Thermoluminescence and optical absorption studies in γ-irradiated KClxBr1–x mixed crystals

Thermoluminescence (TL) and optical absorption measurements have been carried in γ-irradiated KCl, KBr and various compositions of KCl_xBr_1–x mixed crystals as a function of irradiation time and composition. The position of the main glow peak (high temperature peak) and F-band position are found to vary non-linearly with composition, showing a correlation between colour centers and TL. The TL peaks have been analysed by numerical fitting and the trap depths and frequency factors have been calculated for different compositions of the mixed crystals. The thermal ionisation energy of F-centers has been calculated for the mixed crystals and it is found to vary non-linearly with composition. The results obtained in mixed crystals have been discussed in terms of high disorder present in them.     

Thermoluminescence studies in KBrxI1–x mixed crystals

Thermoluminescence (TL) studies have been carried out in KBr, KI, and in different compositions of KBr_xI_1–x mixed crystals as a function of X-irradiation time. The TL glow peaks have been analysed and the trap depths and frequency factors have been calculated for different compositions. The complex TL peaks observed in these crystals were isolated by using thermal cleaning technique. The various glow peaks observed in these crystals were attributed to native impurities, first stage and second stage colour centers and the results have been discussed.     

Kinetics and Trapping Parameters of Thermoluminecence of Sr1−xEuxF2+x Mixed Crystrals

The kinetics and trapping parameters of thermoluminescence of Sr_1−xEu_xF_2+x mixed crystals have been calculated by using different methods. The trap depths, frequency factors, and order of kinetics of glow curve pattern in several compositions of the system revealed variations with composition.     

Effect of change of state of aggregation of impurity on tl and microhardness of KClxBr1–x mixed crystals doped with Ca2+

Microhardness and Thermoluminescence (TL) measurements have been made in KCl_xBr_1–x mixed crystals doped with Ca²⁺ impurity. The variation of hardness in undoped and Ca²⁺ doped KCl_xBr_1–x crystals with quenching temperature is investigated. TL studied of KCl_xBr_1–x crystals doped with Ca²⁺, both in as-grown state and after quenching them from various elevated temperatures indicate that the positions of the glow peak which has been attributed to F-centers is found to depend upon the state of dispersion of impurity.     

Low temperature TL glow curves in KBrxI1-x mixed crystals

Thermoluminescence (TL) glow curves were recorded in KBr, KI and in different compositions of KBr_xI_1-x mixed crystals at LNT. For this a cryostat has been designed and fabricated. The glow peaks observed in these crystals have been attributed to differnent colour centers.     

Glow curves and the emission of BaFCl:Eu2+

Thermoluminescence and the emission of γ-irradiated BaFCl:Eu²⁺ has been studied. A well defined glow peak at 400 K and a shoulder at 480 K are obtained in addition to those obtained as in undoped BaFCl. Thermoluminescence emission has shown a band at about 390 ∼ 400 nm. Additional glow peaks have been attributed to the luminescence centers as caused by europium impurity.     

Thermoluminescence and Optical Absorption Studies of Z1 Centers in KCI Crystals Doped with Praseodymium

Thermoluminescence (TL) of Pr-doped KCI is studied. The influence of pre-heat treatment and optical bleaching of the glow curves and the production of Z₁ centers are discussed. The glow curves of KCI containing 1062 ppm of praseodymium (Pr) shows one shoulder at 365 K (T₁) and two peaks around 408 K (T₂) and 443 K (T₃), respectively. Bleaching of X-irradiated crystals shows that the peak T₂ is enhanced whereas other two (T₁, T₃) get suppressed. Optical absorption studies of the crystals before and after F-bleaching shows that the F-band decreases and shifts towards longer wavelengths. The decrease is accompanied by broadening towards the longer wavelength. The T₂ peak is attributed to Z₁ centres. It is shown that T₁ corresponds to shallow centers and T₃ peak is attributed to F-centers.     

Coloring elimination in Sr1 − x Ce x F2 + x crystals in the visible spectral range during growth from melt

Crystals of the Sr_{1 ? x} Ce _x F_{2 + x} compositions close to the congruent one (x ～ 0.3) are fabricated by the vertical directional crystallization. It is shown that the use of CF₄ to form a fluorinating atmosphere during growth leads to additional spurious absorption in the crystals in the range 350–600 nm. The use of PbF₂ and ZnF₂ for fluorination makes it possible to obtain colorless Sr_{1 ? x} Ce _x F_{2 + x} crystals of the desired optical quality from melt. The thermal conductivity of crystal with x ～ 0.28 in the temperature range 80-500 K lies within 1.50 ± 0.03 W m^?1 K^?1. High ionic conductivity makes the Sr_{1 ? x} Ce _x F_{2 + x} crystals promising for application in solid-state ionics.     

Thermal Expansion of EuF<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript> Single Crystals and Their Thermal Stability

Thermal expansion of an EuF_2.136 nonstoichiometric crystal with the fluorite structure type (Eu _0.864 ²⁺ Eu _0.136 ³⁺ F_2.136, lattice parameter 5.82171(5) Å) has been experimentally investigated in the temperature range of 9–500 K. The coefficient of thermal expansion is α = 15.8 × 10^–6 K^–1 at T = 300 K. The observed anomalies in the behavior of the coefficient of thermal expansion at T > 400 K are related to the oxidation processes with partition of Eu²⁺ ions. It is established by differential scanning calorimetry that the onset temperature of EuF_{2 + x} oxidation in air is 430 K and that this process occurs in three stages. X-ray diffraction analysis shows that the oxidation is accompanied by the formation of a phase mixture based on two modifications of the Eu _{1– y} ³⁺ Eu _y ²⁺ F_3–y solid solution with the structure types of tysonite (LaF₃), orthorhombic β-YF₃ phase, and europium oxyfluorides of variable composition EuO_1–xF_{1 + 2x}, with dominance of the latter.     

Characteristics of traps in Tl2Ga2Se3S single crystals by low‐temperature thermoluminescence measurements

Defect characterization of Tl₂Ga₂Se₃S single crystals has been performed by thermoluminescence (TL) measurements at low temperatures between 10 and 70 K with various heating rate ranging from 0.6 to 1.0 K/s. The TL signal due to the luminescence from trap centers revealed one glow peak having maximum temperature of 36 K. Curve fitting and various heating rate methods were used for the analysis of the glow curve. The activation energy of 13 meV was found by the application of curve fitting method. This practical method also established that the trap center exhibits the characteristics of mixed (general) kinetic order. In addition, various heating rate analysis gave a compatible result (13 meV) with curve fitting as the temperature lag effect was taken into consideration. Distribution of traps was also investigated using an experimental method. A quasi‐continuous distribution was attributed to the determined trap centers.     

Effect of Flux on thermoluminescence in Flux-grown BaFCl crystals

BaFCl crystals have been grown using BaF₂ and BaCl₂ by flux technique. Glow curves, optical absorption, and TL emission spectra of x/r — irradiated crystals are studied. The results have been compared with those BaFCl crystals grown from NaF flux so as to study the effects of flux on these properties. It is found that crystals grown from BaF₂ flux are relatively purer. An additional TL glow peak at 460 K, an optical absorption band at 775 nm and TL emission band at 485 nm have been obtained in the presently grown crystals. The additional glow peak, optical absorption band have been attributed to F(¯F) aggregate centers, whereas the 485 nm TL emission band to impurity centers.     

Glow curves of flux-grown NaMgF3 crystals

Glow curves and optical absorption spectra of X-irradiated flux grown crystals are studied. Two glow peaks at 370, 585 K and three shoulders at 420, 540 and 610 K are obtained. Optical absorption studies reveal two absorption bands at 405 and 475 nm and a well defined peak at 295 nm. Room temperature annealing and bleaching studies have suggested that the glow peaks at 370 and 585 K may correspond to impurities and F-centers of 295 nm band respectively. The other shoulders at 420, 540 and 610 K are attributed to other F-aggregate centers. The glow peaks are analysed using first order kinetics.     

Nanostructured crystals of fluorite phases Sr1 ? xRxF2 + x (R are rare-earth elements) and their ordering: IV. Study of the optical transmission spectra in the 2–17-μm wavelength range

Transmission spectra of two-component crystals of Sr_1−x R _x F_2+x (R = Y, La-Lu; 0 ≤ x ≤ 0.5) in the 1–17-μm wavelength range were studied. The spectral characteristics of these crystals and of single-component crystals of MF₂ (M = Ca, Sr, or Ba) and RF₃ (R = La-Nd) were compared. The transmission cutoff of Sr_1−x R _x F_2+x crystals is shifted to shorter wavelengths with increasing x. The same tendency is observed with the increasing atomic number R of rare-earth elements for two isoconcentration series of Sr_1−x R _x F_2+x (x ∼ 0.10 and 0.28). This tendency is pronounced at large x. The transmission cutoff of Sr_1−x R _x F_2+x crystals can be varied in the range of from 10.7 to 12.2 μm by changing their qualitative (R) and quantitative (x) composition. Hence, these crystals can be assigned to multicomponent fluoride optical materials with controlled optical characteristics. The Sr_1−x R _x F_2+x crystals, where R = Ce-Sm, were shown to be promising materials for the design of selective optical filters in the 2–10-μm spectral range.     

Ionic conductivity of congruently melting Ca0.6Sr0.4F2 and Ca1 ? x ? ySryRxF2 + x (R = La, Ce, Pr, Nd) single crystals with fluorite structure

Single crystals of congruently melting compositions of the Ca_0.6Sr_0.4F₂ and Ca_{1 − x − y} Sr _y R _x F_{2 + x} (R = La, Ce, Pr, Nd; x = 0.16–0.21; y = 0.07–0.16) solid solutions with fluorite structure have been grown by the Bridgman-Stockbarger method. Their electrical properties have been investigated in the range from 473 to 823 K, and it is shown that they are ionic conductors. For Ca_0.6Sr_0.4F₂ crystals, the ionic conductivity σ = 2 × 10⁻⁶ S/cm at 673 K, and the ion transport activation energy E _a = 1.1 eV. For Ca_0.77Sr_0.07La_0.16F_2.16, Ca_0.70Sr_0.11Ce_0.19F_2.19, Ca_0.65Sr_0.15Pr_0.20F_2.20, and Ca_0.58Sr_0.21Nd_0.21F_2.21 crystals, the values of σ lie in the range from 9 × 10⁻⁷ to 2 × 10⁻⁶ S/cm at 500 K, and the activation energy E _a is 0.88–0.93 eV. The concentration and mobility of ionic charge carriers in Ca_{1 − x − y} Sr _y R _x F_{2 + x} crystals have been calculated. Original Russian Text ? N.I. Sorokin, D.N. Karimov, E.A. Krivandina, Z.I. Zhmurova, O.N. Komar’kova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 2, pp. 297–303.     

Isomorphous substitution and luminescence properties of haloapatites synthesized by the low-temperature method

Single-phase polycrystalline fluorapatites of the Ca_{10 − x} Me _x (PO₄)₆F₂:Eu³⁺ (Me = Pb, Mg) composition are obtained by deposition from aqueous solutions. The effect of modifier ions (Pb²⁺, Mg²⁺) with significantly different ionic radii on the structure and spectral luminescence properties of the fluorapatites are studied. It is established that Pb²⁺ and Mg²⁺ ions affect the preferred location of Eu³⁺ ions in the structure of Ca_{10 − x} Me _x (PO₄)₆F₂ crystals.     

Thermoluminescence studies of Al2O3 crystals doped with Cobalt impurity

Thermoluminescence (TL) studies of cobalt-doped Al₂O₃ crystals irradiated with X-rays have shown that the TL glow curve consists of three peaks at 105, 195 and 260°C. Bleaching, annealing and quanching studies have been performed in order to understand the nature of colour centers responsible for the formation of the three peaks. The values of the fundamental parameters like trap depth and frequency factor are estimated from TL data and the results obtained are discussed.     

Nanostructured crystals of Sr1?xRxF2+x fluorite phases and their ordering: 6. Microindentation analysis of crystals

Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr_{1 − x} R _x F_{2 + x} (R are 14 rare earth elements (REEs); 0 < x ≤ 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr_{1 − x} R _x F_{2 + x} (0 < x ≤ 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr_0.90 R _0.10F_2.10 crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr_{1 − x} R _x F_{2 + x} crystals is higher by a factor of ∼2–3 than that of SrF2. The effect of decrease in microstresses in SrF₂ crystals is confirmed by the isomorphic introduction of R ³⁺ ions into this crystalline matrix.     

Nanostructured crystals of fluorite phases Sr1 − x R x F2 + x and their ordering: 9. The defect crystal and real structure of quenched fluorite phases Sr1 − x Ce x F2 + x (x = 0–0.5)

A Sr_0.7Ce_0.3F_2.3 crystal (CaF₂ type, sp. gr. $Fm\bar 3m$ ), obtained by quenching from melt, has been studied for the first time by X-ray diffraction. Fluorine vacancies and interstitial anions are found in the 8c and 32f sites, respectively. The defect ratio in the Sr_0.7Ce_0.3F_2.3 structure corresponds to the tetrahedral cluster configuration of defects {Sr_{4 ? n} Ce _n F₂₆}. The defect structure of quenched (at a rate of ～25 K/min) crystal differs from that of a crystal grown from melt (cooling at a rate of ～3 K/min) by the displacement of some cations (presumably Ce³⁺) along the threefold axis to the 32f site and the anisotropy of thermal vibrations of ions in the cluster core (F _int(32f)3). The concentration dependence of the lattice parameters of quenched Sr_{1 ? x} Ce _x F_{2 + x} phases (x = 0–0.5) is described by a third-order polynomial: a = 5.80009 + 1.166518 × 10^?3 x ? 1.124969 × 10^?5 x ² + 8.258155 × 10^?8 x ³. The compositional dependence of microdistortions is also nonlinear; maximum microdistortions are observed in the SrF₂ crystal. They decrease with an increase in the cerium concentration x to ～ 0.35. The minimum in the range x = 0.30–0.35 correlates with a composition corresponding to the peak (at x ～ 0.29) in the melting curves of the fluorite phase estimated from the phase diagram of the SrF₂-CeF₃ system (the method of thermal analysis).     

Characterization of Eu3+-doped fluorophosphate glasses for red emission

Fluorescence spectra and decay curves of the ⁵D₀ level for different concentrations of Eu³⁺ (4f⁶) ions in K–Ba–Al fluorophosphate glasses have been measured at room temperature and are analyzed. The Judd–Ofelt intensity parameters Ω₂ and Ω₄ have been determined from the intensity ratios of emission peaks corresponding to ⁵D₀ → ⁷F_J (J = 2 and 4) to ⁵D₀ → ⁷F₁ transitions for 1.0 mol% glass. The intensity parameters thus obtained are in turn used to calculate the radiative properties of the fluorescent levels of Eu³⁺ ions. Second and fourth rank crystal-field parameters have been evaluated by assuming a C_2V site symmetry for the local environment of Eu³⁺ ions to estimate the crystal-field strength experienced by Eu³⁺ ions in the present host. The decay profiles of the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions in the present glasses are found to be single exponential for all the studied Eu³⁺ ion concentrations. A marginal increase in lifetime of the ⁵D₀ level has been noticed with Eu³⁺ ion concentration up to 2.0 mol% and then the lifetime marginally decreases for higher Eu³⁺ ion concentrations.