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.     

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.     

Luminescence and scintillation properties of rare-earth-doped LuF3 scintillation crystals

The Nd-doped and Er-doped LuF₃ single crystals were grown by the micro-pulling-down method to study their scintillation properties in the vacuum-ultraviolet (VUV) region. The doubly Nd–Er codoped single crystal was grown to study possibility of scintillation performance improvement by energy transfer from Er³⁺ to Nd³⁺ ions. The LiF flux was to avoid phase transition below melting temperature. The 1%Nd-doped sample showed the highest overall scintillation efficiency under X-ray excitation which was 7 times as high as that of the LaF₃:Nd 8% standard. The leading Nd³⁺ 5d–4f emission was situated at 176 nm, while the Er³⁺ 5d–4f emission for Er-doped samples was observed at 163 nm, which better matches the sensitivity of some VUV-sensitive photodetectors. The optimum Er concentration was determined to be around 1–3 mol%. No Er³⁺ 5d–4f emission was observed for the doubly Er,Nd-codoped sample due to energy transfer from the Er³⁺ to Nd³⁺ ions. Slight improvement of the light yield was observed in the doubly-doped sample with respect to the Nd-only doped one.     

Bright white upconversion luminescence from Er-Tm-Yb doped CaSnO3 powders

Bright white upconversion luminescence from Er³⁺-Tm³⁺-Yb³⁺ doped CaSnO₃ powders is obtained under the diode laser excitation of 980 nm. It is composed of three primary colors of red, green and blue emissions, which originate from the transitions of ⁴F_9/2 → ⁴I_15/2, (²H_11/2, ⁴S_3/2) → ⁴I_15/2 of Er³⁺ ions and ¹G₄ → ³H₆ of Tm³⁺ ions, respectively. The efficient upconversion emission is attributed to the energy transfer between Yb³⁺ and Er³⁺ or Tm³⁺ions. Moreover, it is observed that Tm³⁺ acts as the quenching center for the green upconversion luminescence from Er³⁺ ions, and the sensitizer for the red and blue luminescence when the Tm³⁺ doping content is less than 0.3 mol%. This is interpreted in terms of the efficient energy transfer between Tm³⁺ and Er³⁺ ions. The calculated color coordinates fall within the white region in the standard 1931 CIE chromaticity diagram, indicating the potential applications of Er³⁺-Tm³⁺-Yb³⁺ doped CaSnO₃ in the field of displaying and lasers, etc.     

Design and achieving mechanism of upconversion white emission based on Yb/Tm/Er tri-doped KY3F10 nanocrystals

KY₃F₁₀:Yb³⁺/Tm³⁺/Er³⁺ upconversion nanocrystals are synthesized via a simple hydrothermal procedure. The nanocrystals emit the near equal energy white light with high brightness and favorable color balance when excited using a 980 nm continuous wave diode laser. The research of upconversion mechanism indicates that in addition to the energy transfer processes from Yb³⁺ to Tm³⁺ and Er³⁺, respectively, there exists a new process ¹G₄ (Tm³⁺) + ⁴I_11/2 (Er³⁺) → ³H₄ (Tm³⁺) + ⁴S_3/2 (Er³⁺).     

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 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 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.     

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.     

Upconversion emission from Tm:Yb and Tm:Er:Yb doped Y2SiO5 powders prepared by combustion synthesis

Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were prepared by combustion synthesis with estimated as-prepared weight (wt.) % concentrations of 0.25:0.0:2.0, 0.25:0.5:2.0 and 0.25:1.0:2.0, respectively. Blue (Tm³⁺: ¹G₄ → ³H₆), green (Er³⁺: ⁴S_3/2, ²H_11/2 → ⁴I_15/2) and red (Er³⁺: ⁴F_9/2 → ⁴I_15/2) upconversion (UC) emissions were observed under 975 nm infrared diode laser excitation. The UC process took place via energy transfer from Yb³⁺ to Er³⁺ and Tm³⁺ ions. The CIE chromaticity coordinates of Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were investigated as a function of the diode laser power and Er³⁺ concentration.     

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.     

Structural and optical properties of neodymium-doped lutetium fluoride thin films grown by pulsed laser deposition

Neodymium-doped lutetium fluoride (Nd³⁺:LuF₃) thin films were successfully grown on MgF₂ (0 0 1) substrates by pulsed laser deposition (PLD). It is void of cracks that are otherwise prevalent due to structural phase transitions in Nd³⁺:LuF₃ during thin film deposition and bulk crystal growth. Cathodoluminescence (CL) spectra revealed multiple emission peaks, with a dominant peak in the vacuum ultraviolet (VUV) region at 179 nm. This peak has a decay time of 6.7 ns. The ability to grow high quality Nd³⁺-doped fluoride thin films would enable fabrication of VUV light-emitting devices that will enhance applications requiring efficient VUV light sources.     

Diode-pumped efficient laser operation and spectroscopy of Tm,Ho:YVO4

Spectroscopic characterization of co-doped Tm,Ho:YVO₄ crystal grown by the Czochralski method has been performed including absorption spectrum, emitting spectrum and luminescence decay lifetime. The polarization emitting spectrum around 2 μm is accomplished by exciting a singly Ho³⁺ doped YVO₄ crystal to exclude the influence of Tm³⁺³F₄-³H₆ transition and the emission cross section is deduced from both Fuchtbauer-Ladenburg (F-L) equation and reciprocity method (RM). In addition, we report up to 10.4 W continuous wave (CW) output with a conversion efficiency of 40% and 10.3 W Q-Switch output with 12.5 kHz pulse repetition rate of diode-pumped cryogenic Tm,Ho:YVO₄ laser. For Q-Switch operation, the minimum pulse width of 28.2 ns is obtained, all of which demonstrate that the Tm,Ho:YVO₄ is excellent laser material for 2 μm radiation.     

NIR-to-visible and NIR-to-NIR upconversion in lanthanide doped nanocrystalline GdOF with trigonal structure

Codoped Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Ho³⁺/Yb³⁺ and triply doped Er³⁺/Tm³⁺/Yb³⁺ gadolinium oxyfluoride nanoparticles were prepared in aqueous solution by a simple coprecipitation method and a suitable heat treatment at 500 °C. From the experimental X-Ray powder diffraction patterns, a Rietveld analysis was carried out and it was determined that the nanoparticles are single phase trigonal GdOF. Electron microscopy images show that the average particle size is approximately 25 nm, even though a certain degree of agglomeration is evidenced. The spectroscopic properties of the lanthanide doped nanoparticles are investigated in terms of emission spectra. For proper lanthanide concentrations, the nanoparticles show visible upconversion upon excitation at 980 nm, making them useful as luminescent nanomaterials for photonic applications.     

Comparative study of ceramic and single crystal Ce:GAGG scintillator

Recent study revealed that single crystal Ce:Gd₃(Al,Ga)₅O₁₂ (Ce:GAGG) showed good scintillation response under γ-ray exposure. We discover here that ceramic Ce:GAGG scintillator exhibited better performance than the single crystal counterpart. We developed Ce 1% doped ceramic and single crystal GAGG scintillators with 1 mm thick and compared their properties. In radioluminescence spectra, they showed intense emission peaking at 530 nm due to Ce³⁺ 5d–4f transition. The ¹³⁷Cs γ-ray induced light yields of ceramic and single crystal resulted 70 000 ph/MeV and 46 000 ph/MeV with primary decay times of 165 and 143 ns, respectively. At present, the observed light yield was the brightest in oxide scintillators.     

Influence of Ce on the luminescence properties of Er/Yb:YVO4 crystals

YVO₄ single crystals doped with Ce³⁺, Er³⁺ and Yb³⁺ ions were grown by the Czochralsski technology. The luminescence properties of Er³⁺/Yb³⁺:YVO₄ single crystals with different concentration of Ce³⁺ were studied, and the energy transfer mechanism between Er³⁺, Yb³⁺ and Ce³⁺ was discussed based on their energy level properties. The branching ratios of the ⁴I_11/2 → ⁴I_13/2 transition in different samples were calculated. The results indicate that codopants of Ce³⁺ greatly enhance the population rate of the ⁴I_13/2 level due to the fast resonant energy transfer between Er³⁺ and Ce³⁺, i.e., ⁴I_11/2(Er³⁺) + ²F_7/2(Ce³⁺) → ⁴I_13/2(Er³⁺) + ²F_5/2(Ce³⁺).     

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 of the Tm and energy transfer between Tm→Pr ions in P2O5-CaO-SrO-BaO phosphate glass

A P₂O₅-CaO-SrO-BaO phosphate glass doped with Tm³⁺ and glasses doped with (Tm³⁺, Pr³⁺) were used for this study. The photo-luminescence behaviors of Tm³⁺ and Pr³⁺ in phosphate glass were investigated by absorption, excitation and emission spectroscopy. The energy transfer between Tm³⁺ and Pr³⁺ in phosphate glasses (which exhibit a variety of transfer efficiencies) was studied. The experimental quantum efficiencies of the luminescence of Tm³⁺ η₀ and (Tm³⁺, Pr³⁺) doped phosphate glasses were measured to give η/η₀ = 0.447, 0.305, and 0.179 for (0.4 mol% Pr³⁺, 1.0 mol% Tm³⁺), (0.8%Pr³⁺, 1.0%Tm³⁺) and (1.6 mol% Pr³⁺, 1.0 mol% Tm³⁺), respectively. In order to verify the nature of the ion coupling in our phosphate glass system, we applied the Inokuti-Hirayama model. The non-radiative energy transfer rate from Tm³⁺ to Pr³⁺, transfer efficiencies, and the donor-acceptor distance have been calculated and compared with obtained experimental data. As usual, the efficiency and the probability of energy transfer increase with the concentration of the acceptor.     

Photon-avalanche upconversion of Ho in NaYF4 and enhancement of violet, blue and green emissions induced by sensitization of Tm

Ho³⁺ singly doped and Ho³⁺/Tm³⁺ co-doped hexagonal NaYF₄ powders have been synthesized by a solid-state reaction method. Under excitation of 671 nm diode laser, upconverted blue, green and red emission bands are observed in Ho³⁺ singly doped sample. Temporal evolution and excitation power dependent behavior for the green emission are explored, indicating that a photon-avalanche mechanism is responsible for the upconversion processes in Ho³⁺ singly doped hexagonal NaYF₄ sample. With the introduction of Tm³⁺, the intensities of both blue and green emissions of Ho³⁺ are efficiently enhanced, which are attributed to two energy transfer processes from Tm³⁺ to Ho³⁺, i.e., ³F₄ (Tm³⁺) + ⁵I₈(Ho³⁺) → ³H₆ (Tm³⁺) + ⁵I₇(Ho³⁺) and ¹G₄ (Tm³⁺) + ⁵I₈(Ho³⁺) → ³H₆ (Tm³⁺) + ⁵F₃(Ho³⁺). The result offers a new sensitization approach to enhance the upconversion efficiency of Ho³⁺ under 671 nm excitation.