Crystal growth and scintillation properties of Nd-doped Lu3Al5O12 single crystals with different Nd concentrations

Nd 0.1%, 0.5%, 1% and 3% doped Lu₃Al₅O₁₂ (Nd:LuAG) single crystals were grown in the nitrogen atmosphere by the micro-pulling down (μ-PD) method. The grown crystals had a single-phase confirmed by powder XRD analysis. In absorption spectra, some weak absorption lines due to Nd³⁺ 4f-4f transitions were observed and their intensity increased with the increase of Nd concentration. When excited by ²⁴¹Am α-ray, a broad emission peak due to defects in the host lattice at 320 nm and some sharp lines due to Nd³⁺ 4f-4f transitions at wavelength longer than 400 nm were observed. The decay time profiles of Nd:LuAG under γ-ray excitation were well approximated by two exponential function of 340-760 ns and 3-5 μs for each sample. By pulse height measurement using ¹³⁷Cs, Nd 0.5%:LuAG showed the highest light yield of 7600 ± 760 photons/MeV.     

Crystal growth and scintillation properties of Er-doped Lu3Al5O12 single crystals

Er-doped Lu₃Al₅O₁₂ (Er:LuAG) single crystalline scintillators with different Er concentrations of 0.1, 0.5, 1, and 3% were grown by the micro-pulling-down (μ-PD) method. The grown crystals were composed of single-phase material, as demonstrated by powder X-ray diffraction (XRD). The radioluminescence spectra measured under ²⁴¹Am α-ray excitation indicated host emission at approximately 350 nm and Er³⁺ 4f-4f emissions. According to the pulse height spectra recorded under γ-ray irradiation, the 0.5% Er:LuAG exhibited the highest peak channel among the samples. The γ-ray excited decay time profiles were well fitted by the two-component exponential approximation (0.8 μs and 6-10 μs).     

Investigations of optical and scintillation properties of Tm-doped YAlO3

Pure, 0.1, 0.5 and 1 mol% Tm-doped YAP single crystalline scintillators were grown by the μ-PD method. The XRD analysis confirmed the lattice constants decrease with the Tm concentration. In the transmittance measurement, the absorption bands due to the Tm³⁺ 4f-4f transitions were observed at 265, 360, 485, 690 and 800 nm and they were ascribed to the transition from the ³H₆ ground state to its ¹I₆, ¹D₂, ¹G₄, ³F₃ and ³H₄ excited states, respectively. Strong emission peak due to the ¹I₆-³F₄ transition of Tm³⁺ appeared at 350 nm under X-ray irradiation. The photoluminescence decay time constants related to this transition were evaluated to be from 15.3 to 17.3 μs and the scintillation decay time constants under gamma-ray excitation were estimated to be from 17.5 to 18.8 μs. The Tm 1% doped crystal exhibited the highest light yield of 15, 100 ± 1500 photons/MeV when excited by ¹³⁷Cs gamma-ray radiation.     

Photoluminescence properties of emission-tunable Ca9Y(PO4)7: Tm,Dy phosphor for white light emitting diodes

A white-emitting Ca₉Y(PO₄)₇: Tm³⁺, Dy³⁺ phosphor has been successfully prepared by conventional high-temperature solid-state reaction. X-ray diffraction (XRD) and fluorescence spectrophotometer were used to characterize the as-synthesized phosphors. The excitation and emission spectra show that all the Tm³⁺ and Dy³⁺ co-doped Ca₉Y(PO₄)₇ samples can be effectively excited by UV light and then emit blue and yellow light simultaneously. Furthermore, the emission and color coordinate of as-obtained samples pumped by 365 nm are able to be adjusted around white light by varying the doping concentrations of Tm³⁺ and Dy³⁺. So, the as-fabricated single-composition Ca₉Y(PO₄)₇: Tm³⁺, Dy³⁺ phosphor will have a promising application in the area of white light emitting diodes.     

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.     

Scintillation properties of Ce-doped LuLiF4 and LuScBO3

The crystals of 1 mol% Ce-doped LuLiF₄ (Ce:LLF) grown by the micro-pulling down (μ-PD) method and 1 mol% Ce-doped LuScBO₃ (Ce:LSBO) grown by the conventional Czochralski (Cz) method were examined for their scintillation properties. Ce:LLF and Ce:LSBO demonstrated ∼80% transparency at wavelengths longer than 300 and 400 nm, respectively. When excited by ²⁴¹Am α-ray to obtain radioactive luminescence spectra, Ce³⁺ 5d-4f emission peaks were detected at around 320 nm for Ce:LLF and at around 380 nm for Ce:LSBO. In Ce:LSBO, the host luminescence was also observed at 260 nm. By recording pulse height spectra under γ-ray irradiation, the absolute light yield of Ce:LLF and Ce:LSBO was measured to be 3600±400 and 4200±400 ph/MeV, respectively. Decay time kinetics was also investigated using a pulse X-ray equipped streak camera system. The main component of Ce:LLF was ∼320 ns and that of Ce:LSBO was ∼31 ns. In addition, the light yield non-proportionality and energy resolution against the γ-ray energy were evaluated.     

Luminescence properties of Ca4Y6(SiO4)6O:RE (RE = Eu, Tb, Dy, Sm and Tm) under vacuum ultraviolet excitation

The vacuum ultraviolet excited luminescent properties of Eu³⁺, Tb³⁺, Dy³⁺, Sm³⁺ and Tm³⁺ in the matrices of Ca₄Y₆(SiO₄)₆O were investigated. The bands at about 173 nm in the vacuum ultraviolet excited spectra were attributed to host lattice absorption of the matrix Ca₄Y₆(SiO₄)₆O. For Eu³⁺-doped samples, the O²⁻ → Eu³⁺ CTB was identified at 258 nm. Typical 4f-5d absorption bands in the region of 195-300 nm were observed in Tb³⁺-doped samples. For Dy³⁺-doped and Sm³⁺-doped samples, the broad excitation bands consisted of host absorptions, CTB and f-d transition. For Tm³⁺-doped samples, the O²⁻ → Tm³⁺ CTB was located at 191 nm. About the color purity and emission intensity, Ca₄Y₆(SiO₄)₆O:Tb³⁺ is an attractive candidate of green light PDP phosphor, and Ca₄Y₆(SiO₄)₆O:Dy³⁺ has potential application in the field of mercury-free lamps.     

Polarized spectral properties of Tm:K5Bi(MoO4)4 crystal

Trivalent thulium-doped K₅Bi(MoO₄)₄ single crystals were grown by the Czochralski method. Its polarized absorption and fluorescence spectra and fluorescence decay curves were recorded at room temperature. On the basis of the Judd-Ofelt theory, the spectral parameters of the Tm³⁺:K₅Bi(MoO₄)₄ crystal were calculated. The cross relaxations between Tm³⁺ ions were analyzed. The emission cross sections of the ³F₄ → ³H₆ transition were obtained by the Fuchtbauer-Ladenburg formula and then the gain cross sections around 1.9 μm were calculated. The peak emission cross section and width of emission band around 1.9 μm are comparable to those for Tm³⁺:YAG and the tunable range is about 280 nm for the potential ∼1.9 μm laser operation via the ³F₄ → ³H₆ transition.     

Scintillation properties of Nd, Tm, and Er doped LuF3 scintillators in the vacuum ultra violet region

In order to develop novel vacuum ultra violet (VUV) emitting scintillators, we grew Nd 0.5%, Tm 0.5%, and Er 0.5% doped LuF₃ scintillators by the μ-pulling down method, because LuF₃ has a very wide band gap and Nd³⁺, Tm³⁺, and Er³⁺ luminescence centers show fast and intense 5d-4f emission in VUV region. Transmittance and X-ray induced radioluminescence were studied in these three samples using our original spectrometer made by Bunkou-Keiki company. In the VUV region, transmittance of 20-60% was achieved for all the samples. The emission peaks appeared at approximately 180, 165, and 164 nm for Nd³⁺, Tm³⁺, and Er³⁺ doped LuF₃, respectively. Using PMT R8778 (Hamamatsu), we measured their light yields under ²⁴¹Am α-ray excitation. Compared with Nd:LaF₃ scintillator, which has 33 photoelectrons/5.5 MeV α, Nd:LuF₃ and Tm:LuF₃ showed 900±90 and 170±20 ph/5.5 MeV-α, respectively. Only for the Nd doped one, we can detect ¹³⁷Cs 662 keV γ-ray photoabsorption peak and the light yield of 1200±120 ph/MeV was measured. We also investigated their decay time profiles by picosecond pulse X-ray equipped streak camera, and the main decay component of Nd:LuF₃ turned out to be 7.63 ns.     

Optical properties and gamma-ray response of Czochralski grown Pr:Lu3Al5O12 scintillating garnet crystals with different Pr content

Pr:LuAG single crystalline scintillators with different Pr³⁺ concentration, 0.1, 0.18, and 0.22 mol% were grown by the Czochralski method. The crystals were cut to dimensions of 2.2 × 2.2 × 15 mm³ and polished, simulating sensors for Positron Emission Tomography (PET). Their absorption coefficients were examined, and the absorption strength was found to be proportional to the Pr concentration. The α-ray induced emission spectra of the samples demonstrated two emission lines peaking at 310 and 370 nm. The emission intensities in the radio luminescence spectra were also proportional to the Pr content. The absolute light yields and intrinsic energy resolution under γ-ray irradiation were evaluated at +20, 0, and −20 °C using avalanche photodiode as a photodetector. Pr 0.22% doped crystal had strongest light output of 16 400 ph/MeV, and its intrinsic energy resolution was around few % at several hundred keV. When coupled with PMT, the decay time was around 25 ns, and it was almost independent on concentration.     

Eu-doped LiF-SrF2 eutectic scintillators for neutron detection

Eu²⁺ 0.05%, 0.1%, and 0.2% activated LiF-SrF₂ eutectic scintillators were prepared by the Bridgman method using ⁶Li enriched (95%) raw material. The α-ray-induced radio luminescence spectra showed intense emission peak at 430 nm due to an emission from Eu²⁺ 5d-4f transition in the Eu:SrF₂ layers. When excited by ²⁵²Cf neutrons, all the samples exhibited almost the same light yields of 5000-7000 ph/n with a typical decay times of several hundreds ns.     

Mid-infrared emission characteristics and energy transfer processes in doubly doped Tm, Tb: KPb2Br5 and Tm, Nd: KPb2Br5

We present spectroscopic studies on the ∼5 μm mid-infrared emission and energy transfer properties of Tb³⁺ doped KPb₂Br₅ and Nd³⁺ doped KPb₂Br₅ sensitized by Tm³⁺ ions. A series of co-doped Tm, Tb: KPb₂Br₅ and Tm, Nd: KPb₂Br₅ samples were prepared from purified starting materials of PbBr₂, KBr, and rare-earth bromides. Resonant excitation into the ³H₆ → ³F₄ absorption transition of Tm³⁺ at ∼1.76 μm resulted in an enhanced 5 μm emission from Tb³⁺ and Nd³⁺ ions in Tm, Tb: KPb₂Br₅ and Tm, Nd: KPb₂Br₅, respectively. The existence of energy transfer between Tm → Tb and Tm → Nd in KPB was further evidenced by the quenching of the emission decay times of the ³F₄ → ³H₆ transition of Tm³⁺ in doubly doped Tm, Tb: KPb₂Br₅ and Tm, Nd: KPb₂Br₅ compared to singly doped Tm: KPb₂Br₅.     

Photoluminescence of nanocrystalline YVO4:TmxDy1−x prepared by a modified Pechini method

This paper reports the luminescence effects of Tm³⁺ doped YVO₄:Dy nanocrystalline synthesized by a modified Pechini method. The structure and morphology were characterized by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The relationship between the ratio of Tm³⁺/Dy³⁺ and the chromaticity is studied, i.e. Tm³⁺ ion doping effectively tunes the emission color of YVO₄:Tm_xDy_1−x phosphors. The best white light emission was observed with YVO₄:1%(Tm_0.6Dy_0.4). These results indicate that thulium doped YVO₄:Dy phosphors are promising white-emitting luminescence materials.     

Crystal growth and scintillation properties of Nd:CaF2

Nd³⁺ doped CaF₂ single crystal scintillator has been investigated. We tried to grow 1%, 5%, 10%, 20%, 30% and 40% Nd³⁺ doped CaF₂ single crystals by the simple melt-solidifying method. Powder X-ray diffraction (XRD) patterns were measured to identify the phase of all the samples. The XRD patterns of all the samples were similar to CaF₂. Those samples are compared in terms of their X-ray-excited radioluminescence spectra, transmittance, α-ray-excited decay time and light yield. When the X-ray is used for excitation, luminescence is observed in the VUV region. Transmittance of the crystals is more than 70% at wavelengths longer than about 180 nm. In the decay kinetics, the fast components of the samples are distributed in less than 25 ns time range and the slow components of sample are distributed in more than 90 ns. These decay times became shorter with increasing Nd³⁺ concentration. They are related to the Nd³⁺ 5d-4f VUV emission. The light yields of samples are distributed in 5-2500 photon/5.5 MeV α-ray and decrease with increasing Nd³⁺ concentration.     

Sol-gel synthesis of yellow-emitting La4Ca(SiO4)3O:Ce phosphors for white-light emitting diodes

Ce³⁺ doped La₄Ca(SiO₄)₃O phosphors with silicate oxyapatite structure were synthesized by the sol-gel process. The X-ray diffraction (XRD) patterns showed that a pure phase was formed when sintering temperature was higher than 1300°C. The optical properties of La₄Ca(SiO₄)₃O:Ce³⁺ phosphors with varying sintering temperature and concentration were investigated by examining their excitation and emission spectroscopy. The phosphors exhibited a broad emission band centered at 550nm which could be attributed to the 5d-4f transition of Ce³⁺ and a stronger excitation peak around 467nm as well as several shoulder bands, nicely matching with the widely applied blue LED chips. Higher emission intensity was observed when firing temperature above 1300°C, due to increasing crystallinity of the powders. When Ce³⁺ concentration was equal to 5 at%, the sample exhibited the optimum excitation and emission efficiency. The results indicate that La₄Ca(SiO₄)₃O:Ce³⁺ is a promising candidate in the application of blue chip excited white light emitting diodes (LEDs).     

Synthesis and photoluminescence properties of new NaAlSiO4:Eu phosphors for near-UV white LED applications

A new NaAlSiO₄:0.1Eu²⁺ phosphors were synthesized at different temperatures using a liquid phase precursor (LPP) technique. The XRD patterns indicate the presence of hexagonal nepheline phase for all the samples. The synthesized phosphors can be excited efficiently in the broad near-UV region. The PL emission spectra showed a broad emission peak at around 551 nm corresponding to 5d → 4f transition of Eu²⁺ ions. The synthesized phosphors showed better thermal stability when compared with the standard YAG:Ce³⁺ phosphor.     

Up-conversion emission in KGd(WO4)2 single crystals triply-doped with Er/Yb/Tm, Tb/Yb/Tm and Pr/Yb/Tm ions

Triply-doped single crystals KGd(WO₄)₂:Er³⁺/Yb³⁺/Tm³⁺, KGd(WO₄)₂:Tb³⁺/Yb³⁺/Tm³⁺ and KGd(WO₄)₂:Pr³⁺/Yb³⁺/Tm³⁺ were grown by the Top Seeded Solution Growth (TSSG) method, with an aim of getting efficient up-converted multicolored luminescence, which subsequently can be used for generation of white light. Such an aim determined the choice of the triply doped compounds: excitation of the Yb³⁺ ions in the infrared spectral region is followed by red, green and blue emission from other dopants. It was shown that all these systems exhibit multicolor up-conversion fluorescence under 980 nm laser irradiation. Detailed spectroscopic studies of their absorption and luminescence spectra were performed. From the analysis of the dependence of the intensity of fluorescence on the excitation power the conclusion was made about significant role played by the host’s conduction band and other possible defects of the KGd(WO₄)₂ crystal lattice in the up-conversion processes.     

Photoluminescence properties of Eu doped Ba2ZnS3 phosphor for white light emitting diodes

The synthesis and photoluminescence properties of novel Eu²⁺ doped Ba₂ZnS₃ phosphors for white light emitting diodes (LEDs) are reported. Diffuse reflection spectra of Ba₂ZnS₃ host and synthesized phosphors have been measured. The excitation spectra of synthesized phosphors consist of three broad bands between 250 nm and 550 nm and are consistent with the diffuse reflectance spectra. The emission spectra show the characteristic 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ion and there exists efficient energy transfer from host to Eu²⁺ ions when excited by 350-nm light. The dependence of emission spectra on temperature is also measured; the possible reasons applied to explain the experimental results are also discussed. The fluorescence lifetime of Eu²⁺ in Ba_1.995ZnS₃:0.005Eu²⁺ is measured and the values are 1.49 and 23.4 μs.     

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 the Ce-doped multicomponent garnet epitaxial films

(Lu,Y,Gd)₃(Al,Ga)₅O₁₂:Ce garnet scintillator single crystalline films were grown onto LuAG, YAG and GGG substrates by liquid phase epitaxy method. Absorption, radioluminescence spectra and photoluminescence excitation, emission spectra, and decay kinetics were measured. Photoelectron yield, its dependence on amplifier shaping time and energy resolution were determined to evaluate scintillation performance. Most of the samples exhibited strong UV emission caused by trapped excitons and/or Gd³⁺ 4f–4f transition. However, emission spectrum of the best performing Gd₂YAl₅O₁₂:Ce is dominated by the Ce³⁺ fast 5d–4f luminescence. This sample has outperformed photoelectron yield of all the garnet films studied so far.