Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol–gel method

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO₂:Eu³⁺) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC₃H₇)₄]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO₂ network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO₂:Eu³⁺ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 ^°C, respectively. TL response of ZrO₂:Eu³⁺ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu³⁺)-doped ZrO₂ was found to be more sensitive to beta radiation than undoped ZrO₂ obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.     

Thermoluminescence,photoluminescence and EPR studies on Mn2+ activated yttrium aluminate (YAlO3) perovskite

Thermoluminescence (TL) measurements were carried out on undoped and Mn²⁺ doped (0.1 mol%) yttrium aluminate (YAlO₃) nanopowders using gamma irradiation in the dose range 1–5 kGy. These phosphors have been prepared at furnace temperatures as low as 400 °C by using the combustion route. Powder X-ray diffraction confirms the orthorhombic phase. SEM micrographs show that the powders are spherical in shape, porous with fused state and the size of the particles appeared to be in the range 50–150 nm. Electron Paramagnetic Resonance (EPR) studies reveal that Mn ions occupy the yttrium site and the valency of manganese remains as Mn²⁺. The photoluminescence spectrum shows a typical orange-to-red emission at 595 nm and suggests that Mn²⁺ ions are in strong crystalline environment. It is observed that TL intensity increases with gamma dose in both undoped and Mn doped samples. Four shouldered TL peaks at 126, 240, 288 and 350 °C along with relatively resolved glow peak at 180 °C were observed in undoped sample. However, the Mn doped samples show a shouldered peak at 115 °C along with two well defined peaks at ～215 and 275 °C. It is observed that TL glow peaks were shifted in Mn doped samples. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped, and Mn doped samples were determined at different gamma doses using the Chens glow peak shape method and the results are discussed in detail.     

Nanoparticles size effects in thermoluminescence of oxyfluoride glass-ceramics containing Sm<Superscript>3+</Superscript>-doped CaF<Subscript>2</Subscript> nanocrystals

Oxyfluoride glass-ceramic in the system SiO₂–Al₂O₃–CaF₂–SmF₃ containing Sm³⁺-doped CaF₂ nanocrystals in the range from 15 to 150 nm size were produced by using the controlled ceramization of the precursor glass. The incorporation of the Sm³⁺-dopant ion in the glass ceramic creates new electron-trapping centers and thermoluminescence (TL) method has been used in order to trace their evolution during glass ceramization. The 370 °C TL peak observed in precursor glass has been assigned to the recombination of the electrons released from the Sm²⁺-traps in the amorphous glass network. In the glass-ceramic sample containing nanocrystals with about 15 nm size the new weak TL peaks at 270, 290, and 310 °C were attributed to the recombination of the electrons released from the Sm²⁺-traps located mainly at the surface of the CaF₂ nanocrystals. In the glass-ceramic sample containing nanocrystals with about 150 nm size, the new TL peaks at 232, 270, and 302 °C size have been assigned to the recombination of the electrons released from the Sm²⁺-traps located inside the CaF₂ nanocrystals.     

Thermoluminescence and photoluminescence characteristics of K2YF5: Tb3++PTFE irradiated with 90Sr/90Y beta particles

This article presents results of thermoluminescence (TL) and photoluminescence (PL) measurements performed on beta-irradiated K ₂YF ₅:Tb ³⁺+PTFE pellets. K ₂YF ₅ crystals doped with 0.1% of trivalent optically active Tb ³⁺ ions in pellets form were investigated. The TL glow curve of K ₂YF ₅:Tb ³⁺+PTFE has a simple structure with two well-defined peaks centered at 170 and 307 °C. The TL sensitivity of the K ₂YF ₅:Tb ³⁺+PTFE irradiated with beta radiation was found to be higher than that of commercial phosphor TLD-100 (LiF:Mg,Ti), at the same conditions of irradiation and readout. Moreover, PL measurements performed on the terbium doped material show the presence of Terbium as Tb ³⁺ in the material.     

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.     

Radiation induced defects in KBr:Tl+ crystals

The defects produced in KBr:Tl⁺ crystals during x-irradiation at 77 K were studied using thermoluminescence (TL), thermally stimulated currents (TSC), and absorption and emission spectra. Three main glow peaks at 165, 193 and 258 K were observed both in the TL and in the TSC curves. A variety of irradiation induced absorption bands were observed in the UV, visible and infrared up to about 2 microns. The 165 K TL peak was found to emit only the 440 nm band assigned to thallium dimers, while the peaks at 193 and 258 K exhibited the UV bands at 310 and 365 nm as well as the 440 nm band.The defects produced during the irradiation were the V_k hole center, the Tl° and the Tl⁺₂ electron centers. Smaller concentrations of Tl²⁺ and (Tl⁺)⁺₂ centers were also produced.An analysis of the results including measurements on lightly and heavily doped crystals enabled to draw conclusions on the nature of the defects and on the recombination processes involved. A close correlation has been found between the temperatures at which changes in the various absorption bands take place and the temperatures of the TL peaks. The analysis enabled also a full classification of the absorption bands.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Luminescence and EPR studies of YBO3:U

Yttrium borate doped with uranium was prepared by mixing and heating yttrium oxide obtained through oxalate precipitation route, boric acid and requisite amount of nuclear-grade uranium oxide at high temperature. Photoluminescence (PL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on gamma-irradiated doped/undoped yttrium borate samples in the temperature range 300-600 K. TSL studies showed the presence of two glow peaks at 414 and 471 K. PL studies along with lifetime decay investigation suggested uranium goes in the matrix as UO₂²⁺. EPR studies showed the presence of O₂⁻radical ion along with electron trapped in defect centres, which might have been produced for charge compensation. Apart from this, CO₂⁻ radical was also observed in the system having its origin from residual oxalate ion. Temperature dependence EPR studies of the observed radical confirmed the involvement of the CO₂⁻ and dioxide radical ion in the observed glow peaks. By correlating the TSL, PL and ESR data, probable mechanism is proposed for the observed TSL glow in the system.     

Synthesis and investigation of the luminescent properties of carbon doped lanthanum aluminate (LaAlO3) for application in radiation dosimetry

LaAlO₃ single crystals grown under hydrothermal conditions and co-doped with Ce and Dy atoms have been recently reported to show high thermoluminescent (TL) outputs for ultraviolet (UV) radiation fields (Oliveira et al., 2011). Due to this property, they have been considered for further investigation for applications in UV dosimetry. Encouraged by these results, we start an investigation about the TL properties of polycrystalline LaAlO₃ grown by an alternative method. In this method, equimolar amounts of Al₂O₃ and La₂O₃ are sintered, producing polycrystalline LaAlO₃ powder. Polycrystals doped with amounts of carbon ranging from 0.0 to 5.0 at.% were synthesized by sintering under hydrogen reducing atmosphere. After irradiation with a UV commercial lamp, the best TL outputs were observed for the undoped sample. The recorded TL glow curves show a main TL peak centered at 175 °C. The TL emission spectrum show a broad emission peak centered at 634 nm and another three narrow peaks centered at 724 nm, 738 nm and 754 nm, respectively. The undoped material show a huge TL output response for UV spectral irradiances ranging from 0.04 to 1.68 mJ cm⁻² that can be fitted by a 2nd order polynomial regression. The investigation demonstrates that undoped polycrystalline LaAlO₃ crystals sintered under reducing atmosphere are very attractive to be investigated as high sensitivity ultraviolet TL dosimeters.     

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.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

Thermoluminescence of rare earth activated CdSO4, SrSO4 and BaSO4

The thermoluminescence (TL) of rare earth (RE) activated sulfates of Cd, Sr and Ba was studied above room temperature. Many of the phosphors prepared exhibit an extremely bright TL following X-irradiation (most notably with Sm, Eu, Tb, Dy and Tm dopants), having an efficiency comparable to that of the highest sensitivity phosphors available for TL dosimetry, and exhibiting activator-induced glow peaks between 405 and 480°K. In a given lattice, the RE³⁺ ions produce a characteristic glow peak at the same temperature (independent of the particular RE ion), whereas Eu²⁺ produces a single glow peak at a different temperature. A decrease in glow peak temperature with increasing interatomic spacing was observed in the homologous SrSO₄-BaSO₄ system - this shift being most pronounced in the Eu²⁺ -doped materials. TL emission spectra were obtained for trivalent Sm, Tb, Dy and Tm and for divalent Eu in these sulfates (and also in CaSO₄).     

Preparation, characterization and study of optical properties of ZnS nanophosphor

In this work the preparation, characterization and photoluminescence studies of pure and copper-doped ZnS nanophosphors are reported, which are prepared by using solid-state reaction technique at a temperature of 100 °C. The as-obtained samples were characterized by X-ray diffraction (XRD) and UV-VIS Reflectance spectroscopy. The XRD analysis confirms the formation of cubic phase of undoped as well as Cu²⁺-doped ZnS nanoparticles. Furthermore it shows that the average size of pure as well as copper-doped samples ranges from 15 to 50 nm. The room-temperature PL spectra of the undoped ZnS sample showed two main peaks centered at around 421 and 450 nm, which are the characteristic emissions of interstitial zinc and sulfur vacancies, respectively. The PL of the doped sample showed a broad-band emission spectrum centered at 465 nm accompanied with shoulders at around 425, 450 and 510 nm, which are the characteristic emission peaks of interstitial zinc, sulfur vacancies and Cu²⁺ ions, respectively. Our experimental results indicate that the PL spectrum confirms the presence of Cu²⁺ ions in the ZnS nanoparticles as expected.     

Defect states in Lu 3 Al 5 O 12 :Ce crystals

Wavelength-resolved TSL measurements after x-ray irradiation at room temperature were performed on undoped, Ce- and (Ce, Zr)-doped Lu 3 Al 5 O 12 crystals. Several glow peaks were observed in the 20-450 v C temperature region, whose intensities and emission spectra are influenced by doping. Namely, the TSL spectra are governed by defect and trace impurity-related emissions in the undoped crystal, while only the Ce 3+ emission is detected in the doped crystals. Moreover, EPR measurements performed at 12 v K revealed typical spectra of Ce 3+ (4f 1 , S =1/2) occupying Lu 3+ substitutional positions. In situ light irradiation (250-330 v nm) of the crystals results in a step-like decrease of the Ce 3+ EPR intensity. Such a behaviour can reflect a creation of Ce 4+ ions under UV irradiation or an increase of the Ce 3+ population in the excited (5d) state.     

Luminescence spectra of doped and undoped lead tungstate crystals

TL spectra of undoped lead tungstate crystals exhibit glow peaks at 30 v K and 85 v K centred at 440 v nm, plus a peak at 50 v K at 530 v nm in an annealed sample. Annealing adds a 170 v K peak. Trivalent dopants of La 3+ and Y 3+ reduce the green luminescence, and Nb 5+ introduces a peak near 100 v K centred at 530 v nm; Sb introduces features between 40 v K and 90 v K and 150 and 180 v K. The luminescence emissions around 50 v K may be attributed to complex intrinsic defect centres, including (WO 4 ) m 3 . Of the four dopants studied in the present research, Sb +5 has the highest luminescence intensity. CL spectra show interesting anomalies near 170 v K which are linked to a phase change of water/ice nanoparticles trapped at dislocations.     

Role of Al or Eu on thermoluminescence of Al- and/or Eu-doped SiO2 crystals

Although SiO₂ crystals have been used in electroluminescence devices and thermoluminescence (TL) dosimeters, the emission mechanism of TL has not yet been clearly explained. Recently, as we could get amorphous and highly pure SiO₂ prepared by the sol-gel method, we have investigated the TL emission mechanism using Al³⁺- and/or Eu³⁺-doped SiO₂ crystalline samples prepared by the heat-treatment under much lower temperature that the melting point of SiO₂. The TL spectrum of the Eu³⁺-doped sample displayed several peaks, including two main peaks due to the electron transitions from ⁵D₂ to ⁷F₅ (ca. 570 nm) and from ⁵D₀ to ⁷F₂ (ca. 610 nm). As doping concentration increased, all the peak intensities reduced from maximum values except that due to the electron transition from ⁵D₀ to ⁷F₂. These observations are thought to result from a cross-relaxation process due to the lack of inversion symmetry at the Eu³⁺ site.     

Effect of 100 MeV swift Si8+ ions on structural and thermoluminescence properties of Y2O3:Dy3+nanophosphor

Nanoparticles of Y₂O₃:Dy³⁺ were prepared by the solution combustion method. The X-ray diffraction pattern of the 900°C annealed sample shows a cubic structure and the average crystallite size was found to be 31.49?nm. The field emission scanning electron microscopy image of the 900°C annealed sample shows well-separated spherical shape particles and the average particle size is found to be in a range 40?nm. Pellets of Y₂O₃:Dy³⁺ were irradiated with 100?MeV swift Si⁸⁺ ions for the fluence range of 3?×?10^11_3?×?10¹³ ions cm^?2. Pristine Y₂O₃:Dy³⁺ shows seven Raman modes with peaks at 129, 160, 330, 376, 434, 467 and 590?cm^?1. The intensity of these modes decreases with an increase in ion fluence. A well-resolved thermoluminescence glow with peaks at ～414?K (T_m1) and ～614?K (T_m2) were observed in Si⁸⁺ ion-irradiated samples. It is found that glow peak intensity at 414?K increases with an increase in the dopant concentration up to 0.6?mol% and then decreases with an increase in dopant concentration. The high-temperature glow peak (614?K) intensity linearly increases with an increase in ion fluence. The broad TL glow curves were deconvoluted using the glow curve deconvoluted method and kinetic parameters were calculated using the general order kinetic equation.     

Comparative investigations of TL and OSL in KCI:Eu2+ crystals irradiated with UV and X-rays

Abstract

We present thermoluminescence (TL) glow curves and optical stimulated luminescence (OSL) response from both KCl:Eu²⁺ crystals irradiated with soft X-rays (20 KV, 80 μA) and ultraviolet light (230 nm). Two situations take place. First, we observed that for long time F-light bleaching (560 nm) the typical TL glow curve of X-rays irradiated KCl:Eu²⁺ resembles the TL glow curve of UV-irradiated samples. Second, along with OSL measurements, we have performed a thermal bleaching and we have addressed F and F_z participation in OSL. These results provide us a supportable correlation between F and F_z as responsible centers for OSL and TL processes.     

Luminescence in x-irradiated CaF2:Co

Photoluminescence of X-irradiated CaF₂:Co single crystals is reported. The emission spectrum shows four peaks at 505, 550, 640 and 685 nm, all of them with an excitation band at 275 nm. The same emission spectrum, plus a band at 280 nm, is found in X-ray excited luminescence measurements. Thermoluminescence of 80 K X-irradiated crystals gives a glow curve with five peaks at 100, 125, 145, 190 and 225 K. The spectral distribution of these glow peaks is similar to that of the X-ray excited luminescence. The 280 nm band is associated with electron—hole recombination. The other four bands are associated with electron transitions among excited states of Co²⁺ produced by recombination of holes and Co⁺-ions created by X-irradiation.     

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.