Luminescence and scintillation properties of Ce-doped Cs2ZnCl4 crystals

In this study, we have synthesized scintillation materials based on Ce-doped Cs₂ZnCl₄ crystals. The light yield was enhanced by up to 20% by doping Cs₂ZnCl₄ with Ce³⁺ ions. In the scintillation time profiles, fast components exhibited decay time constants on the order of nanoseconds, which was ascribed to Auger-free luminescence (AFL). The light yield of the AFL component decreased at 10 mol% Ce³⁺ concentration, which is mainly attributed to the reabsorption of AFL photons inside the crystals by Ce³⁺ ions, as seen in the scintillation spectra. Long components had decay time constants of approximately 30 ns. In addition, at 10 mol% Ce³⁺ concentration, a prominent band appeared at approximately 500 nm in the scintillation spectrum, which was not observed in the photoluminescence spectra. The long components in the scintillation time profiles and the 500 nm band in the scintillation spectra were tentatively attributed to self-trapped excitons perturbed by Ce³⁺ ions.     

Growth and characterization of strontium metaborate scintillators

The undoped and 0.5% Ce³⁺-doped strontium metaborate SrB₂O₄ single crystals has been grown successfully by micro-pulling down method with radio frequency (RF) heating system, and scintillation characteristics including optical properties and radiation response were studied for these crystals. The Ce³⁺-doped SrB₂O₄ crystal showed absorption band around 240–320 nm, which is corresponding to the 4f-5d transition of Ce³⁺. Intense emission band at 375 nm due to the Ce³⁺ 5d–4f transition was observed under ²⁴¹Am 5.5 MeV α-ray excitation. The scintillation decay time showed fast (50 ns) and slow (1430 ns) components ascribed to the Ce³⁺ 5d–4f transition and lattice defect in the crystal, respectively. The scintillation light yield of Ce³⁺-doped SrB₂O₄ was calculated to be about 1000 ph/n under ²⁵²Cf irradiation.     

Scintillation properties of Cs2LiLaBr6 (CLLB) crystals with varying Ce concentration

Investigations of Ce³⁺-doped Cs₂LiLaBr₆ (CLLB) crystals show a systematic trend in their scintillation properties with varying Ce concentrations. The concentration studies provide input in the optimization of growth of the CLLB crystals. Scintillation properties viz. radioluminescence, energy resolution, light yield, decay times, and non-proportionality are discussed for samples from 0% to 20% Ce concentration.     

镥基闪烁晶体的研究进展

由于高能物理实验、核医学成像、安全检查和地质探矿等领域的迫切需要,具有高密度、快衰减、高光输出和低成本等优良特性的闪烁晶体成为关注的焦点,特别是Ce~(3+)激活的镥(Lu)基化合物,其开发、研究和应用方兴未艾。简要综述了硅酸镥、氧化镥和铝酸镥等闪烁晶体的生长技术、闪烁性能和应用,并展望了镥基闪烁晶体的发展趋势。     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Ce and Eu activated Na<Subscript>2</Subscript>Zn<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>4</Subscript>, a new promising novel phosphor

A new efficient phosphor, Eu²⁺/Eu³⁺ and Ce³⁺ activated Na₂Zn₅(PO₄)₄ has been synthesized by solid-state reaction technique at high temperature. X-ray powder diffraction analysis confirmed the formation of Na₂Zn₅(PO₄)₄ host lattice. Scanning electron microscopy indicated that the microstructure of the phosphor consisted of irregular fine grains with a size of about 0·5–2 μm. Photoluminescence excitation spectrum measurements of Ce³⁺ activated Na₂Zn₅(PO₄)₄ show that the phosphor can be efficiently excited by UV-Vis light from 280 to 310 nm to realize emission in the visible (blue) range due to the 5d-4f transition of Ce³⁺ ions which is applicable for scintillation purpose, whereas Eu²⁺/Eu³⁺ activated Na₂Zn₅(PO₄)₄ phosphor emits blue, green and red emission spectrum shows at 487 nm, 546 nm with a dominant peak at 611 nm respectively, due to Eu²⁺/Eu³⁺ ions which is promising candidate for solid state lighting. Therefore, newly synthesised, by low cost and easy technique prepared, novel phosphors may be useful as RGB phosphor for solid state lighting application.     

Effect of annealing on the spectroscopy performance of YVO4:Ce3+ single crystals

In this study, 1.0 at.% YVO₄:Ce³⁺ single crystals were grown in the protective atmosphere by using the Czochralski method. The crystals were annealed in Ar and H₂ atmospheres at different temperatures. The absorption and fluorescence spectra of the samples before and after annealing were measured. Results showed that the luminescent efficiency of the crystals was significantly enhanced after annealing in H₂ than after annealing in Ar. This phenomenon can be attributed to the existence of some Ce⁴⁺ ions in the crystal lattice. These Ce⁴⁺ ions can be effectively reduced to Ce³⁺ via annealing in H₂. With a fixed annealing time in H₂, the luminescent intensity significantly increased with increasing annealing temperature. The possibility of the crystal as white light material was also discussed according to the luminescence properties.     

Cathodoluminescence and scintillation characteristics of YAG:Ce crystals grown by horizontal directional crystallization in a protective atmosphere

YAG:Ce crystals have been grown by a new gas-phase horizontal directional crystallization (HDC) technique in a protective atmosphere and their cathodoluminescence (CL) spectra and scintillation characteristics have been studied. Using this HDC technology, it is possible to obtain large (110 × 150 × 35 mm) crystals with a high specific light yield (15 000–18 000 Ph/MeV) and good amplitude resolution (8–10%) for the excitation with 5.15-MeV α particles from a ²³⁹Pu source. In addition to an intense band at 550 nm due to Ce³⁺ ions, the CL spectra of crystals display an intrinsic emission band of YAG in the UV spectral range, which is due to the presence of Y_Al antisite defects.     

Luminescence properties and gamma-ray response of the Ce and Ca co-doped (Gd,Y)F3 single crystals

The Ca0.5% and Ce1%, 3%, 7%, 10% co-doped Gd_0.5Y_0.5F₃ single crystals were grown by the μ-PD method. In the Ca0.5% and Ce3% co-doped sample, Ce³⁺-perturbed luminescence at 380 nm was observed with 32.4 ns photoluminescence decay time. The energy transfer in the sequence of the regular Ce³⁺→ (Gd³⁺)_n→ the perturbed Ce³⁺ sites was evidenced through observation of decay time shortening of the regular Ce³⁺ and Gd³⁺ centers and the change between the Gd³⁺ and Ce³⁺-perturbed emission intensity. The gamma-ray excited scintillation response of the Ca0.5%, Ce7% co-doped Gd_0.5Y_0.5F₃ sample was investigated with the help of the pulse height spectra and the light yield, energy resolution and non-proportionality was evaluated in the interval of energies of 59.4-1274 keV.     

Scintillation and luminescent properties of undoped and Ce3+ doped Y2SiO5 and Lu2SiO5 single crystalline films grown by LPE method

Single crystalline films (SCFs) of undoped and Ce³⁺ doped Y₂SiO₅ (YSO) and Lu₂SiO₅ (LSO) orthosilicates were crystallized for the first time by liquid phase epitaxy method onto undoped YSO substrates from melt-solution based on PbO–B₂O₃ flux. The scintillation and luminescent properties of YSO:Ce and LSO:Ce SCFs were compared with the properties of bulk single crystal counterparts. We show that the peculiarities of luminescent properties of YSO:Ce and LSO:Ce SCFs in comparison with the crystal analogues are caused by the different distribution of Ce³⁺ ions over Y1/Lu1 and Y2/Lu2 positions of YSO and LSO host and strong influence of Pb²⁺ flux-related impurity on luminescent properties of Ce³⁺ ions.     

Growth and optical properties of (Yb3−xYx)Al5O12:Ce single crystals

To improve the infrared emission of Yb³⁺ ions doped in the garnet host Y₃Al₅O₁₂ (YAG) single crystal through the energy transfer from Ce³⁺ to Yb³⁺ ions, the 〈1 1 1〉-oriented YAG:Ce³⁺, YAG:Yb³⁺, YAG:(Ce³⁺, Yb³⁺) and Yb₃Al₅O₁₂:Ce³⁺ (YbAG:Ce³⁺) single crystals were grown using the Czochralski Method, respectively. The excitation and emission spectra of these garnet single crystals were characterized. In YAG:Ce³⁺ crystal, the yellow emission of Ce³⁺ ions present, but it was completely extinguished in YAG:(Ce³⁺, Yb³⁺) crystal and YbAG:Ce³⁺ crystal. However, the characteristic absorption bands of Ce³⁺ still existed in the excitation spectrum of Yb³⁺ ions, which showed that the energy absorbed by Ce³⁺ ions can be transferred to Yb³⁺ ions for its infrared emission.     

Microstructures and luminescent properties of Ce-doped transparent mica glass-ceramics

Transparent mica glass-ceramics were prepared by heating parent glasses that had been doped with 0.5–15 mol% CeO₂. During the melting and heat treatment, Ce⁴⁺ ions in the specimens were reduced to Ce³⁺ ions, and one or both of these ion species were then replaced with Li⁺ ions in the interlayers of the separated mica crystals. However, scanning transmission electron microscope (STEM) and Z-contrast imaging revealed that the mica crystals did not contain the same amount of Ce. On excitation at 254 nm, the parent glasses and glass-ceramics emitted blue light, which originated from the 5d to 4f transition of the Ce³⁺ ions. The emission of the glass-ceramic containing a smaller amount of Ce was attributed to the Ce³⁺ ions in both the glass phase and the mica crystals, whereas that of the glass-ceramics containing a larger amount of Ce was caused mainly by Ce³⁺ ions in the mica crystals. The dependence of the emission band of the parent glasses on the amount of Ce was a unique feature of the Ce-doped transparent mica glass-ceramics and was not observed in previous studies of Eu-doped parent glasses and mica glass-ceramics.     

Luminescence characteristics of Ce-doped Lu1−xScxBO3 solid solution single crystals grown by Czochralski method

Solid solution crystals of Lu_1−xSc_xBO₃:Ce³⁺ (x = 0.2, 0.3, 0.5, 0.7) were grown by Czochralski method. These crystals have high optical transmittance within wavelength concerned, except for an absorption shoulder in Lu_0.8Sc_0.2BO₃:1at%Ce³⁺ crystal from 360 to 530 nm. With the increase of Sc/Lu ratio, the excitation and emission spectra have redshift due to change of Ce³⁺ crystalline environment and the lifetime gradually increases due to the increase of emission wavelength. Efficient energy transfer from the self-trapped excitons to Ce³⁺ ions was observed. Lu_0.8Sc_0.2BO₃:1at%Ce³⁺ crystal, due to high density, short decay time, high scintillation efficiency and non-hygroscopic property, could be a promising scintillator.     

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

Abstract

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd₃Al₅O₁₂, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd³⁺ to the activator. Ce³⁺ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.     

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd₃Al₅O₁₂, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd³⁺ to the activator. Ce³⁺ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.     

Long-lasting phosphorescence in Ce-doped oxides

Although oxide crystals doped with Ce³⁺ are not useful in laser operation, they have advantage in the areas such as scintillators and passive optical sources. Scintillator materials require high light-yield and fast fluorescence decay time. However, when the crystalline quality is degraded by defects created during the crystal growth process, afterglow from the crystals is observable persistently. Such phosphorescence is undesirable for scintillators, but useful in passive optical sources. The phosphorescence observed in Ca₂Al₂SiO₇ doped with Ce³⁺ ions has been investigated in detail and a model is proposed to explain the mechanism responsible.     

Preparation and scintillation properties of YCl3:Ce crystals

Ce³⁺-activated YCl₃ crystals have been grown by the Bridgman-Stockbarger method, and their scintillation properties have been investigated. The luminescence spectrum of YCl₃:Ce has a complex character and consists of two overlapping peaks at 390 and 410 nm, characteristic of Ce³⁺ luminescence. The light output of YCl₃:Ce as a function of Ce³⁺ concentration has a maximum at 1 mol % Ce³⁺. Original Russian Text ? V.L. Cherginets, T.V. Ponomarenko, L.N. Trefilova, N.V. Rebrova, N.N. Kosinov, V.D. Alekseev, O.V. Zelenskaya, 2009, published in Neorganicheskie Materialy, 2009, Vol. 45, No. 8, pp. 1017–1020.     

Effect of BaF2 powder addition on the synthesis of YAG phosphor by mechanical method

Here, we report on the effect of BaF₂ powder addition on the mechanical synthesis of Ce³⁺-doped Y₃Al₅O₁₂ (Y_2.97Al₅O₁₂:Ce_0.03³⁺, YAG:Ce³⁺) phosphors for white light emitting diodes. The YAG phosphors were synthesized by the mechanical method using an attrition-type mill. When BaF₂ was added at 6 wt% to the raw powder materials and milled, the synthesis of YAG:Ce³⁺ was favorably achieved at the vessel temperature of 255 °C, which was about 1200 °C lower than the YAG phosphor synthesis temperature by solid-state reaction. The synthesized YAG:Ce³⁺ phosphor revealed the maximum internal quantum yield of 57%.     

Luminescence and scintillation properties of rare-earth-doped LuF3 scintillation crystals

The Nd-doped and Er-doped LuF₃ single crystals were grown by the micro-pulling-down method to study their scintillation properties in the vacuum-ultraviolet (VUV) region. The doubly Nd–Er codoped single crystal was grown to study possibility of scintillation performance improvement by energy transfer from Er³⁺ to Nd³⁺ ions. The LiF flux was to avoid phase transition below melting temperature. The 1%Nd-doped sample showed the highest overall scintillation efficiency under X-ray excitation which was 7 times as high as that of the LaF₃:Nd 8% standard. The leading Nd³⁺ 5d–4f emission was situated at 176 nm, while the Er³⁺ 5d–4f emission for Er-doped samples was observed at 163 nm, which better matches the sensitivity of some VUV-sensitive photodetectors. The optimum Er concentration was determined to be around 1–3 mol%. No Er³⁺ 5d–4f emission was observed for the doubly Er,Nd-codoped sample due to energy transfer from the Er³⁺ to Nd³⁺ ions. Slight improvement of the light yield was observed in the doubly-doped sample with respect to the Nd-only doped one.     

Luminescence and scintillation properties of Cs3BiCl6 crystals

The optical and scintillation properties of Cs₃BiCl₆ single crystals were characterized, and absorption properties were investigated for thin films. The thin films showed two absorption bands at ∼220 nm and 330 nm; these bands can be attributed to the ¹A_1g → ¹T_1u and ¹A_1g → ³T_1u transitions of Bi³⁺ ions, respectively. A luminescence band was observed at ∼390 nm in the photoluminescence spectra; this band can be attributed to the ³T_1u → ¹A_1g transition of Bi³⁺ ions. In the X-ray-induced radioluminescence spectrum, in addition to the luminescence band at 390 nm, another band was observed at 600–700 nm; this band was tentatively attributed to the radiative recombination of self-trapped excitons. The decay-time constants of photoluminescence and scintillation decay were of the order of nanoseconds. The scintillation light yield was 800 photons/MeV. The results indicate that Cs₃BiCl₆ has a fast scintillation decay and a relatively poor light yield.