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.     

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.     

Synthesis and luminescent properties of novel Ba2−xEuxZr2−yHfySi3O12 phosphor

A series of Eu²⁺ activated luminescent materials according to the composition of Ba_2−xEu_xZr_2−yHf_ySi₃O₁₂ were synthesized using a high temperature solid-state reaction method starting from metal oxides and carbonates. Single phase powders were obtained using two annealing steps and boric acid as a flux. Firstly, starting materials were sintered at 1450 °C for 5 h under CO atmosphere and subsequently annealed at 1200 °C for 5 h under N₂/H₂ (95%/5%) gas flow. All samples were characterized by powder X-ray diffraction (XRD) analysis, thermal quenching (TQ), fluorescence lifetime measurements and photoluminescence (PL) techniques. Moreover, emission colour points, luminous efficacies and quantum efficiencies (QE) were calculated and discussed as a function of Eu²⁺ concentration and Zr/Hf ratio of the host lattice.     

Scintillation properties of CsSrX3:Eu (CsSr1−yEuyX3, X = Cl,Br; 0 ≤ y ≤ 0.05) single crystals grown by the Bridgman method

The single crystals of CsSr_1−yEu_yCl₃ and CsSr_1−yEu_yBr₃ (0 ≤ y ≤ 0.05) grown by the Bridgman method have been investigated for their scintillation properties. The radioluminescence spectra of the crystals demonstrated a narrow band at 400–500 nm which peak position shifts continuously toward larger wavelength as the Eu²⁺ concentration increases. The scintillation light yield achieves maximal value of 33,400 ± 1700 photons per MeV with energy resolution of 11.5% at CsSr_0.95Eu_0.05Cl₃ and 31,300 ± 1600 photons per MeV with energy resolution of 9% at CsSr_0.95Eu_0.05Br₃. The decay times at room temperature are 2.7 ± 0.2 μs and 2.5 ± 0.2 μs, respectively.     

Growth and optical properties of Er,Yb:YAl3(BO3)4 crystal

Single crystal of erbium, ytterbium-codoped yttrium aluminum tetraborate Er,Yb:YAl₃(BO₃)₄(Er,Yb:YAB) has been grown by the flux method. The absorption spectrum in the visible and NIR regions of Er,Yb:YAl₃(BO₃)₄ crystal are measured at room temperature and fluorescence spectrum of Er,Yb:YAl₃(BO₃)₄ crystal are also measured at room temperature, excited by 976 nm laser. Not only the strong NIR emission peaks located at 1548 nm was observed, but also the visible up-conversion luminescence has been found. The specific heat of the Er/Yb:YAB crystal at room temperature is 0.81 J/g °C.     

Effects of polarized excitation on the PJ manifolds emission in KYF4:Pr single crystal

A room temperature spectroscopic investigation on KYF₄:1.25 at%Pr³⁺ is presented. The effects on the optical properties of the multisite-disordered nature of the sample are studied and discussed. In particular we report on the broadening of the ³P_J absorption lines, at 10 and 300 K, and the 450–770 nm emissions as a function of observation and pump polarization. The evidence of a peculiar difference between emission under polarized excitation, parallel or orthogonal to the c axis, is shown. The ³P₀ lifetime was 45 μs in agreement with that measured in other fluoride hosts.     

Growth, thermal and optical properties of Yb:GdYAl3(BO3)4 crystal

Single crystal of Yb:GdYAl₃(BO₃)₄(Yb:GdYAB) has been grown by the flux method. The structure of Yb:GdYAB crystal has been determined by X-ray diffraction analysis. The experiment show that the crystal has the same structure as that of YAl₃(BO₃)₄ crystal and its unit cell constants have been measured to be a = 9.30146 Å, c = 7.24164 Å, Vol = 542.59 Å³. The absorption and fluorescence spectrum of Yb:GdYAl₃(BO₃)₄ crystal have also been measured at room temperature. In the absorption spectra, there are two absorption bands at 938 nm and 974 nm, respectively, which is suitable for InGaAs diode laser pumping. In the fluorescence spectra, there are two fluorescence peaks at 992 and 1040 nm. The thermal properties of Yb:GdYAl₃(BO₃)₄ crystal have been studied for the first time. The thermal expansion coefficient along c-axis is almost 5.4 times larger than that along a-axis. The specific heat of the crystal has been measured to be 0.77 J/g °C at room temperature. The calculated thermal conductivity is 5.26 Wm⁻¹ K⁻¹ along a-direction.     

Third harmonic generation in LiKB4O7 single crystal

The third order nonlinear optical properties of the lithium potassium borate (LiKB₄O₇) single crystal have been investigated by means of the rotational Maker fringe technique using Nd:YAG laser at 1064 nm working in picosecond regime. The value of the third order nonlinear optical susceptibility was calculated using the theoretical model of Kajzar et al. and was found to be about 1.4 × 10⁻²¹ m² V⁻² that is one order higher than that of fused silica.     

Growth and characterization of non-linear optical crystal Cd3Zn3B4O12

Cd₃Zn₃B₄O₁₂ polycrystals were synthesized by solid-state and wet chemical reaction methods. Cd₃Zn₃B₄O₁₂ single crystals with millimeter grade were grown from the self-flux B₂O₃ (Cd:Zn:B = 1:1:1.5); and larger crystals were obtained from the PbO-0.85PbF₂ fluxes easily. As-grown crystals were characterized by differential scanning calorimetry and thermogravimetric, X-ray diffraction, infrared and Raman spectral analysis, respectively. The non-linear optical coefficient of the Cd₃Zn₃B₄O₁₂ crystal is 2.6 times as large as that of KH₂PO₄ crystal. Chemical etching shows that this crystal is very stable in neutral solution and not hygroscopic in air at room temperature.     

Influence of additional Eu coactivator on the luminescence properties of Tb3Al5O12:Ce, Eu

The luminescence properties of doubly activated terbium aluminium garnet samples were investigated in the present study. Commercial Tb₃Al₅O₁₂:Ce³⁺ (TAG:Ce) shows the typical Ce³⁺ ion luminescence of the allowed Ce³⁺ d–f transition. Eu³⁺ co-doping, however, reveals interesting results. In TAG:Ce, Eu, both Ce³⁺ and Eu³⁺ luminescence was measured at different Ce and Eu activator concentrations. The Ce³⁺ ion can be used as a sensitizer in the TAG lattice that transfers its energy directly or via the Tb sublattice to the activator Eu³⁺. The energy-level diagram was proposed to explain the luminescence mechanism. Application of TAG:Ce, Eu with improved chromaticity coordinates CIE (Commission Internationale de l’Eclairage) and color rendering index (CRI) in light emitting diodes (LEDs) is demonstrated.     

Effect of metal halide fluxes on the microstructure and luminescence of Y3Al5O12:Ce phosphors

Yellow-emitting Y_2.95Al₅O₁₂:0.05Ce (YAG:Ce) phosphor particles with high luminescence efficiency under 450 nm ultraviolet (UV) excitation were prepared by a heat treatment of submicrometer-sized oxide powder mixture in a reducing atmosphere at 1550 °C. Prior to the heat treatment, the oxide mixture was blended with 5 wt% of metal halides – BaF₂, BaCl₂, NaF, NaCl, and KF – as a flux. It was observed that YAG:Ce particles prepared with fluorine containing flux demonstrated spherical morphology, high photoluminescence properties, and diameters of 5–20 μm, whereas those prepared with chlorine were small-sized particles (≤5 μm) with relatively low intensity. The highest relative photoluminescence (PL) intensity (∼118%) was obtained for the samples prepared with 5% BaF₂. A set of rules was established for the formation of spherical YAG:Ce particles in the presence of this flux.     

Synthesis and optical properties of (Gd1−x,Eux)2O2SO4 nano-phosphors by a novel co-precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphors were synthesized by a novel co-precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and NaOH starting materials. Composition of the precursor is greatly influenced by the molar ratio of NaOH to (Gd_1−x,Eu_x)₂(SO₄)₃ (the m value), and the optimal m value was found to be 4. Fourier transform infrared spectrum (FT-IR) and thermal analysis show that the precursor (m = 4) can be transformed into pure (Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphor by calcining at 900 °C for 2 h in air. Transmission electron microscope (TEM) observation shows that the Gd₂O₂SO₄ phosphor particles (m = 4) are quasi-spherical in shape and well dispersed, with a mean particle size of about 30-50 nm. Photoluminescence (PL) spectroscopy reveals that the strongest emission peak is located at 617 nm under 271 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 10 mol% and the concentration quenching mechanism is exchange interaction among the Eu³⁺ ions. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions has a single exponential decay behavior.     

Prompt and delayed recombination mechanisms in Lu4Hf3O12 nanophosphors

We study lutetium hafnate, Lu₄Hf₃O₁₂, prepared by acetate and citrate combustion in the form of nanometric powders. Optical properties including X-ray excited luminescence, steady-state and time resolved photoluminescence as well as thermally stimulated luminescence are investigated for undoped as well as Eu³⁺ and Tb³⁺ doped samples. We identify recombination centers in the host matrix and we tentatively associate the principal emission with a radiative transition of the F⁺ center. We also demonstrate that athermal tunneling of charge carriers between traps and recombination centers is the predominant mechanism of delayed radiative recombination following irradiation by ionizing radiation.     

Crystal growth and dielectric characterization of crystals derived from the solid-solution Ba(1−x)NaxTi(1−x)NbxO3 (BTNN)

Single crystals of (1 − x)BaTiO₃ + xNaNbO₃ (BTNN) for x = 0.84 were obtained by high temperature solution growth using Na₂B₄O₇ as solvent. The room temperature crystal structure of BTNN 16/84-phase was determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm. The refinement from 246 independent reflections led to the following parameters: a = b = 5.5845(3) Å, c = 3.9453(2) Å, V = 123.041(11) Å³, Z = 2, with final cR_wp = 0.150 and R_B = 0.041. The structure of BTNN 16/84-phase can be described as a three-dimensional framework built up from (Nb-Ti)O₆ octahedra with Na and Ba in the dodecahedral site of perovskite-like type. Some mm³-sized crystals have been selected and various dielectric measurements (ferroelectric, pyroelectric, and piezoelectric) have been performed. Transition from paraelectric to ferroelectric state at around 460 K has been observed to be in good agreement with ceramics of closer composition. Dielectric, piezoelectric and pyroelectric measurements on crystal confirm the ferroelectric behaviour of BTNN 16/84.     

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.     

Single crystalline Co3O4: Synthesis and optical properties

Crystals of Co₃O₄ have been prepared from thermal decomposition of molecular precursors derived from salicylic acid and cobalt (II) acetate or chloride at 500 °C. A cubic phase Co₃O₄ micro- and nanocrystals have been obtained. The as-synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The images of electron microscopes showed octahedral crystals of Co₃O₄. The volume and polarizability of the optimized structures of molecular precursors have been calculated and related to the particle size. The optical band gap of the obtained crystals has been measured. The results indicated two optical band gaps with values 2.65 and 2.95 eV for (E_g1) (E_g2), respectively.     

Ce dopant segregation in Y3Al5O12 optical ceramics

Ce³⁺-doped YAG garnet optical ceramic have been sintered at the Shanghai Institute of Ceramics in China to characterize dopant distribution in optical ceramics by combining optical spectroscopy and two spatially resolved techniques as imaging confocal microscopy and transmission electron microscopy. A strong Ce³⁺ segregation and spatial variations of content between grains and grain boundaries has been confirmed by quantitative data obtained by TEM microscopy. This observation is another evidence of the inhomogeneous Ce³⁺ distribution across grain and grain boundaries in optical ceramics comparable to that of Nd³⁺ ions in YAG ceramics. These results correlate well with low segregation coefficients of Nd³⁺ and Ce³⁺ observed in the garnet crystals grown from the melt and/or flux.     

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 characterization of Yb-doped Gd3Ga5O12

Single crystals of (Yb_xGd_1−x)₃Ga₅O₁₂ (0.0 ≤ x ≤ 1.0) have been grown by the micro-pulling-down method. Formation of continuous solid solutions with a garnet structure was confirmed. Composition dependence of the lattice constant, thermal diffusivity, specific heat capacity and thermal conductivity was investigated. Assignment of the Yb³⁺-energy levels in Gd₃Ga₅O₁₂-host lattice has been performed by using absorption, emission and Raman spectroscopy measurements at both, room temperature and at 12 K.     

Crystal growth and spectral properties of Pr:La2(WO4)3

Pr³⁺-doped La₂(WO₄)₃ single crystal with dimensions up to Ø 20 mm × 35 mm has been grown by the Czochralski method. The structure of the Pr³⁺:La₂(WO₄)₃ crystal was determined by the X-ray powder diffraction and the Pr³⁺ concentration in this crystal was determined. The absorption and fluorescence spectra of Pr³⁺:La₂(WO₄)₃ crystal were measured at room temperature, and the fluorescence lifetime of main emission multiplets were estimated from the recorded decay curves. The spectral properties related to laser performance of the crystal were evaluated.