Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.     

Thermoluminescence of Al2O3:Cr3+ films synthesized by the nonaqueous sol–gel method

The thermoluminescence (TL) properties of Al₂O₃:Cr³⁺ thin films prepared by the nonaqueous sol–gel method were evaluated. The obtained thin films were characterized by scanning electron microscope and energy dispersive spectrometry. They were irradiated with ⁶⁰Co gamma rays of the different doses. TL glow curves exhibited two peaks centered at 197°C and 322°C.The heights of peaks were found to be sensitive to exposures of ionizing irradiation and the integral area of the TL signals had a linear response in the dose range of 5–60 Gy.This remarkable result suggests that Al₂O₃:Cr³⁺ films might potentially be used for radiation dosimetry.     

Study of TL properties of LaAlO3:Ce,Dy crystals for UV dosimetry

Thermoluminescence properties of lanthanum aluminum oxide (LaAlO₃) crystals doped with optically active rare earth ions have been investigated for ultraviolet dosimetry purposes. Single crystals co-doped with 5.0 at.% of Ce³⁺ and 1.0 at.% of Dy³⁺ ions have two thermoluminescent (TL) peaks at 151 °C and 213 °C which can be sensitized after 1 h of UV exposure. The material shows very high TL output and linear response for UV spectral irradiance ranging from 0.04 to 1.20 mJ cm⁻², that corresponds to 10 times the TL response of the Al₂O₃:C oxides. From 0.62 to 148.0 mJ cm⁻² the dependence is linear with the logarithm of the spectral irradiance. The investigation demonstrates that LaAlO₃:Ce,Dy crystals are very attractive to be investigated as UV dosimeters.     

中子探测晶体Li6Gd(BO3)3:Ce的光谱特性研究

文章用提拉法生长出Li₆Gd(BO₃)₃:Ce晶体,并对其光谱性能与发光过程进行了探索. 借助于真空紫外-紫外透过光谱测试,发现晶体的透过光谱中存在Ce³⁺离子和Gd³⁺的特征吸收峰,同时还存在与Ce⁴⁺离子相关的电荷迁移带. 对晶体的真空紫外-紫外激发发射光谱进行研究发现,在晶体存在着Ce³⁺离子的5d→4f辐射跃迁发光与Gd³⁺离子的4f→4f辐射跃迁发光,而且存在着Gd³⁺→Ce³⁺之间的能量传递. 对Li₆Gd(BO₃)₃:Ce晶体的X射线与γ射线激发发射光谱研究可知,晶体在高能射线激发下的闪烁光主要是Ce³⁺离子的发光. 关键词： 6Gd(BO₃)₃:Ce晶体')" href="#">Li₆Gd(BO₃)₃:Ce晶体 真空紫外-紫外透过光谱 真空紫外-紫外激发发射光谱 能量传递     

Luminescence studies on gamma irradiated KCl: Ce crystals

This paper reports thermoluminescence(TL), optical absorption and TL emission studies that are made on Ce³⁺ doped KCl single crystals irradiated at room temperature. The glow curve and optical absorption studies indicate the participation of Ce³⁺ ions in the TL process. The TL study suggests the presence of low concentration of Ce³⁺ ions which reduces the TL efficiency with respect to pure KCl samples. On F bleaching γ irradiated crystals Z₁ centers are observed. A broader and strongly intense violet blue emission at 290, 370, 423 and 488 nm has been observed with 240 nm excitation. This emission has been attributed due to the transition from 5d(2D) excited energy level to the 4f¹ ground stable energy level (2F_5/2 and 3F_7/2) of Ce³⁺ doped KCl crystals.     

Thermoluminescence characteristics of rare-earth-doped LiCaBO3 phosphor

LiCaBO₃ was synthesized by high-temperature solid-state reaction. The influence of different rare earth dopants, i.e. Dy³⁺, Tb³⁺, Tm³⁺ and Ce³⁺, on thermoluminescence (TL) of LiCaBO₃ phosphor was discussed. We studied the TL properties and some dosimetric characteristics of Ce³⁺-activated LiCaBO₃ phosphor in detail. The effect of the concentration of Ce³⁺ on TL was investigated, the result of which showed that the optimum Ce³⁺ concentration was 1 mol%. The TL kinetic parameters of LiCaBO₃:0.01Ce³⁺ were studied by computer glow curve deconvolution (CGCD) method. The three-dimensional (3D) TL emission spectra were also studied, peaking at 431 and 474 nm due to the characteristic transition of Ce³⁺. We also studied the linearity, annealing condition, reproducibility, fading and different heating rate of the LiCaBO₃:0.01Ce³⁺ phosphor.     

Thermoluminescence of α-Al 2O 3 by neutron irradiation at low temperature

Thermoluminescence (TL) mechanisms of neutron-irradiated α-Al₂O₃ at 20 K is reported. The TL glow curves of neutron-irradiated and γ-ray-irradiated α-Al₂O₃ were observed. The TL emission bands near 340, 430, 530 and 694 nm were observed in the neutron-irradiated α-Al₂O₃. The γ-ray-irradiated α-Al₂O₃ only showed the TL emission line nearly at 694 nm, corresponding to the R lines of α-Al₂O₃:Cr³⁺. Therefore, the first three emission bands are related to the atomic displacement defects as F-type centers caused by neutron irradiation.     

Photoluminescence spectra of thenardite Na2SO4 activated with rare-earth ions, Ce, Sm, Tb, Dy and Tm

Five Na₂SO₄:RE³⁺ phosphors activated with rare-earth (RE) ions (RE³⁺=Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) were synthesized by heating natural thenardite Na₂SO₄ from Ai-Ding Salt Lake, Xinjiang, China with small amounts of rare-earth fluorides, CeF₃, SmF₃, TbF₃, DyF₃ and TmF₃, at 920 °C in air. The photoluminescence (PL) and optical excitation spectra of the obtained phosphors were measured at 300 and 10 K. In the PL spectrum of Na₂SO₄:Ce³⁺ at 300 K, two overlapping bands with peaks at 335 and 356 nm due to Ce³⁺ were first observed. Narrow bands observed in PL and excitation spectra of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors were well identified with the electronic transitions within the 4fⁿ (n=5, 8, 9 and 12) configurations of RE³⁺. The existence of excitation bands with high luminescence efficiency at wavelengths shorter than 230 nm is characteristic of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors. The obtained results suggest that these phosphors are unfavorable as the phosphor for usual fluorescence tubes, i.e., mercury discharge tubes, but may be favorable as the phosphor for UV-LED fluorescent tubes and as cathodoluminescence, X-ray luminescence and thermoluminescence phosphors.     

TL,OA and ESR of spessartine garnet

Thermoluminescence (TL), optical absorption (OA), electron spin resonance (ESR) and their relation to point defects in spessartine have been investigated. The TL glow curve presented four peaks at 150, 220, 260 and 335 °C. The 150 and 335 °C TL peaks growth curves presented a linear growth with radiation dose up to about 400 Gy, supralinearity above this dose, and saturation around 800–1000 Gy. The OA spectrum presented allowed spin transition bands due to Fe³⁺ and Mn²⁺ in dodecahedral environment. Absorption bands due to ultraviolet charge transfer of Fe³⁺ in octahedral and tetrahedral positions were also observed. Two ESR, a strong one around g?～?2 due to Fe³⁺ in octahedral position, and another weaker one at g?～?4 due to Fe³⁺ in tetrahedral position, have been detected. The effect of high temperature annealing (600–900 °C) before irradiation was also investigated.     

改进BaF2闪烁体光输出特征研究

介绍旨在抑制BaF₂闪烁体慢发光成分，拓展其应用领域的紫外滤光膜系设计和 性能测量结果，研究表明，以Al₂O₃/MgF₂/Al/MgF₂为 基本结构优化设计的紫外滤光膜系对来自BaF₂闪烁体不同角度入射的快/慢成分光分别具有高透射和强截止特性.还提供 了用纳秒级脉冲辐射源激发“BaF₂+紫外滤光膜系+光电闪烁探测器”系统获得的BaF₂闪烁体时间响应曲线，并对紫外滤光膜系中子辐照损伤特性进行了研究. 关键词： 2闪烁体')" href="#">BaF₂闪烁体 紫外线 滤光片 时间响应     

Thermoluminescence mechanism in rare-earth-doped magnesium tetra borate phosphors

Magnesium tetra borate (MTB) doped with rare earths (REs) was prepared by the solid state sintering technique. Among the different RE dopants studied in this phosphor, gadolinium-doped phosphors resulted in a dosimetric peak at a relatively higher temperature. The thermoluminescence (TL) emission spectra of RE-doped MTB showed characteristic RE ³⁺ emissions. Electron paramagnetic resonance measurements were carried out in these phosphors to identify the defect centers formed during gamma irradiation and to establish a mechanism for the TL process. Signals corresponding to (BO ₃)^2?, O _v^? were seen upon irradiation which vanished on annealing at 250 °C, showing the role of these centers in the TL process. The thermal activation energies calculated based on the decay of these signals matched well with those calculated on the basis of the usual conventional method showing the validity of the mechanism of TL.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

EPR and optical absorption of manganese doped BaF2 and SrF2

Abstract

Mn⁺ ions in off-centre position along [100] have been produced in BaF₂:Mn by X-irradiation at LNT. Their EPR spectra are characterized by g-2. 0107. D = 265.8·10^?4cm^?1. A = 122.9·10^?4cm^?11 and a superhyperfine structure arising from 8 surrounding F^? nuclei. In the optical absorption spectrum they show up by a band at 411 nm. This behaviour is compared with the results found for SrF₂:Mn. After X-irradiation at room temperature beside a different Mn⁺ centre two species of Mn⁰ appear in non-cubic position. Both interact dominantly with two F^? neighbours. Possible models for these species are discussed.     

Enhanced luminescent properties and optical absorption of γ-irradiated KI: Ce, Tb crystals

This paper reports that KI doped with Ce³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by the Bridgman-Stockbarger method and characterized by optical absorption photoluminescence (PL), thermoluminescence (TL), photostimulated emission (PSL) and TL emission. The optical absorption measurement indicates that F and V₁, V₂ centers are formed in the crystals during the γ irradiation process. It was attempted to incorporate a broad band of Ce³⁺ activator into the narrow band emission of Tb³⁺ in the KI host without the reduction of emission intensity. Ce³⁺-co-doped KI and Tb crystals showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to the ⁵D₃-⁷F_j (j=3,4,5,6) transition of Tb³⁺, when they were excited at 240 nm.These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in the KI host. Co-doping Ce³⁺ ions greatly intensified the excitation peak at 260 nm for the emission at 393 nm of Tb³⁺, which means that more lattice defects, involved in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ co-doping. The integrated light intensity is an order of magnitude higher as compared to the undoped samples for similar doses of irradiation and heating rates. The defects generated by irradiation were monitored by optical absorption and TSL Trap parameters for the TL process are calculated and presented.     

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.     

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.     

White light generation through the zinc metaphosphate glass activated by Ce, Tb and Mn ions

The photoluminescence of Ce³⁺, Tb³⁺ and Mn²⁺ ions was investigated in the Zn(PO₃)₂ glass. The blue and green emissions of Tb³⁺ ions and the red emission of Mn²⁺ ions are enhanced upon UV excitation through a non-radiative energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions. The efficiency of this transfer was estimated in at least 62%. It is demonstrated that this glass activated with three ions (Ce³⁺, Tb³⁺ and Mn²⁺) can generate white light emission (x=0.420 and y=0.423 chromaticity coordinates and 3440 K colour temperature) under excitation at 254 nm, i.e., using an AlGaN-based LED as excitation source.     

Spectral-kinetic characteristics of crystals and nanoceramics based on BaF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript>: Ce

Optical characteristics of BaF₂ and BaF₂: Ce single crystals and nanoceramic materials prepared from these single crystals by uniaxial hot pressing have been studied. It has been shown that the introduction of Ce₃₊ ions into BaF₂ hardly affects the ultrafast (∼0.9 ns) luminescence component. The integrated luminescence intensity of the BaF₂: Ce nanoceramics is higher than that of the corresponding single crystal and considerably higher that the intensity of the undoped BaF₂ crystal. It has been demonstrated that the slow (several hundred nanoseconds) component of the luminescence decay of BaF₂: Ce is due to the energy transfer from excitons to Ce³⁺ ions.     

Luminescence studies of a combustion-synthesized blue–green BaAlxOy:Eu,Dy nanoparticles

Blue–green emitting BaAl_xO_y:Eu²⁺,Dy³⁺ phosphor was synthesized by the combustion method. The influence of various parameters on the structural, photoluminescence (PL) and thermoluminescence (TL) properties of the phosphor were investigated by various techniques. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. In the PL studies, broad-band excitation and emission spectra were observed with major peaks at 340 and 505 nm, respectively. The observed afterglow is ascribed to the generation of suitable traps due to the presence of the co-doped Dy³⁺ ions. Though generally broad, the peak structure of the TL glow curves obtained after irradiation with UV light was non-uniform with suggesting the contribution to afterglow from multiple events at the luminescent centers. Further insight on the afterglow behavior of the phosphor was deduced from TL decay results.     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.