Evaluation of characterization of rare-earth doped sesquioxide ceramic scintillators

We investigated basic optical and scintillation properties of pure Y₂O₃, Tm³⁺-doped Y₂O₃, pure Lu₂O₃ and Nd³⁺-doped Lu₂O₃ transparent ceramics made by a sintering method. All ceramic samples showed 60–80% transparency, and some absorption bands due to Nd³⁺ 4f–4f transition were observed in Nd³⁺:Lu₂O₃ ceramic. Both Tm³⁺:Y₂O₃ and Nd³⁺:Lu₂O₃ ceramics showed sharp luminescence lines corresponding to the 4f–4f transition under 285 nm (Tm³⁺:Y₂O₃) and 340 nm (Nd³⁺:Lu₂O₃) excitation. The photoluminescence decay times were calculated to be about 24 μs for Tm³⁺:Y₂O₃ and 1 μs for Nd³⁺:Lu₂O₃, respectively. In radioluminescence measurements, Tm³⁺ and Nd³⁺ 4f–4f luminescence were observed for Tm³⁺-doped Y₂O₃ and Nd³⁺-doped Lu₂O₃ ceramics under ²⁴¹Am 5.5 MeV α-ray excitation. Finally scintillation light yield was investigated with pulse height analysis.     

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.     

Photoluminescence,photo-stimulated luminescence and thermoluminescence properties of CaB2O4 crystals activated with Ce3+

Photoluminescence (PL), photo-stimulated luminescence (PSL), and thermoluminescence (TL) properties of a Ce-doped CaB₂O₄ crystal were studied. The Ce-doped crystal was prepared by the simple solidification method using a Pt crucible under nitrogen atmosphere. A PL emission band in the 350–370 nm wavelength range was obtained under excitation at 325 nm owing to the 5d (t_2g)–4f (²F_5/2, ²F_7/2)-allowed transition of the Ce³⁺ emission center. The fluorescence quantum efficiency and the decay time of Ce³⁺ were estimated to be about 70% and 29 ns, respectively. The 5d–4f emission band of Ce³⁺ also appeared in the 350–370 nm wavelength range in the TL and PSL spectra. Good linear TL and PSL responses were observed in the 1–1000 mGy and 1–10,000 mGy X-ray dose range, respectively.     

Luminescence characteristics of LuAG:Pr and YAG:Pr single crystalline films

Emission and excitation spectra and luminescence decay kinetics were studied for Pr³⁺-doped Lu₃Al₅O₁₂ and Y₃Al₅O₁₂ single crystalline films (SCF) grown by the liquid phase epitaxy method from a PbO-based flux. The influence of lead-induced centers on their scintillation characteristics was clarified. It was found that the influence of single Pb²⁺-based centers on the characteristics of Pr³⁺ centers due to the Pb²⁺ → Pr³⁺ energy transfer was weak. However, an overlap of the emission spectra of single and dimer lead-induced centers with the emission spectrum of Pr³⁺ ions, and especially a strong overlap of the 4f–5d₁ absorption band of Pr³⁺ ions with the slow emission of localized excitons in the 290 nm band had a considerable influence on the scintillation characteristics of the Pr³⁺-doped SCF.     

The development of Ce3+-activated (Gd,Lu)3Al5O12 garnet solid solutions as efficient yellow-emitting phosphors

Abstract

Ce³⁺-activated Gd₃Al₅O₁₂ garnet, effectively stabilized by Lu³⁺ doping, has been developed for new yellow-emitting phosphors. The powder processing of [(Gd_1?xLu_x)_1?yCe_y]₃Al₅O₁₂ solid solutions was achieved through precursor synthesis via carbonate precipitation, followed by annealing. The resultant (Gd,Lu)AG:Ce³⁺ phosphor particles exhibit typical yellow emission at ～570 nm (5d–4f transition of Ce³⁺) upon blue-light excitation at ～457 nm (the ²F_5/2–5d transition of Ce³⁺). The quenching concentration of Ce³⁺ was determined to be ～1.0 at% (y = 0.01) and the quenching mechanism was suggested to be driven by exchange interactions. The best luminescent [(Gd_0.9Lu_0.1)_0.99Ce_0.01]AG phosphor is comparative to the well-known YAG:Ce³⁺ in emission intensity but has a substantially red-shifted emission band that is desired for warm-white lighting. The effects of processing temperature (1000–1500 °C) on the spectroscopic properties of the phosphors, especially those of Lu³⁺/Ce³⁺, were thoroughly investigated and discussed from the centroid position and crystal field splitting of the Ce³⁺ 5d energy levels.     

Scintillation and optical properties of Pb-doped YCa4O(BO3)3 crystals

This communication reports optical properties and radiation responses of Pb²⁺ 0.5 and 1.0 mol%-doped YCa₄O(BO₃)₃ (YCOB) single crystals grown by the micro-pulling-down (μ-PD) method for neutron scintillator applications. The crystals had no impurity phases according to the results of X-ray powder diffraction. These Pb²⁺-doped crystals demonstrated blue-light luminescence at 330 nm because of Pb²⁺¹S₀-³P_0,1 transition in the photoluminescence spectra. The main emission decay component was determined to be about 250-260 ns under 260 nm excitation wavelength. When irradiated by a ²⁵²Cf source, the relative light yield of 0.5% Pb²⁺-doped crystal was about 300 ph/n that was determined using the light yield of a reference Li-glass scintillator.     

YAG:Ce3+, Gd3+ nano-phosphor for white light emitting diodes

YAG:Ce³⁺, Gd³⁺ nano-phosphors were synthesised by the glycothermal method. The X-ray diffraction measurements showed that the samples can be well-crystallised at 600°C. The transition electron microscope showed that the particles have sizes mostly in the range between 35 and 100?nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow with a peak at 532?nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 to 568?nm was achieved doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White light emitting diodes (LEDs) were obtained by combining blue LED chip (InGaN-based 460?nm emitting) with (Y_{2.94? x} Ce_0.06Gd _x )Al₅O₁₂ phosphor. As x has the value of 0.8, an intense white LED with good colour rendering of 86 was obtained.     

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。     

Optical properties of divalent samarium-doped fluorochlorozirconate glasses and glass ceramics

Glass ceramics comprising Sm²⁺-doped barium chloride in both hexagonal and orthorhombic phases embedded in a fluorochlorozirconate glass matrix have been prepared. Divalent samarium doping was effected with the aid of NaBH₄ to partly reduce Sm³⁺ in the starting materials to Sm²⁺. The optical absorption spectrum in unannealed samples shows a strong, broad 4f → 5d band centred at around 340 nm and attributed to Sm²⁺, but no photoluminescence is observed. Following annealing to induce crystallisation of Sm²⁺-doped barium chloride crystals in the glass, photoluminescence is observed in the form of sharp line 4f → 4f transitions, and two broad 5d → 4f bands, the latter centred at around 680 and 900 nm. The 680 nm band disappears below about 250 K whilst the 900 nm band intensity increases with decreasing temperature. The 4f → 4f transitions for Sm²⁺ ions in the orthorhombic phase of barium chloride show an abrupt change in the relative intensity of transitions originating from the ⁵D₁ and ⁵D₀ levels at around 90 K. The effect is attributed to the role of the 5d level in thermally assisted indirect transitions between the ⁵D₁ and ⁵D₀ levels. In contrast, transitions from only the ⁵D₀ level are observed for the hexagonal phase. The temperature dependence of the photoluminescence intensity, and the observation of a different crystal field splitting pattern for the ⁷F₁ level, can be used to distinguish between the two phases. The splitting pattern for the ⁷F₁ level for the hexagonal phase of barium chloride suggests that both possible crystallographic barium sites are occupied by Sm²⁺ ions.     

Effect of Al3+ on the photoluminescence properties of Ce3+-doped Zn3(BO3)2 nanoparticles

Zn₃(BO₃)₂ nanoparticles doped with Ce³⁺ and Al³⁺ have been prepared by co-precipitation method. The study on the XRD pattern and Fourier transform infrared spectroscopy (FT-IR) shows that the diffraction lines are in good agreement with monoclinic crystalline phase of Zn₃(BO₃)₂. Ce³⁺-doped Zn₃(BO₃)₂ nanoparticles show a broader emission band at 405 nm, which is attributed to the d–f transition 5d–4f¹ of Ce³⁺. The effect of Al³⁺ on luminescence properties of Ce³⁺ has been studied. The results show that the fluorescence intensity of Ce³⁺ is enhanced greatly.     

Scintillation properties of Tm-doped Lu3Al5O12 single crystals

Using the micro-pulling-down (μ-PD) method, Tm-doped Lu₃Al₅O₁₂ (Tm:LuAG) single crystals were grown to examine their scintillation properties. In transmittance spectra, they exhibited about 80% transparency in the wavelengths longer than 320 nm and five absorption lines due to Tm³⁺ 4f–4f transitions were observed. ²⁴¹Am α-ray excited radioluminescence spectra were measured and intense 4f–4f emission peaks were observed with the host emission. When excited by ¹³⁷Cs γ-Ray to obtain pulse height spectra, Tm 1% doped LuAG showed the highest light yield coupled with a photomultiplier (PMT) or a silicon avalanche photodiode (Si-APD). The light yield was estimated to be 5800 and 7300 photons/MeV for PMT and Si-APD, respectively. Decay time profiles consist of two exponential components and the fast and slow components are considered to be attributed to the host and the combination of the host and Tm³⁺ 4f–4f emission, respectively.     

Photoluminescence and radioluminescence of pure and Ce activated Na3Gd(PO4)2

The spectroscopic properties of Na₃Gd(PO₄)₂ and Na₃Gd(PO₄)₂:Ce³⁺ phosphors in the VUV-UV spectral range were investigated. Five excitation bands of Ce³⁺ ions at Gd³⁺ sites are observed at wavelengths of 205, 246, 260, 292, and 321 nm. Doublet Ce³⁺ 5d → 4f emission bands are observed at 341 and 365 nm with a decay constant τ_1/e around 26 ns. The X-ray excited luminescence of Na₃Gd_0.99Ce_0.01(PO₄)₂ at room temperature shows a photon yield of ∼17,000 photons/MeV of absorbed X-ray energy.     

Long wavelength Ce emission in Y6Si3O9N4 phosphors for white-emitting diodes

Y₆Si₃O₉N₄:Ce³⁺ phosphor was prepared by a solid-state reaction in reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of Y₆Si₃O₉N₄:Ce³⁺. Scanning electron microscopy (SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 5 μm. Photoluminescence (PL) measurements showed that the phosphor can be efficiently excited by near ultraviolet (UV) or blue light excitation, and exhibited bright green emission peaked at about 525 nm. Compared with Ce³⁺-doped Y₄Si₂O₇N₂ phosphors, Ce³⁺-doped Y₆Si₃O₉N₄ phosphors showed longer wavelengths of both excitation and emission. The Y₆Si₃O₉N₄:Ce³⁺ is a potential green-emitting phosphor for white LEDs.     

VUV–UV spectroscopic properties of RE (RE = Ce, Eu and Tb)-doped KMLn(PO4)2 (M = Ca, Sr; Ln = Y, La, Lu)

The VUV excited luminescent properties of Ce³⁺, Eu³⁺ and Tb³⁺ in the matrices of KMLn(PO₄)₂ (M²⁺ = Ca, Sr; Ln³⁺ = Y, La, Lu) were investigated. The bands at about 155 nm in the VUV–UV excitation spectra are attributed to the host lattice absorption, which indicates that the optical band gap of KMLn(PO₄)₂ is about 8.0 eV. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 300–450 nm, and the energy transfer from host lattice to Ce³⁺ is efficient. For Eu³⁺-doped samples, the O²⁻–Eu³⁺ CTBs are observed to be at about 228 nm except KSrLu(PO₄)₂:Eu³⁺ (247 nm). As for Tb³⁺-doped samples, typical 4f → 5d absorption bands in the region of 175–250 nm were observed.     

Investigation on the luminescence of RE3+ (RE = Ce,Tb, Eu and Tm) in KMGd(PO4)2 (M = Ca,Sr) phosphates

The VUV excited luminescent properties of Ce³⁺, Tb³⁺, Eu³⁺ and Tm³⁺ in the matrices of KMGd(PO₄)₂ (M = Ca, Sr) were investigated. The bands at about 165 nm and 155 nm in the VUV excitation spectra are attributed to host lattice absorptions of the two matrices. For Ce³⁺-doped samples, the Ce³⁺ 5d levels can be identified. As for Tb³⁺-doped samples, typical 4f–5d absorption bands in the region of 175–250 nm were observed. For Eu³⁺ and Tm³⁺-doped samples, the O²⁻–Eu³⁺ and O²–Tm³⁺ CTBs are observed to be at about 229 nm and 177 nm, respectively. From the standpoints of color purity and luminescent efficiency, KCaGd(PO₄)₂:Tb³⁺ is an attractive candidate of green light PDP phosphor.     

Combustion synthesis and properties of fine particle fluorescent aluminous oxides

Fine particle fluorescent aluminous oxide materials like Cr³⁺-doped α-Al₂O₃ (ruby), MgAl₂O₄, LaAlO₃, Y₃Al₅O₁₂ and Ce³⁺-doped Y₃Al₅O₁₂, LaMgAl₁₁O₁₉, CaAl₁₂O₁₉ and CeMgAl₁₁O₁₉ have been prepared by the combustion of the corresponding metal nitrate-aluminium nitrate-urea/carbohydrazide mixtures at 500°C in less than 5 min. Formation of these Cr³⁺- and Ce³⁺-doped aluminous oxides has been confirmed by their characteristic XRD, colour, UV-visible and fluorescence spectra as well as decay time measurements. Ruby (Cr³⁺/α-Al₂O₃) powder showed characteristic excitation bands at 406 and 548 nm and emission band at 695 nm with the decay time of 3·6 ms. Presented at the “Materials Research Society (India) Foundation Meeting”, Defence Metallurgical Research Laboratory, Hyderabad, India, February 10–11 (1989).     

Efficiency issues in Ce doped YAG nanocrystals

Nanoparticles of Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺, 1%) were synthesized via the glycothermal method. The particle sizes were estimated by transmission electron microscopy, X-ray diffraction, surface area determination and by dynamic light scattering. We found primary particles of 10–14 nm in diameter, which form agglomerates of approximately 100 nm. For the 4f → 5d transition of Ce³⁺ an internal quantum efficacy of up to 46% was measured. The particles consist of 6–10% of 1,4-butanediol attached on the surface, as determined by carbon content measurements in combination with IR and absorption spectroscopy. In particular, limiting drawbacks due to inevitable surface coatings for glycothermal syntheses and nanoscale associated scattering are elucidated.     

Luminescence properties and preparation of Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> powder doped with Ce and Pr ions

Lu₃Al₅O₁₂:Ce³⁺ phosphor powder, which exhibits green emission band, was synthesized by the high-temperature solid-state reaction method with a flux BaF₂. X-ray diffraction (XRD), photoluminescence (PL) spectra, and fluorescent lifetime spectra were used to characterize the structure and luminescent properties of the sample. The XRD patterns indicated that when prepared at 1550 °C for 3 h with 4 wt% flux, Lu₃Al₅O₁₂:Ce³⁺ phosphors powder is the garnet cubic crystal system structure. Photoluminescence (PL) spectra showed that the Lu₃Al₅O₁₂:Ce³⁺ phosphor powder can be effectively excited by near ultraviolet and blue light, emitting broad band peaking at 505 nm, which is attributed to ²F_5/2?→?²D_5/2 transition. The self-concentration quenching mechanism of Ce³⁺ is the dipole–dipole interaction. Small amount of Pr³⁺ increased red light emission at 610 nm. Photoluminescence (PL) spectra and fluorescent lifetime spectra indicated that there was an efficient energy transfer process between Ce³⁺ and Pr³⁺.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.