Thermoluminescence studies on Cu-doped Li2B4O7 single crystals

Lithium tetraborate (Li₂B₄O₇) is a tissue equivalent material and single crystals of this material doped with Cu are promising for dosimetric applications. In the present study highly transparent single crystals of lithium tetraborate (Li₂B₄O₇) doped with Cu (0.5 wt%) have been grown using the Czochralski technique. The Li₂B₄O₇:Cu crystals were studied using photoluminescence, X-ray diffraction (XRD), UV-vis transmission, time resolved fluorescence and thermoluminescence (TL) techniques. The TL readout of Li₂B₄O₇:Cu crystals showed two well-defined glow peaks at 402 K (peak-1) and 513 K (peak-2) for a 4 K/s heating rate. While the low temperature TL peak-1 fades completely within 24 h at room temperatures, the main dosimetric peak-2 remains the same. The TL sensitivity of the grown single crystal is found to be 3.3 times that of a conventional TL phosphor, TLD-100. The Li₂B₄O₇:Cu crystals showed a linear TL dose-response in the range from 1 mGy to 1 kGy. The TL analysis using a variable dose method revealed first order kinetics for both the peaks. Trap depth and frequency factor for peak-1 were found to be 0.81 eV and 5.2×10⁹ s⁻¹, whereas for peak-2 the values were 1.7 eV and 1.7×10¹⁶ s⁻¹, respectively.     

Optical absorption of isotopically enriched Li2B4O7 single crystals irradiated by thermal neutrons

Induced absorption spectra in the range 200–900 nm at 77 and 290 K for Li₂B₄O₇ single crystals, isotopically Li and B enriched are presented after irradiation of these crystals by thermal neutrons with fluence 1.8×10¹⁶ cm⁻². The dependence of induced absorption spectra on the isotope composition was revealed: for ⁶Li₂¹⁰B₄O₇ and ⁷Li₂¹⁰B₄O₇ crystals intensive band in the region of 280–294 nm was observed. Under substitution of ⁷Li isotope by ⁶Li in the lithium tetraborate lattice no changes in the absorption spectra were observed. The nuclear reaction ¹⁰B(n,)⁷Li is proposed to be the main mechanism of formation of the radiation defects.     

Influence of reducing annealing on the luminescent properties of Li2B4O7:Cu single crystals

Li₂B₄O₇:Cu single-crystal annealing in the reducing environment results in a sharp drop of intensity of thermoluminescence (TSL) and X-ray luminescence (XL) peaks. It was suggested that during annealing in the reducing environment, an oxygen vacancy is produced in the LTB structure at the bridging oxygen atom site. Oxygen vacancy charge compensation takes place at the expense of reduction of the doping Cu⁺ ion to the Cu⁰ state. In this case the A⁰-type thermoluminescence center formation mechanism due to irradiation becomes impossible.     

Li2B4O7晶体的晶格振动光谱

在室温下测量了Li₂B₄O₇单晶的各种振动类的偏振Raman散射谱和该晶体粉末样品的红外吸收谱(200—4000cm^-1)。根据LO-TO劈裂的实验结果,计算出该晶体极化模的有效电荷和振子强度。通过与BBO和LBO晶体的结构和B—O伸缩振动模频率比较,得出:Li₂B₄O₇晶体可能有较大的非线性光学系数。 关键词：     

Luminescence characteristics of Cu- and Eu-doped Li2B4O7

Photoluminescence, radioluminescence as well as optical absorption techniques were used to characterize Cu- and Eu-doped lithium tetraborate. The effect of host modification (single crystal and glassy state) and a limited range of dopant content were investigated. Time-resolved measurements were helpful to identify the emitting species.     

Influence of different annealing conditions on the luminescent properties of Li2B4O7:Mn single crystals

The influence of reducing annealing and repeated oxidizing annealing of the Li₂B₄O₇:Mn single crystals on their thermostimulated luminescence (TSL) and X-ray luminescence (XL) has been studied. Because of the oxygen vacancies formation and the dopant ions reduction, the reducing annealing results in a drastic decrease of the luminescence intensity along with the simultaneous shift of a part of the maxima and redistribution of the peak intensities. The repeated annealing in the oxidizing environment leads only to the partial reduction of the luminescent properties of the Li₂B₄O₇:Mn crystals.     

Synthesis and characterization of thermoluminescent Li2B4O7 nanophosphor

Lithium borate (Li₂B₄O₇) is a low Z_eff, tissue equivalent material that is commonly used for medical dosimetry using the thermoluminescence (TL) technique. Nanocrystals of lithium borate were synthesized by the combustion method for the first time in the laboratory. TL characteristics of the synthesized material were studied and compared with those of commercially available microcrystalline Li₂B₄O₇. The optimum pre-irradiation annealing condition was found to be 300 °C for 10 min and that of post-irradiation annealing was 300 °C for 30 min. The synthesized Li₂B₄O₇ nanophosphor has very poor sensitivity for low doses of gamma up to 10¹ Gy whereas from 10¹ to 4.5×10² Gy this phosphor exhibits a linear response and then from 4.5×10² to 10³ Gy it shows supralinearity. Thermoluminescence properties of Li₂B₄O₇ nanophosphor doped with Cu has also been investigated in this paper. It shows low fading and a linear response over a wide range of gamma radiation from 1×10² to 5×10³ Gy. Therefore the synthesized lithium borate nanophosphor doped with Cu may be used for high dose measurements of gamma radiations.     

Electron paramagnetic resonance and thermoluminescence study of Ag ions in Li2B4O7 crystals

Electron paramagnetic resonance (EPR) is used to investigate the effects of ionizing radiation on Ag-doped lithium tetraborate (Li₂B₄O₇) crystals. Two similar, yet distinct, trapped-hole centers (Ag²⁺ ions substituting for Li⁺ ions) are produced by 60 kV x rays. One Ag²⁺ ion, labeled Center A, has no nearby defects and the other Ag²⁺ ion, labeled Center B, has a neighboring impurity which is most likely a Ag⁺ ion substituting for a Li⁺ ion. The production and thermal decay properties of the two Ag²⁺ ions are described and their g matrices and ¹⁰⁷Ag and ¹⁰⁹Ag hyperfine matrices are obtained from the EPR angular dependences. The principal values of the g matrices are similar for the two centers, but the hyperfine principal values differ significantly (Center B has smaller values than Center A). There are also differences in the directions of the principal axes for the two centers. Together, these results imply (1) that the unpaired spin is less localized for Center B and (2) that the ground-state positions of the neighboring oxygen ions are different for Centers A and B. This explains why the peaks of the Ag²⁺ charge-transfer photoluminescence bands associated with Centers A and B occur at different wavelengths (502 and 725 nm, respectively). An isochronal pulsed thermal anneal shows that these radiation-induced Ag²⁺ ions serve as the recombination site for the intense thermoluminescence peak observed near 152 °C.     

Radioluminescent mechanism of Li2B4O7:Cu crystal

The structure of the radioluminescent (RL) spectrum of Li₂B₄O₇:Cu crystal is complex, having no normal Gauss peaks. The RL spectrum recorded showed one sharp and strong peak near 365 nm. For the purpose of explaining this phenomenon, we used the self-trapped exciton (STE) model to analyze experimental data of absorption spectrum, emission spectrum, radioluminescence spectrum and decay-time curves. We found a short lifetime component (of the order of ns) from phosphorous signals of Li₂B₄O₇:Cu. We realized that the short lifetime component related to inherent signal of host lattice and the d-p transitions of Cu⁺. This result is applicable in the detector system with high time resolution.     

Li2B4O7晶体及其熔体结构的拉曼光谱研究

采用高温原位拉曼光谱技术,研究了Li₂B₄O₇从常温至1 373 K温度范围内的拉曼光谱。在升温过程中,晶体的拉曼光谱出现展宽和红移现象,且强度降低。晶体熔化时,由2个[BO₄]和2个[BO₃]组成的[B₄O₉]环状结构转变成(B₃O₆)3- 六元环和[BO₃]结构,[BO₄]结构减少直至消失。基于密度泛函理论,计算了Li₂B₄O₇晶体的拉曼光谱,对其振动模式进行了分析归属。利用量子化学从头计算法计算了由[B₃O₆-BO₃]为基础相互连接形成的x(Li₂B₄O₇)(x=2, 3, …, 9)的环状团簇模型的拉曼光谱,对Li₂B₄O₇熔体的结构进行了模拟分析。计算结果表明Li₂B₄O₇熔体的阴离子基元为三个(B₃O₆-BO₃)组成的大三元环超级结构。     

Effect of doping on the luminescence properties of Li2B4O7

In this work, we have investigated the influence of doping agents on the luminescence properties of multiply doped Li₂B₄O₇ and the temperature lag between TSL materials and the heating element. The results of thermoluminescence studies show that the Ag doping leads to the appearance of a new glow curve peak at 165 °C and the increasing sensitivity of Li₂B₄O₇:Cu,Ag,P is correlated with copper and phosphate concentrations. Under the excitation at 245 nm the emission spectra show maxima at 365 and 450 nm in the ceramic, crystal and glass. The low energy shift in the latter system might be related to the local structural distortion in the glass around Cu⁺ ions.     

Thermoluminescence glow curves analysis of pure and CeO2-doped Li2O-Al2O3-SiO2 glass ceramics

A comparative study of the thermoluminescence (TL) emission between beta-irradiated lithium aluminosilicates, Li₂O-Al₂O₃-SiO₂ (LAS), and beta-irradiated CeO₂-doped lithium aluminosilicates, Li₂O-Al₂O₃-SiO₂-CeO₂ (LAS:Ce), grown by sol-gel technique and preannealed at 1250 °C is presented. It is found that doping reinforces the result of preannealing the sample; the incorporation of CeO₂ at low concentrations shifts the TL curves towards higher temperatures and increases the total intensity with respect to samples without the dopant. This behavior, together with the fact that CeO₂ is a good densification agent, suggests the possibility of using CeO₂ to improve the technological properties of LAS. Deconvolution analysis of the thermoluminescence glow curves of doped materials under general order kinetics shows that the relevant temperatures at which the component signals appear are virtually the same as for pure samples. This suggests that CeO₂ does not introduce new types of traps, but only changes the population and distribution of impurities responsible for the TL in the original matrix of LAS. Finally, the kinetic parameters for the deconvoluted curves are reported. They corroborate that changes in CeO₂ concentration only vary the depth and distribution of the same kind of original traps.     

非晶态离子导体Li2B2O4的核磁共振研究

本文报道了非晶态离子导体Li₂B₂O₄的⁷Li核磁共振研究。测量了⁷Li核磁共振谱与温度的关系。实验中发现,Li₂B₂O₄的晶态、非晶态和部分晶化样品的⁷Li核磁共振谱有很大的不同,且在部分晶化样品的⁷Li核磁共振谱上有附加的小峰,它与LiCl(Al₂O₃)的⁷Li核磁共振谱上附加的小峰相类似。我们也对非晶态离子导体B₂O₃-0.7Li₂O-0.7LiCl进行了⁷Li核磁共振研究,其结果与上面的类似。研究结果表明,它们都起因于非晶母体与微晶的界面效应。 关键词：     

Li2B4O7晶体生长及其二次谐波系数

用恰克拉斯基（Ｃｚｏｃｈｒａｌｓｋｉ）法特殊工艺生长出尺寸为Φ３０×３０ｍｍ的优质Ｌｉ２Ｂ４Ｏ７单晶，讨论了工艺参数对晶体宏观缺陷的影响。用Ｍａｋｅｒ条纹测量了晶体的二次谐波系数ｄ３１和ｄ３３，结果表明，Ｌｉ２Ｂ４Ｏ７的ｄ３３是石英晶体ｄ１１的三倍。     

X-ray and thermoluminescence of LiKB4O7 single crystals

The thermoluminescent (TL) and X-ray luminescent (XL) spectra of undoped LiKB₄O₇ (LKBO) single crystals had been investigated in the temperature range 80-300 K. It was found that in LKBO crystals, there are two intensive TL peaks at 112 and 132 K. The only one band emission spectra of sharply defined Gaussian shape, confirming the same mechanism of XL and TL by the radiation annihilation of the strongly localized self-trapped excitons (STE), had been observed in the TL and XL spectra. The possible models of these localization centers STE have been discussed.     

Ferroelectric and paramagnetic properties of Li2Gd4 (MoO4)7 single crystals

Thermal behavior of such fundamental physical properties as polarization, pyroelectric current, dielectric constant and paramagnetic susceptibility are reported for dilithium heptamolybdotetragadolinate, Li₂Gd₄ (MoO₄)₇. The ferroelectric transition point has been determined by various methods and the results compared. The most reliable value of the Curie point has been obtained by the measurement of differential magnetic susceptibility as a function of temperature and is found to be 52±2°C. The room temperature values for the relative dielectric constant and paramagnetic susceptibility are 51.5 and 59.8 x 10^-6 cm³. g^-1, respectively. From the susceptibility measurements the values obtained for the Curie constant, C, and the paramagnetic Curie point, θp, are 1.79 x 10^-2 cm³ . g^-1 . deg and 247°K, respectively. It is believed that Li₂Gd₄ (MoO₄)₇ could be antiferromagnetic between 273 and 325°K.     

非晶态离子导体Li2B2O4晶化前期的离子导电性

本文研究了非晶态离子导体Li₂B₂O₄的离子电导率与温度的关系,特别着重于晶化前期的离子迁移特性。当温度低于T_K(≈310℃)时,离子电导率遵从Arrhenius关系。当高于晶化温度(≈411℃)时,以晶态中的离子迁移为主。在T_kc时,电导率偏离热激活机制呈反常增高。我们把这一过程称为晶化前期过程。可以用自由体积模型进行描述。晶化前期又可分为两部分:当温度低于、T_p(≈380℃)时,由于自由体积的重新分布,导致了电导率的增高;当T>T_p时,出现了少量微晶,但晶化量小于5%,由于非晶母体与微晶之间的界面效应使得离子导电性显著增强。可以通过室温淬火,把晶化前期非晶态的状态保持到室温,从而有可能制备出离子电导率高于纯非晶态的材料。 关键词：     

Optical studies in gamma irradiated Mg doped CaF2 single crystals

Pure and Mg doped CaF₂ single crystals grown by the Bridgman method were irradiated with gamma rays (γ-rays) for doses ranging from 97 Gy to 9.72 KGy. The pristine samples showed minimal absorption indicating the purity of the samples. The γ-irradiated pure CaF₂ crystals showed prominent and strong absorption with a peak at ~ 374 nm besides three weak ones at ~ 456, 523 and 623 nm. However γ-rayed Mg doped crystals showed a prominent absorption with a strong peak at ~ 370 nm and a broad one at ~ 530 nm. The absorption indicated the generation of F and F-aggregate centers in the irradiated crystals. The photoluminescence (PL) emission spectrum of both pure and Mg doped crystals showed prominent emission at ~ 390 nm when they were excited at ~ 250 nm. Also, when the samples were excited at 323 and 363 nm strong emissions were observed at ~ 430 and 422 nm respectively. The optical absorption and PL intensities were found to increase with increase in dose.     

Growth, optical and EPR properties of Li1.72Na0.28Ge4O9 single crystals pure and slightly doped with Cr

Single crystals of lithium-sodium-tetragermanate, a member of the solid solution series Li_2−xNa _x Ge₄O₉ with x=0.28, pure and slightly doped with Cr³⁺ ions (0.03 mol.% and 0.1 mol.%), were grown in ambient atmosphere by the Czochralski technique from stoichiometric melt. The crystals with dimensions up to 20 mm in diameter and 50 mm in length were obtained. The crystal structure has been determined by means of X-ray diffraction. Phase analysis and structural refinement of the Li_1.72Na_0.28Ge₄O₉ crystals were performed by X-ray powder diffraction using Ni-filtered Cu Kα radiation with a Siemens D5000 diffractometer. The absorption, excitation and photoluminescence spectra of the crystals were measured in the UV-VIS and IR range at low temperatures. EPR investigations were performed using a conventional X-band Bruker ELEXSYS E 500 CW-spectrometer operating at 9.5 GHz with 100 kHz magnetic field modulation. Temperature and angular dependences of the EPR spectra of the crystal samples were recorded in the 3–300 K temperature range.     

Growth and optical properties of Eu/Li-co-doped SrB4O7 single crystals

This paper reports the growth and optical properties of Eu²⁺/Li⁺-co-doped SrB₄O₇ single crystals. High-quality Eu,Li:SrB₄O₇ crystals without macro-defects or cracks were grown using the top-seeded solution growth (TSSG) method. The absorption and luminescent properties were measured and different spectra were observed in the as-grown crystals. As the doping amount of lithium increases, the absorption peak at 300 nm becomes stronger and the emission peak shifts to a longer wavelength. This phenomenon could be attributed to the doping lithium ions, which might affect the electric field distribution in the lattice structure.