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.     

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.     

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 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.     

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 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).     

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 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.     

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.     

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.     

Analysis of VUV and optical spectra of Cs2NaYF6 crystals doped with Tm

This study presents a detailed interpretation and analysis of the reported interconfigurational spectra of Tm³⁺ in Cs₂NaYF₆ [V.N. Makhov, N.M. Khaidukov, D. Lo, J.C. Krupa, M. Kirm, E. Negodin, Opt. Mater. 27 (2005) 1131]. Since only spin-forbidden d–f emission bands are observed for Tm³⁺ in this host, it is unsuitable for use as a scintillator because the emission lifetime is too long. The d–f emission spectrum is well-explained by calculation and most of the intensity is located in one band: 4f¹¹5d¹ (high-spin) → 4f^{12 3}H₆. Measurements from the bands in the d–f excitation spectrum do not provide the accurate separation energy of the high and low-spin states. Strict O_h point group selection rules are operative for the optical spectra. The electronic states of the 4f¹¹5d¹ configuration (briefly, d-electron states, hereafter) are calculated to span from 58,318 cm⁻¹ to 86,900 cm⁻¹. At least five structured bands are observed in the excitation spectrum and their intensities are fairly well simulated by calculation. The 4f¹² → 4f¹³ (np₆)⁻¹ charge transfer band is assigned between 140 and 120 nm (83,000–71,000 cm⁻¹) and excitation into this band leads to f–f emission, bypassing the d-electron states.     

Spectroscopic behavior of Nd in a new microcrystalline ZnY4W3O16 tungstate

In the framework of systematic investigations of the optical properties of a new tungstate ZnY₄W₃O₁₆ in which Y³⁺ cations allow for rare-earth ions doping, the compounds doped with neodymium Nd³⁺ ion were synthesized, analyzed and considered as a possible laser material. The crystalline stoichiometric sample of the chemical formula ZnNd₄W₃O₁₆ and their yttrium diluted analogues 0.5, 1, 5 and 10 mol% Nd³⁺-doped ZnY₄W₃O₁₆ were obtained by a solid-state reaction. X-ray powder diffraction analysis as well as the IR spectra were used to the structural characterization of the compounds. Electron microscopy has been used to analyze the grain size, the presence of aggregates, and the type of boundary between the microcrystals. In order to study spectroscopic properties, the high resolution absorption and emission spectra at room and low temperature were measured in visible and IR regions. The radiative transition probabilities in those tungstates were calculated and analyzed. Based on the 4 K absorption spectra in the range of ⁴I_9/2 → ²P_1/2 transition the number of metal sites occupied by the dopants was determined. The strong fluorescent emission involving the ⁴F_3/2 → ⁴I_9/2, ⁴I_11/2, ⁴I_13/2 transitions at 298 and 77 K were observed under pulsed laser and xenon lamp excitation. The dynamics of the Nd³⁺ excited states were characterized by decay times measurements and compared to earlier reported data for neodymium tungstates.     

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.     

Optical properties of Sm doped Mg:LiNbO3 and Zn:LiNbO3 single crystals

Sm³⁺ doped Mg:LiNbO₃ and Zn:LiNbO₃ are grown by Czochralski method. Optical transmittance and emission spectra are measured and Judd-Ofelt theory is applied to determine phenomenological intensity parameters, oscillator strengths, radiant transition rates, total radiant lifetimes, and branching ratios. The calculations show that Judd-Ofelt parameters with the relation of Ω₄ > Ω₂ > Ω₆ exist, and ΣΩ_ξ (ξ = 2, 4 and 6) in Sm:Zn:LiNbO₃ decreases. Fluorescence spectra indicate that visible fluorescence of Sm³⁺ is made up of 570, 606, 613 and 654 nm emission bands in these crystals under 409 nm excitation.     

Shaped single crystal growth and scintillating application of Yb:(Gd,Lu)3(Ga,Al)5O12 solid solutions

Shaped single crystals of (Yb_0.05Lu_xGd_0.95−x)Ga₅O₁₂ (0.0x0.9) and Yb_0.15Gd_0.15Lu_2.7(Al_xGa_1−x)O₁₂ (0.0x1.0) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃(Ga,Al)₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect––host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Efficient Bi → Nd energy transfer in Gd2O3:Bi,Nd

Bi³⁺,Nd³⁺ co-doped Gd₂O₃ were prepared by solid state reaction and the optical properties were investigated. The results show that the near-infrared emission of Nd³⁺ ions is significantly enhanced by the introducing of Bi³⁺ in co-doped samples. An efficient energy transfer from Bi³⁺ to Nd³⁺ corresponds to the near-infrared emission enhancement. The energy transfer efficiency reaches 64.1% for the sample with the strongest near-infrared emission, which has the optimized doping concentrations of 0.5% for Bi³⁺ and 2% for Nd³⁺. The interesting optical properties make Bi³⁺,Nd³⁺ co-doped Gd₂O₃ promising as the luminescent down-conversion layers in front of c-Si solar cells to enhance the performance of the solar cells.     

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.     

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.     

Optical properties of MgO doped near-stoichiometric LiTaO3 single crystals

Comparative study of the optical properties of undoped and 1-3 mol% MgO doped near-stoichiometric LiTaO₃ (SLT) crystals were undertaken. It was observed that the red shift in the absorption edge occurred with the increasing MgO doping concentration. The infrared absorption spectrum of the OH-stretch-mode in SLT was measured for crystals of undoped and 1-3 mol% MgO doped compositions. The coercive field for the crystals was measured to be 0.913, 0.610 and 0.735 kV/mm for 1-3 mol% MgO doped SLT, respectively. Photorefractive damage of SLT single crystals with 1-3 mol% MgO doping levels was measured to be 136.29, 180.25 and 222.54 MW/cm².