium strontium mixed sulfate have been studied by irradiation with Argon ions. The sample was recrystallized by chemical co-precipitation techniques using H₂SO₄. The X-ray diffraction study of prepared sample suggests the orthorhombic structure with average grain size of 60 nm. The samples were irradiated with 1.2 MeV Argon ions at fluences varying between 10¹¹ and 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. Thermally stimulated luminescence (TSL) glow curves of ion irradiated Ba_0.12Sr_0.88SO₄ phosphor exhibit broad peak with maximum intensity at 495 K composed of four 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). Thermoluminescence (TL) glow curves were recorded for each of the ion fluences. A linear increase in intensity of TL glow peaks was found with the increase in ion dose from 59 kGy to 5.9 MGy. The kinetic parameters associated with the prominent glow peaks were calculated using glow curve deconvolution (GCD), different glow curve shape and sample heating rate methods.     

Afterglow mechanism and thermoluminescence of red-emitting CaS:Eu,Pr phosphor with incorporated Li ion upon visible light irradiation

This paper reports on the afterglow mechanism and thermoluminescence (TL) of a red-emitting CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion upon irradiation by visible light (D₆₅ lamp). In the TL glow curve of the CaS:Eu²⁺,Pr³⁺ phosphor, a TL peak was observed near 120 °C. The luminescence center of the CaS:Eu²⁺,Pr³⁺ phosphor was the Eu²⁺ ion and the trap depth of the CaS:Eu²⁺,Pr³⁺ phosphor with the cation vacancy (Trap 1) which formed by incorporation of the Pr³⁺ ion was 0.202 eV. A cation vacancy (Trap 2) was formed by incorporation of the Li⁺ ion in the CaS:Eu²⁺,Pr³⁺ phosphor. In the TL glow curve of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion, two TL peaks were observed near 120 and 200 °C. The TL luminance of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion increased with an increase in the initial Li/Ca atomic ratio. The two TL peaks moved to the high-temperature side with an increase in heating rate. The cation vacancy (Trap 2) calculated from the Hoogenstraaten method was 0.118 eV. The afterglow time of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion was prolonged by generation of a shallow trap.     

Effect of ion irradiation on the thermoluminescence properties of K2Ca2(SO4)3 phosphor

This paper presents the thermoluminescence (TL) studies of ion-irradiated potassium–calcium mixed sulfate phosphor. The sample was prepared by the solid-state diffusion method. The X-ray diffraction study of the prepared sample suggests an orthorhombic structure with an average particle size of 0.16 μ m. The samples were irradiated with 1.2 MeV argon ions at fluences varying between 10¹¹ and 10¹⁵ ions/cm². The argon ions penetrate to a depth of 1.93 μ m and lose their energy mainly via electronic stopping. Due to ion irradiation, a large number of defects such as oxygen vacancies, radicals and color centers are formed in the sample. TL glow curves were recorded for each of the ion fluences. A linear increase in the intensity of TL glow peaks was found with an increase in the ion dose from 72 kGy to 720 MGy. The kinetic parameters associated with the prominent glow peaks were calculated using glow curve deconvolution, different glow curve shapes and sample heating rate methods.     

Luminescence studies of a combustion-synthesized blue–green BaAlxOy:Eu,Dy nanoparticles

Blue–green emitting BaAl_xO_y:Eu²⁺,Dy³⁺ phosphor was synthesized by the combustion method. The influence of various parameters on the structural, photoluminescence (PL) and thermoluminescence (TL) properties of the phosphor were investigated by various techniques. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. In the PL studies, broad-band excitation and emission spectra were observed with major peaks at 340 and 505 nm, respectively. The observed afterglow is ascribed to the generation of suitable traps due to the presence of the co-doped Dy³⁺ ions. Though generally broad, the peak structure of the TL glow curves obtained after irradiation with UV light was non-uniform with suggesting the contribution to afterglow from multiple events at the luminescent centers. Further insight on the afterglow behavior of the phosphor was deduced from TL decay results.     

Synthesis, photoluminescence, thermoluminescence and electron spin resonance investigations of CaAl12O19:Eu phosphor

The present paper describes the synthesis of europium-doped calcium aluminate phosphor using the combustion method. An efficient blue emission phosphor can be prepared at reaction temperatures as low as 500 °C in a few minutes by this method. Characterization of the powder was done by X-ray diffraction, transmission electron microscopy, scanning electron microscope analysis and the optical properties were studied by photoluminescence spectra. Thermoluminescence (TL) studies also have been carried out on CaAl₁₂O₁₉:Eu²⁺ phosphor. The TL glow curve shows peaks at 174 and 240 °C. Defect centres formed in irradiated phosphor have been studied using the technique of electron spin resonance. Step annealing measurements indicate that one of the annealing stages of a defect centre appear to correlate with the release of carriers resulting in TL peak at 174 °C. The centre is characterized by an isotropic g-value of 2.0046 and is assigned to a F⁺ centre.     

Determination of kinetic parameters of thermally stimulated luminescence of Cu-doped BaSO4

Studies of thermally stimulated luminescence (TSL) of doped BaSO₄ with Cu activator have been carried out. The polycrystalline sample of Cu-doped BaSO₄ is prepared by recrystallisation method. The characterization and elemental analysis of BaSO₄:Cu compound are carried out by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX). The compound has orthorhombic structure at room temperature. The TSL studies of Cu-doped BaSO₄ sample show two glow peaks at 160 and 227 °C. Comparison of TL intensity of the most intensive glow peak of Cu- and Mn-doped BaSO₄ compounds with that of undoped BaSO₄ shows that addition of Cu and Mn impurity in BaSO₄ compound enhances the TL intensity by about 9 and 3 times, respectively. Among the studied samples, namely undoped, Cu- and Mn-doped BaSO₄, Cu-doped BaSO₄ is found to be the most sensitive. The trap parameters namely order of kinetics (b), activation energy (E), frequency factor (s) and Balarin parameter (γ) associated with the most intensive glow peak, i.e. the 227 °C glow peak of BaSO₄:Cu phosphor were determined by using isothermal decay method and glow curve shape (Chen's) method and these parameters are in good agreement.     

Synthesis and thermoluminescence characterization of Na6Mg(SO4)4:RE (RE = Ce,Tb) phosphors

Thermoluminescence (TL) properties of sulfate-based phosphors activated by different rare earths have received tremendous attention to the field of radiation dosimetry. Those TL materials based on CaSO₄ have been widely applied for medical and environmental dosimetry. Taking this fact into account we have synthesized Na₆Mg(SO₄)₄ doped with Ce and Tb by wet chemical method. The prepared phosphor was characterized by XRD, FTIR, photoluminescence (PL) and thermoluminescence. For TL study, the phosphor is irradiated with γ-rays from ⁶⁰Co source. For studying luminescence properties, the prepared phosphor was annealed at different temperatures and effects of these annealing temperatures on Na₆Mg(SO₄)₄ samples are investigated and quantified. The changes in the glow curve and PL emission spectrum are also investigated as a function of annealing temperature and the annealing temperature was optimized. For calculation of trapping parameters various methods such as peak shape (PS) method, initial rise (IR) method, various heating rate (VHR) method, and computerized glow curve deconvolution (CGCD) are employed.     

Cu+ emission in Li2BPO5 material for thermoluminescence dosimetry

In this study, Li₂BPO₅ doped with Cu and that co-doped with Mg are synthesized by the wet chemical technique and exposed to γ rays of ⁶⁰Co to determine their thermoluminescence (TL) properties. The X-ray diffraction technique shows the crystalline nature of the prepared material. The photoluminescence (PL) emission spectra of Li₂BPO₅:Cu phosphor show the strong prominent peak at 368 nm in the violet region of the visible spectrum due to the transition of 3d⁹4s¹ ? 3d¹⁰ of monovalent copper ion. The PL emission of Li₂BPO₅:Cu is enhanced by the addition of Mg. The TL glow curves of γ-irradiated Li₂BPO₅:Cu sample show one glow peak at 143°C, indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak of Li₂BPO₅:Cu are calculated using the glow curve shape (Chen's) method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. A linear TL response is observed in Li₂BPO₅:Cu in a long span of exposures. The sensitivity of Li₂BPO₅:Cu sample is observed to be 7.8 times that of (TLD-100) LiF:Mg, Ti.     

Defect centres and thermoluminescence in SrS:Bi phosphor

Thermoluminescence (TL) and electron spin resonance studies have been carried out on SrS:Bi phosphor. The TL glow curve is broad and indicates a dominant peak at 120 ^°C with two additional peaks, not clearly resolved, appearing as shoulders at around 180 and 250 ^°C. Two defect centres are observed at room temperature. One of them is characterized by an isotropic g-value 2.0034 and is assigned to an F⁺ centre. Step annealing measurements indicate a possible association between the F⁺ centre and the three TL peaks.