High pressure luminescence and time resolved spectra of La2Be2O5:Pr

We present luminescence, luminescence excitation and luminescence time resolved spectra of La₂Be₂O₅:Pr³⁺ system. We used high pressure spectroscopy approaches, with high pressure applied in diamond anvil cell (DAC) and sapphire anvil cell (SAC), for detailed analysis of luminescence related to the 4f5d → 4f² and 4f² → 4f² transitions. We present effect of up-converted luminescence related to 4f5d → 4f² transition excited with 488 nm. We also discussed possibility of existence of praseodymium trapped exciton (PTE) states in La₂Be₂O₅:Pr³⁺ system. Lack of the PTE is attributed to high quantity of bulk modulus of this material.     

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.     

Low temperature luminescence of KMgF3:Eu crystal

Paper presents luminescence spectra and time resolved spectra of KMgF₃:Eu²⁺ system obtained at different temperatures and pressures, under excitation with 325 nm. At temperatures between 200 K and 292 K the spectra consist of sharp line peaked at 27,830 cm⁻¹ related to ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺ accompanied by the phonon sideband. Under pressure the red spectral shift with the rate equal to −0.6 cm⁻¹/kbar is observed. Luminescence decay is single-exponential with the lifetime equal to 5.2 ms independent of pressure and temperature. The emission spectra obtained at temperatures lower than 125 K consist of 5 sharp lines peaked at 27,590 cm⁻¹, and 27,670 cm⁻¹, 27,722 cm⁻¹, 27,766 cm⁻¹ and 27,809 cm⁻¹, that relative intensity depends on temperature. Pressure shift of these lines was found to be equal to −0.6 cm⁻¹/kbar; the same as ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺, whereas their lifetime is shorter and is equal to 0.7 ms at 100 K. These new lines disappear at temperature greater than 200 K. We tentatively related them to the luminescence of Eu²⁺-F center (fluorine vacancy with electron) complex.     

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.     

Time-resolved spectroscopy of intrinsic luminescence of Y3Ga5O12 and (LaLu)3Lu2Ga3O12 single crystals

The nature of intrinsic luminescence of Y₃Ga₅O₁₂ (YGG) and (LaLu)₃Lu₂Ga₃O₁₂ (LLGG) single crystals grown from a melt was determined. In the case of a YGG single crystal containing Y_Ga antisite defects with a concentration of 0.25–0.275 at.% the intrinsic luminescence was considered as a superposition of luminescence of self-trapped excitons (STE), luminescence of excitons localized near antisite defects (LE(AD) centers) and luminescence caused by a recombination of an electron with a hole captured at Y_Ga antisite defects. Due to a large (2–3%) concentration of Lu_La antisite defects in LLGG single crystals the intrinsic luminescence was a superposition mainly of the LE(AD) center emission and the recombination luminescence of Lu_La antisite defects. The energy structure of the mentioned centers in YGG and LGGG hosts was determined from the excitation spectra of their luminescence under excitation by synchrotron radiation in the range of the fundamental absorption edge of these garnets.     

Concentration effects on Pr luminescence in LaAlO3 crystals

Concentration dependant emission spectra and fluorescence dynamic profiles have been investigated in Pr_xLa_1−xAlO₃ single crystals in order to better understand processes responsible for concentration quenching of the praseodymium ³P₀ and ¹D₂ emissions. The cross-relaxation transfer rates were experimentally determined as a function of Pr³⁺ concentration. Decays were modeled and nearest-neighbor trapping rates were calculated.     

Enhanced photoluminescence of CaTiO3:Pr phosphor films deposited on SiO2 buffered Si substrates

CaTiO₃:Pr³⁺ films have been prepared by pulsed-laser deposition method on SiO₂-buffered Si substrates, and their microstructure and photoluminescence properties have been compared with those of the films deposited directly on bare Si substrates. The SiO₂ buffer layers were prepared using thermal oxidization and HF-etching. Photoluminescence intensities of CaTiO₃:Pr³⁺ films on the SiO₂-buffered Si substrates are significantly higher (up to 800%) than those of the films on bare Si substrates, which is attributed to the low refractive index and low light absorption of the SiO₂ buffer layer. This study reveals that the presence of the buffer layer is effective in improving the red emission brightness of CaTiO₃:Pr³⁺ films without sacrificing the surface roughness.     

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).     

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.     

Laser-induced time-resolved luminescence of orange kyanite Al2SiO5

Manganese is a very important microelement performing a large number of biological functions in human body. We have detected by spectroscopic measurements manganese in mineral kyanite. In this paper we present laser-induced time-resolved luminescence and optical absorbance spectra of orange, Mn containing kyanite. It was proven the orange color is caused by Mn³⁺. Several luminescence lines and bands were found and ascribed to Mn⁴⁺ and Mn³⁺, emission centers. The spectroscopic technique can be utilized for detection of small amounts of manganese in minerals.     

Emission properties of (SrTiO3-TiO2):Pr eutectic with self-organized fractal microstructure

An investigation of spectroscopic properties of (SrTiO₃-TiO₂):Pr³⁺ eutectic and, for comparison, of bulk SrTiO₃:Pr³⁺ and TiO₂:Pr³⁺crystals is presented. Luminescence spectra have been measured under both 450 nm and 350 nm excitation wavelength. For UV excitation they are characterized by a dominant red luminescence corresponding to transition from the ¹D₂ level of Pr³⁺ ions. The mechanism responsible for quenching of blue (from ³P₀ state) and intensification of red luminescence is proposed to be thermally-induced radiationless relaxation involving a low-lying Pr³⁺-Ti⁴⁺ intervalence charge transfer state. Measured decay constants of ¹D₂ excited state of Pr³⁺ are compared with values obtained for other praseodymium doped titanate hosts.     

Red and infrared luminescence from tetragonal YSZ:Pr single crystal fibres grown by LFZ

Single crystal fibres of Pr³⁺-doped tetragonal yttria stabilized zirconia were grown by the laser floating zone method. The fibres show strong red luminescence at room temperature under ultraviolet optical pumping, which is due to the transition between the ¹D₂ and ³H₄ multiplets of the Pr³⁺ ion. Additionally, in the infrared spectral range main transitions were found at ∼1140 nm and 1560 nm. Their intensity ratio was shown to be dependent on the excitation wavelength, suggesting the presence of multiple Pr³⁺-related centres.     

Pechinin synthesis and luminescence properties of Y3Ga5O12(YGG):Tb thin film

YGG:Tb thin films were successfully prepared by Pechni sol-gel process. The structure, surface morphology, evolution of film crystallization and their luminescent properties were investigated. We find the annealing process is very important to the YGG:Tb film crystallization. Uniform crack-free films can be obtained by conventional annealing for 1 h after rapid thermal treating for 10 min at 800 °C. The excitation and emission spectra of photoluminescence (PL) were used to characterize the luminescent properties. The excitation spectrum of YGG:Tb is dominated by the 4f-4f5d transition of Tb³⁺at 260 nm. The emission peaks of phosphor thin film lie at 488 and 543 nm. It can be used as a promising phosphor material for FED or ELD application.     

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.     

The influence of the Pr 4f5d configuration on the S0 emission efficiency and lifetime in LaPO4

The photoluminescence and excitation spectra of Pr³⁺ activated LaPO₄ has been investigated in the 1.6-300 K temperature region. At room temperature, the luminescence of LaPO₄:Pr³⁺ is composed of the interconfigurational 4f¹5d¹ → 4f² emission transitions. However, in the 1.6-60 K temperature range, the emission spectrum also consists of the intraconfigurational emission transitions that emanate from the ¹S₀ state. A radiative lifetime of 145 ns is measured for the Pr³⁺¹S₀ → ¹I₆ emission transition in LaPO₄. This is one of the shortest radiative lifetime observed for this transition in a solid. The energy position of the Pr³⁺¹S₀ state in LaPO₄ is established by high-resolution emission spectrum at 46 375 ± 5 cm⁻¹. A detailed analysis of the thermal quenching of the ¹S₀ lifetime and emission intensity is presented. It is proposed that the lowest energy state of the relaxed 4f¹5d¹ configuration is situated energetically below that of the ¹S₀ state.     

Improved luminescence from Y2Sn2O7:Tb nanoparticles co-doped with Sb ions

Very small nanoparticles (size 3-5 nm) of Y₂Sn₂O₇, Y₂Sn₂O₇:Tb³⁺ and Sb³⁺ co-doped Y₂Sn₂O₇:Tb³⁺ were prepared at a relatively low temperature of 700 °C. Y₂Sn₂O₇ host is characterised by an emission around 436 nm, which is arising from the oxygen vacancies present in the lattice. Tb³⁺ emission improves significantly when Sb³⁺ ions are co-doped with Y₂Sn₂O₇:Tb³⁺ nanoparticles. Incorporation of Sb³⁺ ions at the Y³⁺ site of Y₂Sn₂O₇ lattice and associated lattice distortion around Tb³⁺/Y³⁺ ions brought about by the difference in the stable coordination number of Sb³⁺ and Y³⁺ ions are responsible for the improved Tb³⁺ emission from the co-doped samples.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.     

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.     

Photoluminescence characteristics of Li-doped CaTiO3:Pr thin films grown on Si (100) substrate by PLD

The effects of Li-doped CaTiO₃:Pr³⁺ thin films have been investigated by varying the lithium ion concentrations from 0 to 5 wt.%. The films have been deposited on Si (100) substrate using a pulsed laser deposition technique. Structural properties of these films have been studied by the measurement of their XRD, SEM, and AFM. The variation of Li⁺ concentration influences the crystallinity and surface morphology of the CaTiO₃:Pr³⁺ thin films. As Li⁺ content increases from 0 to 1 wt.%, the crystallinity and intensity of emission increases. The dominant emission is from ¹D₂ → ³H₄ transition at 613 nm. The ¹D₂ emission quenching has also been observed in highly doped sample and is related to the cross-relaxation process between Pr³⁺ ions.     

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.