Photoluminescence studies of γ-irradiated CaF2:Dy:Pb:Na single crystals

The optical absorption (OA) and photoluminescence (hereafter referred to as luminescence) studies were made on CaF₂:Dy:Pb:Na single crystals (Dy—0.005 at%, Pb—0.188 at% and Na—0.007 at%) before and after γ-irradiation. The unirradiated crystal exhibited a strong OA band around 6.36 eV attributed to the ‘A’ band absorption of Pb²⁺ ions. The γ-irradiated crystal exhibited OA bands around 2.06, 3.28, 3.75 (broad shoulder) and 2.48 eV. The first three bands could be tentatively attributed to M_Na centre when compared with that of the coloured CaF₂:Na. The origin of 2.48 eV band was not explicitly known. Luminescence emission and excitation of Pb²⁺ and Dy³⁺ ions were negligible in the unirradiated crystal. Irradiated crystal exhibited a strong excitation spectrum with overlapping bands, due to different colour centres, in the UV-vis region for the 2.15 eV emission characteristic of Dy³⁺ ion. When excited, the absorbed energy (may be a part) was transferred from a colour centre to nearby Dy³⁺ ions and Dy³⁺ characteristic emission was observed. Exciting the irradiated crystal around 3.28 eV yielded emission at 2.56, 2.15 and 1.76 eV. The first two emission bands were due to Dy³⁺ ions. The excitation spectrum for the 1.76 eV emission showed two prominent bands around 2.02 and 3.08 eV and hence the emission was attributed to the M_Na centre. The luminescence mechanism was described.     

Stimulated self-trapped exciton emission in CsI:Pb

Defects of the type of V_K and Pb⁺ centres were created in CsI:Pb under the 4.03 eV XeCl laser line irradiation at 10 K. After irradiation, the self-trapped and localized exciton emission excited by the same XeCl laser line was observed as a result of the recombination of electrons, optically released from Pb⁺, with the V_K centres. A strongly superlinear dependence of the emission intensity on the excitation intensity was found for the 3.65 eV emission of the self-trapped exciton. A much weaker superlinearity was observed for the visible localized exciton emission. Optical amplification of the exciton emission was considered as the most probable reason of the observed phenomenon. At 10 K, optical gain G=3.74 was calculated for the self-trapped exciton emission.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Luminescence spectroscopy of the Bi single and dimer centers in Y3Al5O12:Bi single crystalline films

Luminescence of the Bi³⁺ single and dimer centers in UV and visible ranges is studied in YAG:Bi (0.13 and 0.27 at% of Bi, respectively) single crystalline films (SCFs), grown by liquid phase epitaxy from a Bi₂O₃ flux. The cathodoluminescence spectra, photoluminescence decays, and time-resolved spectra are measured under the excitation by accelerated electrons and synchrotron radiation with energies of 3.7 and 12 eV, respectively. The energy level structure of the Bi³⁺ single and dimer centers was determined. The UV luminescence of YAG:Bi SCF in the bands that peaked at 4.045 and 3.995 eV at 300 K is caused by radiative transitions of Bi³⁺ single and dimer centers, respectively. The excitation spectra of UV luminescence of Bi³⁺ single and dimer centers consist of two dominant bands, peaked at 4.7/4.315 and 5.7/6.15 eV, related to the ¹S₀→³P₁ (A band) and ¹S₀→ ¹P₁ (C-band) transitions of Bi³⁺ ions, respectively. The excitation bands that peaked at 7.0 and 7.09 eV are ascribed to excitons bound with the Bi³⁺ single and dimer centers, respectively. The visible luminescence of YAG:Bi SCF presents superposition of several wide emission bands peaking within the 3.125-2.57 eV range and is ascribed to different types of excitons localized around the Bi³⁺ single and dimer centers. Apart from the above mentioned A and C bands the excitation spectra of visible luminescence contain wide bands at 5.25, 5.93, and 6.85 eV ascribed to the O²⁻→Bi³⁺ and Bi³⁺→Bi⁴⁺ + e charge transfer transition (CTT) in Bi³⁺ single and dimer centers. The observed significant differences in the decay kinetics of visible luminescence under excitation in A and C bands of Bi³⁺ ions, CTT bands, and in the exciton and interband transitions confirm the radiative decay of different types of excitons localized around Bi³⁺ ions in the single and dimer centers.     

Short-living absorption and emission of CsI(Na)

This paper investigates the short-living absorption and the emission of CsI(Na) under a pulsed electron beam (Е_e=0.25 MeV, t_1/2=15 ns and W=0.003…0.16 J/cm²). The bands of singlet self-trapped excitons, as well as Na⁰ and V_k color centers have been detected in the transient absorption spectrum of CsI(Na). It has been found that the activator luminescence spectrum, peaking at 3.0 eV, fits a Gaussian (E_m=3.0 eV and FWHM=0.44±0.02 eV at 80 K) and remains the same at different time delays within 10⁻⁸-10⁻³ s. The decay kinetics of the 3.0 eV emission has one nanosecond exponential component and two microsecond ones with time constants 1.0 and 3.0 μs, which remain unchanged within 78-150 K. It is concluded that the activator emission is due to the radiative annihilation of sodium-perturbed two halide excitons from the non-relaxed singlet state. The pathways of such excitons creation are discussed.     

Emerging blue‐UV luminescence in cerium doped YAG nanocrystals

Time‐resolved luminescence properties of Ce³⁺ doped Y₃Al₅O₁₂ (YAG) nanocrystals have been studied by means of vacuum‐ultraviolet excitation spectroscopy. It was discovered that additionally to the regular Ce³⁺ yellow‐green emission which is well‐known luminescence in YAG, new emission covering a broad spectral range from 2.7 eV to 3.5 eV was revealed in the luminescence spectra for all YAG:Ce nanocrystals studied. This blue‐UV emission has fast decay time about 7 ns as well as intensive well‐resolved excitation band peaking at 5.9 eV and, in contrast to green Ce³⁺ emission, practically is not excited at higher energies. The origin of the blue‐UV emission is tentatively suggested and discussed. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.     

Photoluminescence and excited state structure in Bi3+-doped Y2SiO5 single crystalline films

Single crystalline films of Bi-doped Y₂SiO₅ are studied at 4.2–350 K by the time-resolved luminescence methods under excitation in the 3.8–6.2 eV energy range. Ultraviolet luminescence of Y₂SiO₅:Bi (≈3.6 eV) is shown to arise from the radiative decay of the metastable and radiative minima of the triplet relaxed excited state (RES) of Bi³⁺ centers which are related to the ³P₀ and ³P₁ levels of a free Bi³⁺ ion, respectively. The lowest-energy excitation band of this emission, located at ≈4.5 eV, is assigned to the ¹S₀ → ³P₁ transitions of a free Bi³⁺ ion. The phenomenological model is proposed to describe the excited-state dynamics of Bi³⁺ centers in Y₂SiO₅:Bi, and parameters of the triplet RES are determined.     

Luminescence and energy transfer processes in Lu2SiO5:Ce scintillator

The energy transfer processes in Lu₂SiO₅:Ce³⁺ luminescence was investigated through the temperature dependent luminescence under excitation with VUV-UV. Ce1 center emission peaking at 393 and 422 nm and Ce2 center emission peaking at 462 nm were observed. Ce2 center emission is enhanced with the temperature, which can be explained by the rate of energy transfer from Ce1 center increases when the temperature rises. The Ce1 emission shows the thermal quenching effect under the direct excitation of Ce³⁺ at 262 nm. However, under the interband excitation of 183 nm, the Ce1 center emission exhibits undulating temperature dependence. This is because the emission is governed by thermal quenching and possible thermal enhancement of the transport of free carriers with the rising temperature.     

Effect of ZnO as modifier on up and downconversion properties of Ho/Yb doped tellurite glasses

Optical absorption and photoluminescent properties of Ho³⁺/Yb³⁺ co-doped tellurite and zinc tellurite glasses are investigated. The effect of zinc oxide as a modifier on the luminescence properties of above mentioned samples has been explored. Two intense upconversion emission bands centered at 546 (⁵F₄ + ⁵S₂ → ⁵I₈) and 660 nm (⁵F₅ → ⁵I₈) are observed on excitation with 976 nm diode laser. Zinc oxide acts as a quencher for 976 nm excited upconversion emission. The up and downconversion emission spectra are recorded with 532 nm excitation source also. In this case zinc oxide improves the up and downconversion emissions. A large enhancement in upconversion intensity has been observed when Ho³⁺ ion is co-doped with Yb³⁺ ion. The dependence of upconversion intensities on excitation power and on temperature has also been studied. The power dependence study shows a quadratic dependence of the fluorescence intensity on the excitation power while a decrement in emission intensity of all the transitions at different rates with increase in temperature is observed in temperature dependence study. The possible mechanisms are also discussed in order to understand the upconversion and energy transfer processes.     

Luminescence spectra of lead-doped NaCl,KCl and KBr

The luminescence spectra of lead-doped NaCl, KCl and KBr have been systematically investigated. Special attention has been paid to the effects of concentration and thermal history of the crystals. In the three systems, the emission spectra for A and C band excitation consists mainly of two well-defined emission bands whose energy separation is ～0.7 eV. It has been concluded that none of the bands can be attributed to a single type of lead center but are both typical of Pb²⁺ luminescence. In fact, their behavior can be correlated with that found for most monovalent ions and interpreted in a similar way. The excitation spectra for the two emissions have shown that the A-band is complex. One of the components appearing in very low doped and quenched samples is ascribed to dipoles, whereas additional side bands are attributed to complexes or small aggregates involving Pb²⁺ ions.     

TL and PL studies on defect-assisted green luminescence from doped strontium sulfide phosphor

Defect-assisted luminescence of Pr³⁺-doped SrS has been investigated and reported in this paper. The polycrystalline sample of phosphor was prepared by conventional solid-state reaction method and checked for crystallization and phase by X-ray diffraction study. The thermally stimulated luminescence studies of the phosphor samples with various activator concentrations, irradiated by a blacklight source, are conducted and show a broad single peak around 365-382 K. Computerized glow curve deconvolution tool is used to evaluate the effective trapping parameters and suggests quasi-continuous distribution of traps in the range of 0.5−0.9 eV. A critical survey on the application of first-order kinetics in the present phosphor is undertaken. Photoluminescence studies reveal three excitation bands at 287, 314, 355 nm and defect-related emission at 517, 494 nm for two concentrations of activator atoms in the present phosphor. The 314-355 nm broad excitation bands correspond to a charge transfer transition of Pr³⁺-S²⁻.     

Emission and decay time studies on Pb2+ centers in KBr,RbBr, and RbCl

The emission spectra and the luminescence decay times of KBr, RbBr, and RbCl crystals doped with Pb²⁺ and excited in the A-absorption band have been studied in the temperature range 5–300 K. The emission-lineshape spectra have been analysed in terms of skew-Gaussian bands. New bands have been observed in RbCl and RbBr at very low temperatures. While the luminescence decay of KBr:Pb²⁺ and RbBr:Pb²⁺ show only a single component with a decay time τ ～ 20 ns, RbCl:Pb²⁺ shows a short and a long component. The reason for the missing long component in KBr:Pb²⁺ and RbBr:Pb²⁺ is tentatively attributed to an anomaly in the structure of the adiabatic potential energy surface (APES) of the excited states.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

Luminescence channels of manganese-doped spinel

Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl₂O₄. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state ⁴T₁ to the ground state ⁶A₁ of Mn²⁺ (3d)⁵ ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion.     

Studies on the origins of the absorption spectra in PbWO4 crystal

The electronic structures and absorption spectra for both the perfect PbWO₄ (PWO) crystal and the three types of PWO crystals, containing V_Pb²⁻, V_O²⁺ and a pair of V_Pb²⁻-V_O²⁺, respectively, have been calculated using CASTEP codes with the lattice structure optimized. The calculated absorption spectra indicate that the perfect PWO crystal does not occur absorption band in the visible and near-ultraviolet region. The absorption spectra of the PWO crystal containing V_Pb²⁻ exhibit seven peaks located at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), respectively. The absorption spectra of the PWO crystal containing V_O²⁺ occur two peaks located at 370 nm and 420 nm. The PWO crystal containing a pair of V_Pb²⁻-V_O²⁺ does not occur absorption band in the visible and near-ultraviolet region. This leads to the conclusions that the 370 and 420 nm absorption bands are related to the existence of both V_Pb²⁻ and V_O²⁺ in the PWO crystal and the other absorption bands are related to the existence of the V_Pb²⁻ in the PWO crystal. The existence of the pair of V_Pb²⁻-V_O²⁺ has no visible effects on the optical properties. The calculated polarized optical properties are well consistent with the experimental results.     

ESR and optical spectroscopy of copper-doped PLZT electro-optic ceramics

2+ spectra in axial and cubic crystal fields. Cu²⁺ substitutes for Ti⁴⁺ and the excess charge can be compensated by La³⁺ on a nearest-neighbor site, thus creating axial symmetry. The centers of cubic symmetry are those where the charge is compensated in distant spheres. In contrast to pure PLZT, PLZT:Cu exhibits a new luminescence band peaking at 1.18 eV. This emission is ascribed to the ²T₂(D)→²E(D) transition of Cu²⁺(3d⁹) which can be excited either in the resonant 1.87 eV band or via charge-transfer excitation bands at 2.40, 2.57, and 3.03 eV. The absorption band at 1.45 eV is assumed to be that of Cu⁺ ions. Annealing in hydrogen and in oxygen atmospheres caused decrease and restoration, respectively, of the ESR and luminescence intensities as a consequence of Cu²⁺ conversion into Cu¹⁺ and vice versa. Received: 14 November 1997/Accepted: 8 December 1997     

Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

Luminescence and defects creation under photoexcitation of CsI : Tl crystals in Tl-related absorption bands

Characteristics of the defects created at 4.2 K by the UV-irradiation of CsI : Tl crystals in the Tl⁺-related absorption bands (by photons of 5.8-4.8 eV energy) have been studied. The dependences of the intensities of the thermally stimulated luminescence peaks appearing near 60, 90 and 125 K and of the recombination luminescence photostimulation bands peaking at 2.35, 1.92, 1.33 and 0.89 eV on the irradiation energy and duration, uniaxial stress and thallium concentration have been examined. The mechanisms of the processes, responsible for the appearance of the intense visible (2.55 and 2.25 eV) luminescence of excitons localized near Tl⁺ ions and creation of defects pairs of the type of Tl⁰-V_K and Tl⁺-V_K with various distances between the components, have been discussed.     

Effect of Ca and Sr alkaline earth ions on luminescence properties of BaAl12O19:Eu nanophosphor

Nanosized barium aluminate materials was doped by divalent cations (Ca²⁺, Sr²⁺) and Eu²⁺ having nominal compositions Ba_1−xMxAl₁₂O₁₉:Eu (M=Ca and Sr) (x=0.1-0.5), were synthesized by the combustion method. These phosphors were characterized by XRD, scanning electron microscopy-energy-dispersive spectrometry (SEM-EDS) and photoluminescence measurement. The photoluminescence characterization showed the presence of Eu ion in divalent form which gave emission bands peaking at 444 nm for the 320 nm excitation (solid-state lighting excitation), while for 254 nm it gave the same emission wavelength of low intensity (1.5 times) compared to 320 nm excitation. It was also observed that alkaline earth metal (Ca²⁺ and Sr²⁺) dopants increase the intensity of Eu²⁺ ion in BaAl₁₂O₁₉ lattice, thus this phosphor may be useful for solid-state lighting.