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).     

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.     

Crystal growth and scintillation characteristics of the Nd doped LiLuF4 single crystals

Sixty millimeter diameter single crystal of Nd³⁺ doped LiLuF₄ was successfully grown by the Czochralski technique. No remarkable absorption due to unfavorable impurities was observed from optical absorption measurements in the vacuum ultra-violet spectral region. The high crystallinity and homogeneous luminescence characteristics were found from X-ray rocking curve and cathode-ray luminescence respectively. X-ray excited luminescence spectrum was measured and the significant 4f²5d-4f³ luminescence at 182 nm was observed in the grown crystal. The pulse height spectrum was taken upon γ-ray irradiation. As a result, the grown crystals demonstrated sufficient response to the γ-ray showing the light yield of 420 ± 30 photons/MeV. The decay curve under α-ray irradiation was also investigated and described by two component decay kinetics which consists of the decay constants of 34 and 450 ns.     

Basic study of Europium doped LiCaAlF6 scintillator and its capability for thermal neutron imaging application

Eu²⁺ 0.1, 0.5, 1, and 2 mol% doped LiCaAlF₆ single crystalline scintillators were grown by the micro-pulling down (μ-PD) method. Eu²⁺ 2 mol% doped LiCaAlF₆ was also prepared using the Czochralski method. In the transmittance spectra, 4f-5d absorption lines appeared around 200-220 and 290-350 nm. An intense emission at 375 nm due to Eu²⁺ 5d-4f transition was observed under ²⁴¹Am α-ray excitation. When ²⁵²Cf excited pulse height spectra were measured, Eu 2% doped one showed the highest light yield of 29,000 ph/n with 1.15 μs decay time. Using the 2 inchφ Czochralski grown one coupled with the position sensitive photomultiplier tube covered by Cd mask with various size (1, 2, 3, and 5 mm) pin holes, thermal neutron imaging was examined. As a result, the spatial resolution turned out to be better than 1 mm.     

Crystal growth and scintillation properties of (NaxCa1−2xLux−yNdy)F2 single crystals

Na_xCa_1−2xLu_x−yNd_yF₂ single crystals were grown from the melt using the precise atmosphere control type Micro-Pulling-Down (μ-PD) method to investigate their potential as a vacuum-ultraviolet (VUV) scintillators. The grown crystals were single-phase materials with fluorite-type structure (Fm-3m, Z = 4) as confirmed by XRD. The crystals demonstrated 80-90% transmittance above 200 nm wavelength and Nd³⁺ 5d-4f luminescence (when exited by X-ray) observed around 185 nm. The radioluminescence measurements under 5.5 MeV α-ray excitation (²⁴¹Am) demonstrated the light yield of 48 [Ph/5.5 MeV-α] and the decay time of 6.4-7.7 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.     

Crystal growth and optical properties of the Nd doped LuF3 single crystals

Thirty millimeter diameter single crystal of Nd³⁺ doped LuF₃ was grown using LiF as solvent. The single phase crystallization was confirmed by the powder X-ray diffraction, and high structural perfection was demonstrated by X-ray rocking curve (XRC) measurements. FWHM of XRC for 220 reflection was 32 arcsec. No remarkable absorption due to unfavorable impurities was observed from optical absorption measurements in the VUV spectral region. The crystal showed the VUV luminescence peaking around 178 nm that is consistent with the 4f²5d-4f³ transition of Nd³⁺ ion. The luminescence intensity of Nd:LuF₃ under X-ray irradiation was significantly higher than that of reported VUV scintillators such as Nd:LaF₃ or Nd:LiLuF₄.     

Crystal growth and thermal neutron scintillation response of Ce doped KLiYF5

K⁶Li(Y_1−xCe_x)F₅ (x = 0.003, 0.02) single crystals were grown from the melt using the precise atmosphere control type Micro-Pulling-Down (μ-PD) method to examine their potential as a new thermal neutron scintillators. The grown crystals were single-phase materials as confirmed by XRD. The crystals demonstrated 40-60% transmittance above 320 nm and Ce³⁺ 5d-4f luminescence observed around 340 nm when exited by α-ray. The radio luminescence measurements under thermal neutron excitation (²⁵²Cf) demonstrated the light yield of 890 (Ph/neutron) and the decay time excited by α-ray exhibited 20 and 259 ns.     

Crystal growth and spectroscopic studies of novel Yb-doped K5Nd(MoO4)4 single crystals

K₅Nd(MoO₄)₄ crystals with different Yb³⁺ concentrations were grown using Czochralski technique. Room-temperature absorption spectra were recorded and assigned on the basis of Dieke's diagram for Nd³⁺ ion; the standard Judd-Ofelt theory has been used to analyze the spectra. Increase of Yb³⁺ concentration leads to variation of the corresponding Judd-Ofelt intensity parameters. Significant contribution of the Yb↔Nd energy transfer into the formation of the Nd³⁺ absorption spectra causes the observed changes. After illumination of the crystals with CW Nd:YAG laser changes of the birefringence for the laser line of CW He-Ne laser at 633 nm were studied. Birefringence changes show good correlation with the content of Yb ions.     

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.     

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.     

Crystal growth and scintillation properties of Ce and Eu doped LiSrAlF6

Ce and Eu doped LiSrAlF₆ (LiSAF) single crystals for the neutron detection with different dopant concentrations were grown by the micro-pulling-down method (μ-PD). In Ce:LiSAF, intense emission peaks due to Ce³⁺ 5d-4f transitions were observed at approximately 315 and 335 nm in photo- and α-ray induced radio-luminescence spectra. In case of Eu:LiSAFs, an intense emission peak at 375 nm due to Eu²⁺ 5d-4f transition was observed in the radio-luminescence spectra. The pulse height spectra and decay time profiles were measured under ²⁵²Cf neutron irradiation to examine the neutron response. The Ce 3% and Eu 2% doped LiSAF showed the highest light yield of 2860 ph/n with 19 ns main decay time component and 24,000 ph/n with 1610 ns.     

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.     

Generation of annularly symmetric periodic ferroelectric domains in Nd doped near stoichiometric LiTaO3 crystals by the vapor transport equilibration processing

Annually symmetric periodic ferroelectric domain and near stoichiometry have been generated simultaneously from Nd-doped congruent LiTaO₃ crystals by using the vapor transport equilibration (VTE) processing for the first time. The periodic width in the domain structure of 0.5 mol% Nd doped stoichiometric LiTaO₃ crystal was found to be about 70 μm, and the wavelength decreased with the increasing Nd concentration. It can be noticed by transmission spectra that VTE treated LT crystals shows blue shift as compared to congruent LT crystals. Also, various absorption bands were observed in Nd-doped LiTaO₃ crystals corresponding to the transitions from ⁴I_9/2 ground state of Nd³⁺ ions, indicating its potential in the self-lasing quasi-phase matching (QPM) applications.     

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.     

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.     

Growth, spectroscopic properties and laser performance of Nd-doped potassium ytterbium tungstate laser crystal

The 5 at.% Nd³⁺-doped potassium ytterbium tungstate (Nd³⁺:KYb(WO₄)₂, hereafter Nd:KYbW) laser crystal with the dimension up to 28 mm × 15 mm × 12 mm was grown by the top seeded solution growth (TSSG) method. The infrared spectrum of crystal sample was measured, and the vibrational peaks were assigned. According to the absorption and emission spectra of crystal sample, the absorption and emission cross-sections are 16.03 × 10⁻²⁰ cm² at 808 nm and 10.72 × 10⁻²⁰ cm² at 1067 nm, respectively. The fluorescence life of ⁴F_3/2 energy level is 196.33 μs, and the fluorescence branching ratio for the ⁴F_3/2-⁴I_11/2 transition at 1067 nm is 55.74%. The energy transfer between Nd³⁺ and Yb³⁺ ions was observed from the fluorescence spectra pumped by 808 and 980 nm LD sources and the Stark levels of Yb³⁺ in Nd:KYbW crystal were determined. Highly efficient laser output up to 305 mW of Nd:KYbW crystal at 1067 nm has been achieved under pumping by a CW 808 nm laser diode at room temperature. The optical-optical conversion efficiency is 33.9% and the slope efficiency is 46.8%.     

Basic study of single crystal fibers of Pr:Lu3Al5O12 scintillator for gamma-ray imaging applications

Single-crystalline fibers were grown from 0.25, 0.70, and 1.50 mol% Pr-doped Lu₃Al₅O₁₂ (LuAG) melts by the micro-pulling down (μ-PD) method with a diameter of 0.3-0.5 mm and a length of about 200 mm. They were cut to 10 mm long specimens, and their scintillation properties, including light yield and decay time profile, were examined. These results were compared with corresponding properties of the specimens (0.8×0.8×10 mm³) cut from the bulk crystals produced by conventional Czochralski (CZ) growth. The μ-PD-grown fibers demonstrated relatively low light yield and had the same decay time constant when compared with those of the samples cut from the CZ-grown crystals. The fiber crystals were used to assemble scintillating arrays with dimensions of Ø 0.5×10 mm²×20 pixels and Ø 0.3×10 mm²×30 pixels coated by a BaSO₄ reflector. After optical coupling with a position sensitive photomultiplier tube, the fiber-based arrays demonstrated acceptable imaging capability with a spatial resolution of about 0.5 mm.     

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.     

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.