Effect of M+2 ions on the luminescence of Pb+2 in NaCl

The effect of additional doping with M⁺² ions on the luminescence of NaCl:Pb⁺² has been systematically investigated. The data show that the same two emissions at 310 and 380 nm are observed for mixed Pb⁺²-M⁺² clusters as for Pb⁺² aggregates. Moreover, the presence of a M⁺² ion associated to a Pb⁺² ion in a mixed cluster shifts the 310 nm emission (predominantly observed for free Pb⁺²-vacancy dipoles) to 380 nm. The results are consistent with the Fukuda's model, involving an emission at 310 nm from tetragonal (T) minima in the adiabatic potential energy surface (APES) and another one from less symmetry (X) minima at 380 nm. The data for NaCl:Pb⁺²:Mn⁺², show that an excitation transfer is taking place from the X minima of the ³T_1u state of Pb⁺² to Mn⁺².     

Infrared and visible spectroscopic studies of the ytterbium doped borate Li6Y(BO3)3

The spectroscopic study of trivalent ytterbium doped Li₆Y(BO₃)₃ is conducted in the UV-visible and infrared range. An excitation in the charge transfer band of ytterbium has been selected in order to reduce the reabsorption effect on the IR emission intensity. The maximum of the emission is located at 972 nm for an excitation at 230 nm. The energy level assignment has been successfully conducted using vibrational spectroscopy to distinguish the pure electronic transitions from the phonon-assisted ones. The splitting of the ²F_5/2 and ²F_7/2 components is equal to 523 cm⁻¹ and 676 cm⁻¹, respectively. The decay time dependence as a function of the concentration is also reported. The calculated value τ_rad is about (1.03 ± 0.01) ms for the 1% doped material. For the highest concentration, an IR excitation gives rise to the observation of a blue-green luminescence caused by two mechanisms: an erbium emission at 550 nm after upconversion and a cooperative luminescence of ytterbium ions.     

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.     

Effect of annealing temperature on luminescence of Eu ions doped nanocrystal zirconia

Effect of annealing temperature on luminescence of Eu³⁺ ions was studied in nanocrystal zirconia prepared by co-precipitation. The XRDs reveal with annealing temperature increasing the tetragonal crystal phase of the samples is stable. The emission spectra show the strong emission at 595 and 604 nm at 394 nm excitation. Under continuous UV (394 nm) irradiation the 604 nm emission intensity changes of the samples show as a function of irradiation time. In addition, the charge-transfer states of the samples are affected by the annealing temperature. These are associated with the defects at/in the surface of the nanocrystalline ZrO₂ with Eu³⁺ ions.     

Investigation of luminescence properties in SiO2: Tb,Yb upconversion inverse opal

The SiO₂: Tb, Yb inverse opals with photonic band gap at 465 or 543 nm were prepared, and an effect of photonic band gap on upconversion spontaneous emission from Tb³⁺ was investigated. The results show that the photonic band gap has a significant influence on the upconversion emission of the SiO₂: Tb, Yb inverse opals. The upconversion luminescence of the Tb³⁺ ions is suppressed in the inverse opal compared with the luminescence of that of the reference sample.     

Near infrared and charge transfer luminescence of Yb-doped LaPO4 at room temperature

The Yb³⁺-doped LaPO₄ was prepared by hydrothermal reaction under fine acidity control and identified by X-ray diffraction and FT-IR spectroscopy. The obtained powders crystallize in the monoclinic phase of LaPO₄. The spectroscopic study at room temperature (RT) of the Yb³⁺-doped LaPO₄ powder was investigated. Thus a wide band, characteristic of the fundamental ²F_5/2↔²F_7/2 transition in near infrared (NIR) range, has been located for La_(1−x)Yb_xPO₄ (x = 5, 10%). Four Stark levels of the ground ²F_7/2 state are located on the emission spectra between 976 nm and 1030 nm, after excitation at 925 nm. Low re-absorption of the 0-phonon transition was registered. Charge transfer band (CTB) luminescence of Yb³⁺, which is not observed in LaPO₄ in later works, was appeared under 266 nm excitation. In the UV–Visible spectra, double band typical for the CTB luminescence of Yb³⁺ are observed. The decay time dependence as a function of the concentration is also reported and compared to other works. The room temperature radiative lifetimes of the IR emission and charge transfer band luminescence are compatible with potential applications of this phosphor respectively as solid-state lasers and scintillators.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.     

Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Luminescence of nanocrystalline ZnS:Cu

Temperature dependent luminescence and luminescence lifetime measurements are reported for nanocrystalline ZnS:Cu²⁺ particles. Based on the variation of the emission wavelength as a function of particle size (between 3.1 and 7.4 nm) and the low quenching temperature (T_q=135 K), the green emission band is assigned to recombination of an electron in a shallow trap and Cu²⁺. The reduction in lifetime of the green emission (from 20 μs at 4 K to 0.5 μs at 300 K) follows the temperature quenching of the emission. In addition to the green luminescence, a red emission band, previously only reported for bulk ZnS:Cu²⁺, is observed. The red emission is assigned to recombination of a deeply trapped electron and Cu²⁺. The lifetime of the red emission is longer (about 40 μs at 4 K) and the quenching temperature is higher.     

Emission characteristics of Dy3+ ions in lead antimony borate glasses

Glasses with the composition 30PbO–25Sb₂O₃–(45?x)B₂O₃–xDy₂O₃ for x=0 to 1 were prepared in steps of 0.2 by the melt-quenching method. Various physical parameters, viz., density, molar volume, and oxygen packing density, were evaluated. Optical absorption and luminescence spectra of all the glasses were recorded at room temperature. From the observed absorption edges optical band gap, the Urbach energies are calculated; the optical band gap is found to decrease with the concentration of Dy₂O₃. The Judd–Ofelt theory was applied to characterize the absorption and luminescence spectra of Dy³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties, like transition probability A, branching ratio β and the radiative life time τ for different emission levels of Dy³⁺ ions, have been evaluated. The radiative lifetime for the ⁴F_9/2 multiplet has also been evaluated from the recorded life time decay curves, and the quantum efficiencies were estimated for all the glasses. The quantum efficiency is found to increase with the concentration of Dy₂O₃.     

Thermo-and photostimulated luminescence of CaI2: Tl and CaI2: Pb crystals

Thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb scintillation crystals under optical and X-ray excitation is studied. It is shown on the basis of the results obtained with account for the data of studies of photo-and X-ray-luminescent properties of these scintillators that Tl⁺ and Pb²⁺ ions form complex capture centers with host defects. These centers are responsible for the thermostimulated luminescence in the temperature range of 150–295 K, and the centers of charge carrier trapping are spatially separated from the centers of recombination emission. An assumption is made that thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb crystals under optical excitation is observed mainly due to the delocalization of charge carriers from hydrogen-containing centers responsible for the excitation band at 236 nm and the photoluminescence of CaI₂ with a maximum at 395 nm. The luminescence of CaI₂: Tl crystals in the 510-nm band and CaI₂: Pb crystals in the 530-nm band is determined by the radiative decay of near-activator excitons.     

Temperature dependent single photon emission in InP/GaInP quantum dots

Intensity correlation measurements on single InP/GaInP quantum dots (QDs) show antibunching at zero delay time, indicative of single photon emission. The antibunching time τ_R increases or decreases with temperature depending on the QD size as a result of the competition between: (1) thermal excitation of holes dominant in smaller QDs and (2) dark-to-bright exciton transition dominant in larger QDs. The antibunching minimum g⁽²⁾(0) remains below 0.2 up to 45 K.     

Luminescence of neodymium-doped yttria

Pulsed cathodoluminescence of Nd³⁺: Y₂O₃ nanopowders of the cubic and monoclinic phases and the ceramics synthesized from these nanopowders has been investigated in the spectral range 350–850 nm. It is found that the IR emission band of neodymium ions in the Nd³⁺: Y₂O₃ cubic phase is located at λ₁ ≈ 825 nm. When there is a monoclinic phase admixture, two additional luminescence bands of Nd³⁺ arise in the spectrum at λ₂ ≈ 750 nm and λ₃ ≈ 720 nm. The emission spectrum of all Nd³⁺: Y₂O₃ materials also contains a wide intrinsic band of yttrium oxide at λ ≈ 485 nm; however, the presence of neodymium decreases the intensity of this band and increases the its structurization. It is suggested that the structure of this band in Nd³⁺: Y₂O₃ materials is mainly determined by local absorption (self-absorption) of neodymium ions.     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

Optimization red emission of SrMoO4: Eu3+ via hydro-thermal co-precipitation synthesis using orthogonal experiment

In the present study, the SrMoO₄:Eu³⁺ phosphors has been synthesized through hydro-thermal co-precipitation method, and single factor and orthogonal experiment method was adopted to find optimal synthesis condition. It is interesting to note that hydro-thermal temperature is a prominent effect on the luminescent intensity of SrMoO₄:Eu³⁺ red phosphor, followed by co-precipitation temperature, calcining time, and the doping amount of Eu³⁺. The optimal synthesis conditions were obtained: hydro-thermal temperature is 145 °C, co-precipitation temperature is 35 °C, the calcining time is 2.5 h, and the doping amount of activator Eu³⁺ is 25%. Subsequently, the crystalline particle size, phase composition and morphology of the synthesized phosphors were evaluated by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results show that these phosphors possess a scheelite-type tetragonal structure, and the particle size is about 0.2 μm. Spectroscopic investigations of the synthesized phosphors are carried out with the help of photo-luminescence excitation and emission analysis. The studies reveal that SrMoO₄: Eu³⁺ phosphor efficiently convert radiation of 394 nm–592 and 616 nm for red light, and the luminescence intensity of SrMoO₄:Eu³⁺ phosphors is improved. SrMoO₄:Eu³⁺ phosphors may be a potential application for enhancing the efficiency of white LEDs.     

A red oxide phosphor, Sr2ScAlO5:Eu2+ with perovskite-type structure, for white light-emitting diodes

Sr2ScAlO5:Eu2+,a red oxide phosphor with a perovskite-type structure,has been synthesized through a solid-state reaction and its luminescence properties have been investigated.An absorption band centering at 450 nm is observed from the diffuse reflection spectra and the excitation spectra,indicating that the phosphor can match perfectly with the blue light of InGaN light-emitting diodes.A broad red emission band at 620 nm is found from the emission spectra,originating from the 4f 6 5d-4f 7 transition of the Eu 2+ ions.The best doping content of Eu in this material is about 5%.Sr2ScAlO5:Eu2+is a highly promising red phosphor for use in white light-emitting diodes.     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

Luminescence spectroscopy of Ti ions in Li2O-CaF2-P2O5 glass ceramics

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of TiO₂ (ranging from 0 to 0.8 mol%) were crystallized at 500 °C. The photo luminescence spectra of these samples excited with the wavelengths corresponding to their absorption edges have been recorded at room temperature. The spectra exhibited an emission band in the wavelength region 470-500 nm. The emission band is identified due to the charge transfer from O²⁻ ion in to empty 3d orbital of octahedrally positioned Ti⁴⁺ ions. The analysis of the results further indicates the highest luminescence efficiency for the glass ceramic sample crystallized with 0.6 mol% of TiO₂.     

Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.