Growth and scintillation properties of Yb doped aluminate, vanadate and silicate single crystals

For the purpose of quick screening for charge transfer (CT) transitions of Yb³⁺ in various hosts, (Lu_1−xYb_x)₃Al₅O₁₂ (Yb:LuAG) with x=0.05, 0.15, 0.30 and (Y_1−xYb_x)AlO₃ (Yb:YAP) with x=0.05, 0.10, 0.30 were grown by the micro-pulling-down method. (Y,Yb)VO₄ with strong wetting was grown by edge defined film-fed growth method and materials, which require moderate temperature gradient, such as Ca₈(La,Yb)₂(PO₄)₆O₂ and (Gd,Yb)₂SiO₅ were grown by Czochralski method. Strong dependence of the CT luminescence decay time and intensity on temperature was observed for Yb-doped LuAG and YAP. Super fast decay with 0.85 ns decay time was observed in Yb(30%) doped YAP at room temperature. Though the emission intensity is weak at room temperature, it exceeds several times that of PbWO₄. In addition, CT luminescence of Yb:YAP occurs at longer wavelength than in BaF₂, which enables the usage of glass-based photomultiplier for the detection. In addition, higher stopping power will be expected due to the higher density host compared with BaF₂.     

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.     

Luminescence of Yb, Yb co-doped silica glass for white light source

Yb²⁺, Yb³⁺ co-doped silica glasses were prepared by solid state reaction under vacuum condition for the first time. The luminescence properties of Yb²⁺-doped silica glass were investigated. There are four strong absorption bands in the Ultraviolet (UV) light region due to the 4f¹⁴-4f¹³5d¹ transition of the Yb²⁺ ions. The main emission wavelength of the Yb²⁺-doped silica glass was around 530 nm by the excited wavelength of 398 nm. The full width at half maximum (FWHM) of the excitation and emission bands were 137 nm, 165 nm respectively. The results suggest the Yb²⁺-doped silica glasses may be the potential medium for white light sources based on near UV LED chip.     

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.     

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).     

Synthesis and photoluminescence properties of Yb doped Ba5(PO4)3Cl phosphor for white light-emitting diodes

Yb²⁺ ion doped Ba₅(PO₄)₃Cl phosphor was synthesized by solid state reaction. Four distinct absorption bands were observed in the Ultraviolet (UV) light region due to the electronic transitions of Yb²⁺ ion from ¹S₀ ground state to ²F_5/2(t_2g), ²F_5/2(e_g), ²F_7/2(t_2g), and ²F_7/2(e_g) excited states. The main emission wavelength of the phosphor was around 630 nm. The optimized Yb²⁺ ion concentration was 0.2 mol% (λ_exc. = 400 nm). The calculated critical distance was about 8.729 Å and the concentration quenching was observed above 0.2 mol% due to the electric dipole–dipole interaction.     

EPR and vibrational studies of YVO4:Tm, Yb single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic 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.     

Crystal growth and luminescence properties of Yb2Si2O7 infra-red emission scintillator

(Ce_xYb_1−x)₂Si₂O₇ (x = 0.00, 0.01) single crystals were grown by the micro-pulling-down method to test the possibility of its application as infra-red scintillator for medical imaging. Powder X-ray diffraction analysis indicated that the crystals were single-phase materials. The radioluminescence spectra of the crystals demonstrated presence of two near infra-red emission peaks (at 1010 and 1030 nm). The emission peaks at 420 and 580 nm ascribed to defects were also observed in the crystals. The human body has maximum transmission in wavelength range from 650 to 1200 nm. Therefore, Yb₂Si₂O₇ is expected to be used as efficient infra-red scintillator for medical applications.     

Mechanisms of Yb sensitization to Tm for blue upconversion luminescence in fluorophosphate glass

The sensitization mechanisms of Yb³⁺ to Tm³⁺ for the blue upconversion luminescence in fluorophosphate glass were studied. Two different mechanisms exist in the sensitization. One is the sequential sensitization that Tm³⁺ is excited from ³H₆ to ¹G₄ through absorbing three photons transferred from Yb³⁺ one by one. Another is the cooperative sensitization that two Yb³⁺ ions form a couple cluster firstly, and then the couple cluster Yb³⁺ ions transfer their energy to Tm³⁺ and excite it to ¹G₄. With the increment of the concentration of Yb³⁺ ions, the sequential sensitization becomes weak and the cooperative sensitization becomes intense, and the transformation trend of sensitization mechanism with the increment of Yb³⁺ concentration can be clarified by the introduction of Tb³⁺ ions in the glass.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Growth of Yb-doped YLiF4 laser crystal by the Czochralski method. Attempt of Yb energy level assignment and estimation of the laser potentiality

YLiF₄ (YLF) single crystals undoped and Yb³⁺-doped with different concentrations were grown by the Czochralski technique under CF₄ atmosphere. Detailed analysis of Yb³⁺-doped YLF spectroscopy were made to contribute to the determination of energy levels in this host. We are dealing with temperature and concentration dependences of both π and σ polarizations of the infrared (IR) absorption and emission spectra. Raman spectra were also used to give an attempt of interpretation of electronic and vibronic levels. The radiative energy transfer (self-trapping) and strong phonon–electron coupling make the assignment of Yb³⁺ energy levels difficult. Evaluation of the laser potentiality of this fluoride host is also presented.     

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.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

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.     

Temperature dependence of luminescence behavior in Er/Yb co-doped transparent phosphate glass ceramics

The effect of temperature on the luminescence intensity of up-conversion and near infrared in Er³⁺/Yb³⁺ co-doped phosphate glass ceramics has been investigated. Efficient green and red up-conversion luminescence and strong infrared fluorescence at 1.54 μm wavelength are observed under excitation of 975 nm. The fluorescence intensity is changing at different temperature and the results are explained with the level transitions in Er³⁺/Yb³⁺ co-doped system. Meanwhile, the lifetime of Er³⁺:⁴I_13/2 level corresponding to different operating temperature and pump power is also discussed, and the experimental results are fitted using multiphonon relaxation theory.     

Pulsed pumped Yb3+-doped double-cladding fiber amplifier

A pulsed pumped Yb³⁺-doped double-cladding fiber (DCF) amplifier is reported, Seeded by a passive mode-locked Yb³⁺-doped fiber laser, the fiber amplifier can generate 200 W peak-power and 120 ps duration pulses at 100 Hz repetition rate. Because of the pulsed pump approach, the amplified spontaneous emission (ASE) and the spurious lasing between pulses are well avoided.     

Understanding the up-conversion dynamics in high efficiency Yb-Tm systems for solar cells

Up-conversion emission processes have been studied in a transparent oxyfluoride nano-structured glass-ceramic co-doped with Yb³⁺ and Tm³⁺ ions. The decay and rise times, and pump power dependence of the different emission peaks have been analysed. The aim was to achieve a complete picture of the dynamics in this multiphoton excitation system. A method based on balance equations for the involved energy levels has been proposed in order to evaluate the up-conversion and decay rates from these levels. The results are analysed from the point of view of potential application to photovoltaic cells.     

Spectroscopic characterization and optical waveguide fabrication in Ce, Tb and Ce/Tb doped zinc–sodium–aluminosilicate glasses

A spectroscopy investigation of Ce³⁺ and Tb³⁺ ions in sodium–zinc–aluminosilicate glasses is performed using the photoluminescence technique. Blue–white light, with x = 0.24 and y = 0.24 CIE chromaticity coordinates, is obtained for the Tb³⁺ singly-doped glass excited at 351 nm. When the sodium–zinc–aluminosilicate glass is co-doped with Ce³⁺ and Tb³⁺ a non-radiative energy transfer from Ce³⁺ to Tb³⁺ ions is observed upon 320 nm excitation. From an analysis of the cerium emission decay curve, the Ce³⁺ → Tb³⁺ energy transfer microscopic parameter and efficiency are obtained. Different concentrations of Ce³⁺ and Tb³⁺ ions in the glass host gives rise to blue and blue–green emissions, with different CIE coordinates. Optical waveguides were produced in the samples by Ag⁺–Na⁺ ion-exchange, and their characterization is presented.