Mechanism of thermoluminescence in Sm- and Eu-doped barium sulphate

Thermoluminescence, TL emission spectra, ESR and optically excited luminescence of BaSO₄:Sm and BaSO₄:Eu were investigated. The optically excited luminescence studies showed that samarium ions were stabilized in the trivalent state in doped samples, and a fraction of these ions was reduced to the divalent state on γ-irradiation. These reduced ions were reoxidized on thermal annealing. Europium was found to be stabilized in the divalent form in BaSO₄:Eu phosphor, both before and after γ-irradiation. These results were further confirmed from the emission spectra of different glow peaks from BaSO₄:Sm and BaSO₄:Eu samples. The ESR spectra of these samples, recorded after γ-irradiation and various post-irradiation thermal annealings, revealed that anion radicals (such as SO₄^?, SO₃^?, SO₂⁺ and O₃^?) are formed on γ-irradiation and get annihilated at temperatures which corresponds to some of the glow peaks. An attempt is made to explain the results by a mechanism, suggested earlier for other impurity-doped BaSO₄ phosphors, in which holes released on thermal activation from anion radicals recombine with the electrons trapped at certain defect centres and the energy thus released is non-radiatively transferred to the impurity ions, which give their characteristic emission.     

Thermoluminescence and photoluminescence studies on gamma irradiated CsI: Pb2+ crystals

Pure and Pb²⁺-doped CsI crystals have been grown by the Bridgemann technique. Optical absorption, thermoluminescence (TL) and photoluminescence (PL) measurements have been performed. In undoped and Pb²⁺-doped cesium iodide crystals, F-centers and V-centers have been produced at 770 nm and 350 nm, respectively. In Pb²⁺-doped crystals, additional centers at 373 nm, 290 nm and 258 nm bands have been produced. In undoped samples, only two glow peaks at 343 K and 373 K have been produced, and in Pb²⁺-doped samples additional glow peaks at 383 K and 423 K have been produced. For all the samples, TL emission, PL and excitation measurements have been performed.     

Cr-related centers in Gd3Ga5O12 polycrystals

The luminescence excitation spectra, emission spectra under photo- and X-ray excitation, luminescence decay kinetics and thermostimulated luminescence (TSL) of Gd₃Ga₅O₁₂ garnet (GGG) polycrystalline samples have been investigated. It was established that the spectrum of Cr³⁺ ion emission were present in all TSL peaks. The activation energies of traps that are responsible for appearance of TSL in the region 295-600 K were estimated. It is shown that delocalization of electrons from the Cr³⁺e traps leads to the appearance of thermoluminescence (TL) glow peak at 390 K. The nature of other TSL peaks is discussed. The influence of visible light on the TSL intensity of the preliminary X-ray-irradiated samples is shown.     

Radiation damage in polyacrylonitrile

Radiation damage in polyacrylonitrile (PAN) has been studied in the temperature range 273 to 420 K using thermoluminescence, electron spin resonance and optical absorption techniques. ATL glow peak has been observed with maximum at 362 K. The species responsible for theTL glow peak has been identified to be due to the free radical -CH₂-CH(CN)-ĊH-CH(CN)-CH₂-by correlation with the data obtained by the temperature variation ofESR and optical absorption spectra of thex-irradiated, pre- and post-x-irradiated and thermally-treated samples. A mechanism of formation of network structures accelerated by the free radicals formed on irradiation has been investigated to explain the optical absorption spectra. TheTL glow peak is analysed by various methods and corresponds to an activation energy of 1 eV, following second order kinetics.     

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.     

Thermoluminescence and electron spin resonance after room-temperature X-ray irradiation of NaCl:Mn2+

A parallel investigation of thermoluminescence (TL) and electron spin resonance (ESR) spectra on room-temperature (RT) X-irradiated NaCl:Mn²⁺ has been performed. The TL spectra in the range 20–300°C consist of five glow peaks, numbered from I to V. Temperatures at maximum height are 41°, 68°, 118°, 152° and 216°C, respectively. Peaks I, II and IV obey first-order kinetics, whereas peaks III and V fit second-order behavior. The wavelength spectrum for all glow peaks consists of two bands centered at 595 and 400 nm. The 595 nm emission is attributed to hole capture by Mn⁺ and subsequent deexcitation of Mn²⁺. The 400 nm emission is produced as a consequence of hole-F center recombination.The correlation of TL glow peaks to various defects has been investigated. Peak II is clearly related to manganese-vacancy dipoles and peak I can be roughly associated to free cation vacancies. Peak IV appears to relate to large Mn-aggregates, whereas peak V is intrinsic and not related to impurities.On the other hand, ESR data indicate that each glow peak in the 595 nm emission is associated to the annihilation of a given Mn-center; Peak I to Mn⁰C, peak II to Mn⁰C and Mn⁺, peak III to Mn⁺ and peaks IV and V to Mn⁰-D.     

Radiation damage in single crystal L-Histidine as studied by low-temperature thermoluminescence techniques

X-irradiation of single crystal L-Histidine at 10 K produces TL glow peaks at 38, 72, 84, 122, 162, 204, and 245 K. The 84 K peak is the most intense one and is characterized by a thermal activation energy of 0.073 eV and frequency factor of 1.1×10³s^-1. Moreover, it is readily photobleachable, whereas the other glow peaks are not, and is tentatively correlated with the thermal decay of a carboxyl anion radical. Computer simulation of the Randall-Wilkins first-order TL expression provided a check on the experimentally derived parameters characterizing the 38 and 84 K peaks. The initial-rise method did not produce accurate parameters for the 38 K peak; however, computer simulation yielded an activation energy of 0.022 eV and a frequency factor of 20 s^-1 which were in agreement with the experimental shape of the glow curve. This TL peak is attributed to the thermal destruction of an imidazole cation radical. Emission spectra measurements of the 84 K luminescence (other peaks were of insufficient intensity) indicated that TL results from thermal release of electrons and their subsequent de-excitation to the ground state via the singlet and triplet manifolds. At sufficiently high temperatures (～78 K) one only observes singlet state emission due to intersystem crossing.     

Effect of Pb2+ ions on the photoluminescence characteristics of Mn2+-doped Zn2SiO4

Zn₂SiO₄ single-doped and co-doped with Mn²⁺ ions and Pb²⁺ ions has been prepared by a sol–gel process. The luminescent properties of the samples have been investigated. From the excitation and emission spectral analysis, it was found that the emission peaks vary with the change of the excitation wavelength. An enhanced luminescent characteristic of Mn²⁺ ions (in blue and green spectral zones) has been observed, due to the energy transfer from the Pb²⁺ ion to the Mn²⁺ ion. The emission peaks originate from the d–d transitions of the Mn²⁺ ion. However, the relative intensities of the peaks show a dependence on the concentration of the Pb²⁺ ion. PACS 81.05.Je; 78.55.Hx; 61.72.Ww     

Role of lead centers in the thermoluminescence emission of irradiated NaCl doped with lead

The thermoluminescent glow curve and emission spectra of NaCl : Pb samples irradiated with γ-rays (6 × 10⁴ R) at room temperature have been studied and analyzed. The three TL glow peaks observed are consistent with those reported earlier on X-irradiated NaCl : Pb crystals. Emission spectra obtained for each of the glow peaks keeping the irradiated sample at a constant but lower temperature than the peak temperature have been reported and discussed. The emission due to the first two glow peaks is mainly in the 365 nm (3.4 eV) and 450 nm (2.74 eV) regions. The emission due to the third peak is in the 520 nm region and has already been reported for the case of X-irradiated NaCl : Pb crystals. An explanation of all the glow peaks and the emission bands is attempted, and an energy level diagram involving V-centers and lead centers is proposed.     

Studies of intrinsic luminescence in KCl

Measurements have been made of the luminescence intensity, lifetime, emission spectra, and thermoluminescence associated with self-trapped exciton states in KCl, at temperatures of 7°K and above. These results indicate the presence of another exciton-like state in addition to the well-known state that decays by emission at 2.32 eV. Thermoluminescence glow peaks and spectra are correlated with F + V_k and F + H recombination processes.     

Luminescence and relaxed excited state origin in CsI:Pb crystals

Emission and excitation spectra, luminescence polarization and decay kinetics have been studied for CsI:Pb crystals in the 0.36-300 K temperature range. The origin of the excited states responsible for the optical characteristics has been discussed. It has been concluded that the doublet ≈3.70 eV absorption (excitation) band is caused by the electronic transitions into the Pb²⁺ triplet state split due to the presence of a cation vacancy near a Pb²⁺ ion, while the higher-energy bands are of the charge-transfer origin. Like in CsI:Tl, four emission bands of CsI:Pb have been found to belong to the main luminescence centres. Two emission bands, peaking at 3.1 and 2.6 eV, are suggested to arise from the triplet relaxed excited state of a Pb²⁺ ion. Two visible emission bands, peaking at 2.58 and 2.23 eV, are interpreted as the luminescence of an exciton localized near the Pb²⁺ ion.     

Luminescence studies of rare earth doped yttrium gadolinium mixed oxide phosphor

This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu³⁺) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y_2−x−yGd_x) O₃: Eu_y³⁺ (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for ⁵D₀→⁷F₂ transitions and the photoluminescence excitation spectra show a broad band located around 220–270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 °C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and 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.     

Lattice location of Co implanted in silicon

Thermal treatment of CaF₂ has a significant influence on the number and intensity of the peaks seen by thermo-luminescence. A combination of ion implants and anneal cycles leads to the conclusion that the 90°C glow peak is derived from a defect of a substitutional trivalent impurity (e.g. Ce⁺³) linked to an interstitial fluorine ion. Perturbations of this centre by other defects modify the centre and the glow peak temperature is raised to 110°C.

The peaks at 180, 220 and 350°C all involve intrinsic defect clusters.

The building of models for the different glow peaks was helped by a comparison of impurity and self ion implantations.     

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.     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.     

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.     

Emission and decay time studies on Pb2+ centers in KBr,RbBr, and RbCl

The emission spectra and the luminescence decay times of KBr, RbBr, and RbCl crystals doped with Pb²⁺ and excited in the A-absorption band have been studied in the temperature range 5–300 K. The emission-lineshape spectra have been analysed in terms of skew-Gaussian bands. New bands have been observed in RbCl and RbBr at very low temperatures. While the luminescence decay of KBr:Pb²⁺ and RbBr:Pb²⁺ show only a single component with a decay time τ ～ 20 ns, RbCl:Pb²⁺ shows a short and a long component. The reason for the missing long component in KBr:Pb²⁺ and RbBr:Pb²⁺ is tentatively attributed to an anomaly in the structure of the adiabatic potential energy surface (APES) of the excited states.     

Emission spectra of MgSO4:Dy,MgSO4:Tm and MgSO4:Dy,Mn phosphors

MgSO₄:Dy, MgSO₄:Tm and MgSO₄:Dy,Mn thermoluminescence (TL) phosphors have been prepared and their emission spectra were measured using a linear heater and optical multichannel analyzer. Emission bands at about 480, 580 and 660 nm of MgSO₄ doped with Dy were observed in three dimension (3D) glow curve. Emission bands about 360, 460, and 660 nm were observed in a 3D glow curve of MgSO₄ doped with Tm. The emission spectra of MgSO₄:Dy and MgSO₄:Tm are attributed to the characteristic emission wavelengths from transitions of Dy³⁺ and Tm³⁺ respectively. The results show that the structures of traps in matrix materials determine the activation energy distribution and dopant energy levels of rare earth ions are related with the emission spectrum wavelengths of sulfate phosphors. The intensities of the glow peaks in both bands at about 480 and 580 nm in MgSO₄ doped Dy and Mn were dramatically reduced in comparison with that of MgSO₄ doped Dy except above 300°C. It means that the trapping structures of MgSO₄ :Dy phosphor has greatly been altered by the co-dopant Mn but no change is observed in wavelengths of the emission spectra.     

Studies on shallow traps in Li2B4O7:Eu,Mn

Li₂B₄O₇ (LTB) single crystals doped with 0.5 mol% Mn and 0.005 mol% Eu have been grown by the Czochralski method. The presence of Eu³⁺ has been confirmed by photoluminescence spectra of non-irradiated crystals, whereas the presence of Mn²⁺ by absorption spectra of gamma-irradiated ones, as well as by EPR measurements. Unlike in most thermoluminescence studies on pure and doped LTB, performed usually above 300 K, glow curves have been recorded between 10 and 300 K in order to focus the attention on shallow traps. A broad, intense glow peak is observed around 80 K, with three weaker peaks at 205, 255, and 280 K. Based on supplementary T_max − T_stop experiments, the trap parameters have been derived assuming that the glow curve is in fact formed by a superposition of a double Gaussian band related to a quasi-continuous distribution of trapping levels, and several glow peaks produced by discrete traps. The nature of the traps is also discussed.