Recombination processes in lanthanum beryllate single crystals doped with Ce3+ and Pr3+ ions

The paper presents experimental results on recombination processes in lanthanum beryllate (BLO) single crystals (undoped BLO, and doped with 0.5 at % by Ce³⁺ and Pr³⁺ ions) obtained using XRL-spectroscopy at T = 8, 80 and 290 K and thermoluminescence technique in the temperature range of 8–650 K. The paper discusses spectra of the steady-state XRL-luminescence recorded in the energy range from 1.5 to 6.2 eV at different temperatures between 8 and 290 K; temperature dependences of XRL intensity recorded in the temperature range from 8 to 650 K; thermoluminescence glow curves recorded in spectral-integrated regime after X-ray exposure at T₀ = 8 or 290 K.     

Luminescence and recombination processes in bulky Li6Gd x Y1 − x (BO3)3:Eu crystals

The luminescence and recombination processes in crystals of lithium borates Li₆Gd _x Y_{1 − x} (BO₃)₃:Eu have been investigated. The steady-state X-ray luminescence (XRL) spectra, the temperature dependences of the XRL intensity, and the thermally stimulated luminescence (TSL) spectra have been measured for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃:Eu, and Li₆Gd(BO₃)₃:Eu compounds in the temperature range of 90–500 K. It is established that the band at 312 nm, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ ions and the group of lines at 580–700 nm, which are due to the ⁵ D ₀ → ⁷ F _J (J = 0 … 4) transitions in Eu³⁺ ions dominate in the XRL spectra. The XRL intensity in these bands increases several times with a change in temperature from 100 to 400 K for undoped crystals. The likely mechanisms of the observed temperature dependence of the XRL intensity and their relationship with the features of electronic-excitation energy transfer in these crystals are discussed. The spectra of all crystals under study exhibit a dominant composite TSL peak with a maximum at 110–160 K and a series of weaker peaks, the composition and structure of which depend on the crystal type. The nature of the shallow traps, which are responsible for the TSL at temperatures below room, and their relationship with the defects of lithium cation sublattice are discussed.     

Thermoluminescence and optically stimulated luminescence characteristics of Al2O3 doped with Tb

In the present work policrystals of α − Al₂O₃ doped with terbium were synthesized using the solvent evaporation method. The samples were prepared using Al(NO₃)₃·9H₂O and Tb(NO₃)₃·5H₂O reagents, with Tb concentrations between 1 and 5 mol% and thermally treated at high temperature above ∼1400 °C. X-ray diffraction measurements showed the α-phase formation of samples. TL glow curve presented an intense peak at ∼190 °C and two other with low intensity at 290 and 350 °C after gamma irradiation. The best doping concentration which presented high luminescence was the sample doped with 3 mol% of Tb. TL spectra and fluorescence measurements showed similar luminescence spectra with lines attribute to Tb³⁺ ions. A linear behavior to gamma dose between 1 and 20 Gy was observed in TL, using 190 °C peak as well as in OSL signal, this last carried out using 532 nm wavelength stimulation.     

Identification of F+ centers in hafnia and zirconia nanopowders

Luminescence properties of undoped hafnia and zirconia nanopowders prepared by solution combustion synthesis were investigated under photo- and electron-beam excitation in 10–400 K temperature range. Along with the main luminescence band revealed in investigated materials at low temperatures at 4.2–4.3 eV and ascribed to the emission of self-trapped excitons, there are luminescence bands due to defects and impurities introduced during sample preparation. At room temperature the latter emissions dominate in the luminescence spectra as the intrinsic self-trapped exciton emission is quenched. Analysis of decay kinetics of defect centers allowed identification of F⁺ centers emission at 2.8 eV with lifetimes ∼3–6 ns in hafnia and zirconia under intra-center excitation.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

Thermally stimulated luminescence of bismuth germanate ceramics with the benitoite,eulitine, and sillenite structures

Thermally stimulated luminescence (TSL) of Bi₂Ge₃O₉, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀ and the primary components Bi₂O₃ and GeO₂ was studied under x-ray excitation. Thermal activation energies and frequency factors of trapping centers in the studied ceramics were determined. The relationships of TSL bands of the studied ceramics with maxima at 141–145 and 166–170 K and damage to the Ge sublattice and of TSL bands with maxima at 104–110 and 180–190 K and recombination processes in the Bi sublattice were demonstrated. Recombination processes causing luminescence upon nonequilibrium charge carrier release from trapping centers occur in structural complexes of similar configuration that contain the Bi ion in a nearest environment of O atoms. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 359–364, May–June, 2008.     

Optically Induced Effects in the Thermoluminescence of Dosimetric Anion-Defective Corundum Crystals

This paper considers the influence of light fluxes in the 200–600-nm spectral range on the thermally stimulated luminescence (TL) of TLD-500 radiation detectors based on anion-defective corundum crystals. It has been shown that the luminescent-storing action of light in the above spectral range is due to the optical ionization of F-centers and electronic trapping centers of carriers responsible for the dosimetric peak at 450 K and TL at higher temperatures. The features of the dosimetric information distortion depending on the initial state of population of deep traps and the spectral composition and power of optical radiation are discussed.     

Application of hexagonal boron nitride micropowder for thermoluminescent dosimetry of UV radiation

Thermoluminescence (TL) response of h-BN micropowder, characterized by two peaks near 337 and 584 K, was studied in the 380-nm band after excitation with monochromatic ultraviolet radiation (UVR). On the basis of the obtained results and independent data analysis, assumptions were made on the mechanisms of donor–acceptor recombination with the participation of 1B, O_N, and C_N centers, responsible for the observed thermally activated emission. TL excitation spectra in the 200–380-nm range were analyzed. It was observed that the resolved maxima correspond quite to the characteristic wavelengths of 260 nm (maximum bactericidal efficiency) and 297 nm (maximum skin erythema). It is found that the dose dependence for an integral intensity of high-temperature peak is linear in the suberythemal range of 0.01–0.35 mJ/cm².     

Thermostimulated Luminescence of PbWO4, Bi2WO6, and Y2WO6 Ceramics

Thermostimulated luminescence (TSL) of PbWO₄, Bi₂WO₆, and Y₂WO₆ ceramics on x-ray excitation is investigated. The spectral luminosity of the thermostimulated luminescence is analyzed. The thermal activation energies conforming to the corresponding thermostimulated luminescence peaks are determined. It is established that on emptying trapping centers radiative recombination occurs at the intrinsic-luminescence centers associated with tungsten-oxygen complexes WO₄ ^2–.     

X-Ray Induced and Thermostimulated Luminescence of New Fluorine Containing Compounds (Potential Luminophores,Scintillators and Dosimeters)

X-ray induced luminescence spectra in optical range of wave-lengths (200–700 nm) and thermoluminescence curves for fluoride, fluorosulphate, fluorophosphate and fluorooxalate compounds of the titanium subgroup elements with alkali metals and ammonium have been obtained. Influence of annealing and repeated X-raying on luminescence (XRL) spectra of a number of compounds has been examined. Alloy additives influence on fluorine compounds XRL spectra has been examined. Most of compounds being under study may be used as X-ray luminophores, scintillators and dosimeters. The highest intensity of luminescence was achieved for such compounds as K₂ZrF₆, Cs₂ZrF₆, Rb₂ZrF₆ (especially for doped K₂ZrF₆), K₂HfF₆ and CsZr₂(PO₄)₃. Radiation drifting to long-wave range for a number of fluorophosphatezirconates in comparison with fluorides may be a positive moment in making luminophores on their base.     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

Thermoluminescence of pure and doped ThO2

Thermoluminescence (TL) measurements in the temperature range 295–675 K indicate the existence of at least five trapping centres for single crystals of nominally pure “reduced” ThO₂ and three trapping centres for “oxidized” ThO₂. Deliberate doping with Ca²⁺, Y³⁺ and Ta⁵⁺ impurities decreases TL emission. For reduced ThO₂, accidentally incorporated rare-earth impurities, Pr³⁺, Tb³⁺, Er³⁺ act as the electron-hole recombination sites. In oxidized crystals the impurity Fe³⁺ is thought to be involved in the recombination process. In the temperature range 80–295 K an additional eight trapping centres exist for both oxidized and reduced ThO₂. For the reduced crystals the emission is probably associated with Fe in the +2 state, and in the +3 state for oxidized crystals. The differences in the TL glow curve intensities are partially explained by differences in the temperature dependence of the luminescence efficiency of the different recombination centres.     

Cathodoluminescence studies of un-doped and (Cu,Fe, and Co)-doped tin dioxide films deposited by spray pyrolysis

Un-doped and (Cu, Fe, and Co)-doped SnO₂ were studied using films deposited by spray pyrolysis. Room temperature cathodoluminescence (CL) was measured. Differences in CL spectra were observed as a function of deposition parameters (T_sub-350–550 °C), the nature and concentration of dopants (0–16 at.%), and the resulting high annealing temperature (T_an = 700–950 °C). A possible luminescence mechanism has been discussed. It was established that changes taking place in CL spectra were caused by the change of both the grain size and crystallinity (stoichiometry) of the surface layer. It was concluded that radiative recombination occurs through shallow donor levels associated with O-vacancies and trapped centers. It was assumed that in SnO₂ there are apparently three types of defects forming deep levels located at 0.8–0.9, 1.3–1.4, and ∼1.6 eV from the top of the valence band.     

Features of OSL and TL properties of anion-defective corundum crystals exposed to thermo-optical treatment

The results of systematic investigation of the mechanisms and role of phototransfer in TL and OSL processes in α-Al₂O_3−δ crystals under controlled filling of the main and deep traps depleted at 450 and 720 K, respectively, are presented.Optical depletion spectra of the main and deep traps were measured and compared. It was found that green light stimulation only depletes the main trap, while blue light depletes both the main and deep traps. Optical depletion of the deep trap results in phototransfer of charges that can be realized by 2 mechanisms: either through the main trap to recombination centers or directly to the latter. However, the dominant contribution to the OSL signal is provided by phototransfer through the main trap. It is also found that UV emission at 3.7 eV dominates over F-emission at 3.0 eV in the phototransferred TL spectrum. It is assumed that this UV emission is not related to the F⁺ centers.     

Determination of trapping parameters of thermoluminescent glow peaks of semiconducting Tl2Ga2S3Se crystals

Thermoluminescence (TL) properties of Tl₂Ga₂S₃Se layered single crystals were researched in the temperature range of 290–770 K. TL glow curve exhibited two peaks with maximum temperatures of ~373 and 478 K. Curve fitting, initial rise and peak shape methods were used to determine the activation energies of the trapping centers associated with these peaks. Applied methods were in good agreement with the energies of 780 and 950 meV. Capture cross sections and attempt-to-escape frequencies of the trapping centers were reported. An energy level diagram showing transitions in the band gap of the crystal was plotted under the light of the results of the present work and previously reported papers on photoluminescence, thermoluminescence and thermally stimulated current measurements carried out below room temperature.     

Thermo-and photostimulated luminescence of CaI2: Tl and CaI2: Pb crystals

Thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb scintillation crystals under optical and X-ray excitation is studied. It is shown on the basis of the results obtained with account for the data of studies of photo-and X-ray-luminescent properties of these scintillators that Tl⁺ and Pb²⁺ ions form complex capture centers with host defects. These centers are responsible for the thermostimulated luminescence in the temperature range of 150–295 K, and the centers of charge carrier trapping are spatially separated from the centers of recombination emission. An assumption is made that thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb crystals under optical excitation is observed mainly due to the delocalization of charge carriers from hydrogen-containing centers responsible for the excitation band at 236 nm and the photoluminescence of CaI₂ with a maximum at 395 nm. The luminescence of CaI₂: Tl crystals in the 510-nm band and CaI₂: Pb crystals in the 530-nm band is determined by the radiative decay of near-activator excitons.     

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.     

Features of thermoluminescence in anion-defective alumina single crystals after highdose irradiation

The effect of high-dose irradiation by electron beam with nanosecond duration and by gamma-rays on thermoluminescence (TL) yield of anion-defective dosimetric Al₂O₃:С crystals is studied. It is shown that in a wide dose range up to 10 kGy no significant changes in the TL curve shape and the temperature position of the main dosimetric peak (T = 460 K) are observed. The TL yield of this peak is in saturation in the high-dose range 5–80 kGy. Then anomalous increase in TL yield is registered at the dose growth up to 800 kGy. With that an intensive band appears in the green spectrum region in the photoluminescence spectrum. The role of aggregate defects forming F₂-type centers with the increase of TL yield in Al₂O₃:С crystals under high-dose irradiation is discussed.     

Low-temperature luminescence and thermally stimulated luminescence of BeO: Mg single crystals

Luminescence and thermally stimulated luminescence (TL) of BeO: Mg crystals are studied at T = 6–380 K. The TL glow curves and the spectra of luminescence (1.2–6.5 eV), luminescence excitation, and reflection (3.7–20 eV) are obtained. It is found that the introduction of an isovalent magnesium impurity into BeO leads to the appearance of three new broad luminescence bands at 6.2–6.3, 4.3–4.4, and 1.9–2.6 eV. The first two are attributed to the radiative annihilation of a relaxed near-impurity (Mg) exciton, the excited state of which is formed as a result of energy transfer by free excitons. The impurity VUV and UV bands are compared with those for the intrinsic luminescence of BeO caused by the radiative annihilation of self-trapped excitons (STE) of two kinds: the band at 6.2–6.3 eV of BeO: Mg is compared with the band at 6.7 eV (STE₁) of BeO, and the band at 4.3–4.4 eV is compared with the band at 4.9 eV (STE²) of BeO. In the visible region, the luminescence spectrum is due to a superposition of intracenter transitions in an impurity complex including a magnesium ion. The manifestation of X-ray-induced luminescence bands at T = 6 K in BeO: Mg indicates their excitation during band-to-band transitions and in recombination processes. The energy characteristics of the impurity states in BeO: Mg are determined; the effect of the isovalent impurity on the fluctuation rearrangement of the BeO: Mg structure in the thermal transformation region of STE₁ → STE₂ is revealed.     

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.