Pr3+ luminescence center in Lu2Si2O7 host

Pr³⁺‐doped Lu₂Si₂O₇ (LPS:Pr) microcrystalline phosphor was prepared by the sol–gel method. We study the LPS:Pr luminescence properties under UV and X‐ray excitation within 80–500 K. The emission spectrum is dominated by fast 5d–4f band peaking at 261 nm having 16 ns decay time. By purely optical contactless methods we determine the energy barrier of 300 meV for thermal ionization of the Pr³⁺ 5d₁ relaxed excited state in LPS host. The barrier is high enough to keep the room temperature quantum efficiency of the Pr³⁺ luminescence center close to unity. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Site selective 4f5d spectroscopy of CaF2 : Pr

Spectroscopic investigations were performed on a single crystal of CaF₂ doped with 0.05% Pr³⁺. Three different Pr³⁺ sites with different luminescent properties were identified. The 4f² →4f¹5d¹ excitation spectrum of the first site has a sharp maximum at 221.3 nm. Excitation in the 4f5d bands of this site yields strong 4f5d emissions in the UV/VIS part of the spectrum and also weaker intraconfigurational 4f² emissions. By comparing the intraconfigurational 4f emissions and their decay times with data from the literature, these 4f5d bands are assigned to transitions on Pr³⁺ ions on a site with C_4V symmetry. The fd excitation spectrum of the second site has a zero phonon line at 223.3 nm. Upon selective excitation in this band, only 4f5d emission is observed. Probably, these 4f5d bands correspond to Pr³⁺ ions on a O_h site. The third set of 4f5d bands has a 4f5d onset at 208 nm. By comparison of the luminescence spectra of the intraconfigurational 4f² transitions with literature data, these transitions are assigned to Pr³⁺ on an L site. Excitation in these 4f5d band yields ¹S₀ emission followed by emission from the ³P₀ state. The present results clarify some contradictions reported in the literature.     

Orange emissive Sr3Al2O5Cl2:Eu2+ phosphor for warm-white light-emitting diodes

Orange-emitting Sr₃Al₂O₅Cl₂:Eu²⁺ phosphors were synthesized by a high-temperature solid-state reaction. The excitation spectrum shows a broad band from the UV region to the blue region. The emission spectrum shows strong orange emission peaking at 610 nm, attributed to the d–f transition of the Eu²⁺ ion. By combining the Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor with 420 nm and 460 nm chips, three white light-emitting diodes (LEDs) were fabricated. The warm-white LEDs show color rendering indexes of 76, 66 and 90 with color temperatures of 2447, 3546 and 4300 K, respectively. This new phosphor exhibits the potential to act as a single host doped with Eu²⁺ phosphor for UV or blue chip excited white LEDs.     

Preparation,luminescence and structural properties of rare‐earth‐doped RbLuS2 compounds

Rare‐earth (RE = Ce, Pr, Sm, Tb) doped ternary sulfides of the general formula RbLu_0.99RE_0.01S₂ and undoped RbLuS₂ were synthesized in the form of crystalline hexagonal platelets by chemical reaction in the electric resistance furnace under the flow of hydrogen sulfide. Only a single crystalline phase of the rhombohedral lattice system (space group $ {\rm R}\bar 3{\rm m}) $ was detected by X‐ray powder diffraction. Absorption and luminescence characteristics were measured. The band edge of RbLuS₂ is found at 310 nm, and characteristic Pr³⁺, Sm³⁺ and Tb³⁺ 4f–4f emission lines in the visible spectral range are observed. A charge transfer transition in the Pr³⁺ excitation spectrum in the near UV spectral region is revealed and an efficient energy transfer from the host to the emission centers is found. The application potential for white LED or X‐ray phosphors is discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of fast-decaying bluish green phosphors of Tb3+-doped CaSi2O2N2 for 2D/3D plasma display panels

Oxynitride phosphor powders comprising of CaSi₂O₂N₂ doped with Tb³⁺ were successfully synthesized using a high-temperature solid-state reaction method. The experimentally determined photoluminescence (PL) properties of the produced phosphors meet the requirements of 2D/3D plasma display panels (PDPs). In particular, under the excitation of vacuum ultraviolet (VUV) synchrotron radiation and ultraviolet (UV) irradiation, emission peaks corresponding to the ⁵D₃→⁷F_J (J=6, 5, 4, 3) and ⁵D₄→⁷F_J (J=6, 5, 4, 3) transitions of Tb³⁺ ions were recorded. Monitoring the ⁵D₄→⁷F₅ emission of Tb³⁺ at 545 nm, the excitation bands were assigned to the host-related absorption as well as the 4f–5d (fd) and the 4f–4f (ff) transitions of Tb³⁺. The produced phosphors can be efficiently excited at 147 nm, and have an adequately short decay time (τ_1/10=1.14 ms).     

Line emission of SrBe2Si2O7:Eu2+ and BaBe2Si2O7:Eu2+

The compounds SrBe₂Si₂O₇ and BaBe₂Si₂O₇ both have the barylite structure. With 254 nm excitation, the Eu²⁺-activated compounds give UV emission peaking at 360 nm (Sr) and at 375 nm (Ba). Maximum quantum efficiencies of 40% (Sr) and 65% (Ba) were measured. The emission consists of a 5d-4f band emission as well as 4f-4f line emission, in contrast to many other Eu²⁺-activated oxides which generally show only 5d-4f band emission. At 77°K, both compounds show only the 4f-4f line emission peaking at 360 nm. At higher temperatures, 5d-4f band emission shows up at the cost of the line emission. A thermal equilibrium is assumed between the lowest excited 5d and 4f levels. The energy difference between these levels, calculated from the variation in the line-band intensity ratio with temperature, was computed to be 0.15 eV (Sr) and 0.09 eV (Ba). The occurrence of the line emission in the barylites is correlated with the weakness of the crystal field at the Eu²⁺ ions and with the high quenching temperature of the 5d-4f band emission.     

Enhance luminescence by introducing alkali metal ions (R+ = Li+, Na+ and K+) in SrAl2O4:Eu3+ phosphor by solid-state reaction method

In the present article, the role of charge compensator ions (R⁺?=?Li⁺, Na⁺ and K⁺) in europium-doped strontium aluminate (SrAl₂O₄:Eu³⁺) phosphors was synthesized by the high-temperature, solid-state reaction method. The crystal structures of sintered phosphors were in a monoclinic phase with space group P2₁. The trap parameters which are mainly activation energy (E), frequency factor (s) and order of the kinetics (b) were evaluated by using the peak shape method. The calculated trap depths are in the range from 0.76 to 0.84?eV. Photoluminescence measurements showed that the phosphor exhibited emission peak with good intensity at 595?nm, corresponding to ⁵D₀–⁷F₁ (514?nm) orange emission and weak ⁵D₀–⁷F₂ (614?nm) red emission. The excitation spectra monitored at 595?nm show a broad band from 220 to 320?nm ascribed to O–Eu charge-transfer state transition and the other peaks in the range of 350–500?nm originated from f–f transitions of Eu³⁺ ions. The strongest band at 394?nm can be assigned to ⁷F₀–⁵L₆ transition of Eu³⁺ ions due to the typical f–f transitions within Eu³⁺ of 4f⁶ configuration. The latter lies in near ultraviolet (350–500?nm) emission of UV LED. CIE color chromaticity diagram and thermoluminescence spectra confirm that the synthesized phosphors would emit an orange-red color. Incorporating R⁺?=?Li⁺, Na⁺ and K⁺ as the compensator charge, the emission intensity of SrAl₂O₄:Eu³⁺ phosphor can be obviously enhanced and the emission intensity of SrAl₂O₄:Eu³⁺ doping Li⁺ is higher than that of Na⁺ or K⁺ ions.     

Luminescence spectroscopy of Ce3+-doped ABaPO4 (A=Li, Na, K) phosphors

Ce³⁺ doped ABaPO₄ (A=Li, Na, K) phosphors were prepared by conventional high temperature solid-state reaction. The phosphors were investigated by XRD, photoluminescence excitation and emission spectra, and luminescence decay curves. The five 5d levels corresponding to the 4f¹→4f⁰5d¹ transition of Ce³⁺ ions were identified. The spectroscopic parameters, e.g., the 5d barycenter, the crystal-field splitting, and the Stokes shift, were discussed. LiBaPO₄:Ce³⁺ phosphor could be efficiently excited by the near-UV lights (330–420 nm) and showed a broad emission band in the range of 430–620 nm with the maximum wavelength at 468 nm. In contrast, Ce³⁺-doped NaBaPO₄ and KBaPO₄ showed only excitation bands in a limited UV region (230–370 nm) and have blue emission at 385 nm and 416 nm, respectively. The temperature quenching of luminescence and the chromaticity coordinates were reported. The luminescence properties were discussed by analyzing the crystal structure and the local surroundings of Ce³⁺ ions on the Ba²⁺ sites.     

Nd-doped Lu3Al5O12 single-crystal scintillator for X-ray imaging

The optical and scintillation properties of Nd-doped Lu₃Al₅O₁₂ (Nd:LuAG) crystals grown by the Czochralski (Cz) method were examined under X-ray excitation. Their applicability for X-ray imaging was also inspected. The radioluminescence spectrum induced by X-rays showed a broad host emission and sharp Nd³⁺ 4f–4f emission peaks in the UV to visible wavelengths. The light output current of the Nd:LuAG was 85% of that of a standard CdWO₄ X-ray scintillator. The afterglow value measured 20 ms after X-ray irradiation was 1.5%. An X-ray radiographic image was successfully obtained using the Nd:LuAG scintillator coupled with the charge coupled device (CCD) photodetector.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

Judd–Ofelt analysis and upconversion emission of Er3+–Yb3+ co-doped oxyfluoride glass ceramics containing LaF3 nanocrystals

Er³⁺–Yb³⁺ co-doped glasses and glass ceramics containing LaF₃ nanocrystals were prepared and their absorption spectra obtained. The Judd–Ofelt parameters Ω _t (t?=?2,?4,?6) for f–f transition of Er³⁺, as well as spontaneous emission probabilities, branching ratios and radiative lifetimes for stimulated emission of each band were determined. Addition of Er³⁺ and Yb³⁺ ions into low-phonon energy LaF₃ nanocrystals makes the upconversion emission of Er³⁺–Yb³⁺ co-doped glass ceramic much stronger than that of Er³⁺–Yb³⁺ co-doped glass.     

VUV-UV-visible luminescence of Nd3+, Er3+ and Tm3+ in LiLuF4 single crystal host

An overlook of absorption and luminescence characteristics of Nd³⁺, Er³⁺ and Tm³⁺ centers in LiLuF₄ single crystal is provided. Single crystal doped with the mentioned RE ions were prepared by micro-pulling-down technique in the form of few cm long rods with the diameter of about 2 mm. Excitation and emission spectra and fast decay kinetics in VUV spectral region were measured at SUPERLUMI station at synchrotron DESY, Hamburg and characterization was further completed in UV-visible region at conventional spectrophotometers. Observed absorption and emission peaks are ascribed to the 5d–4f and 4f–4f optical transitions in the doped rare earth ions. Concentration dependence of the decay kinetics is discussed.     

Excitation and Emission Spectra of Cs2NaLnCl6 Crystals Using Synchrotron Radiation

ABSTRACT

The visible emission and vacuum ultraviolet excitation spectra of the series Cs₂NaLnCl₆ (Ln = Y, Nd, Sm, Eu, Tb, Er, Yb) and Cs₂NaYCl₆:Ln³⁺ (Ln = Sm, Er) have been recorded using synchrotron radiation at room temperature, and in some cases at 10 K. The excitation spectra comprise features associated with charge transfer, excitation from the valence to conduction band, and impurity bands. No d–f emissions were observed for these Ln³⁺ ions, so that the emission bands comprise intraconfigurational 4f ^N –4f ^N transitions and impurity bands, whose natures are discussed. Theoretical simulations of the f–d absorption spectra have been included. The comparison with data from the synchrotron at Desy enables a comprehensive account of the ground (or vibrationally excited ground for Ln²⁺) states of the Ln³⁺ 4f ^N , Ln³⁺ 4f ^N?15d, and Ln²⁺ 4f ^N+1 configurations relative to the valence and conduction bands of Cs₂NaLnCl₆, for which the band gaps are between 6.6 and 8.1 eV.     

Luminescence properties and energy transfer investigations of BaAl2B2O7:Ce3+,Tb3+ phosphors

Ce³⁺ and Tb³⁺ co-doped BaAl₂B₂O₇ phosphors were synthesized by the solid-state method. X-ray diffraction (XRD) was used to characterize the phase structure. The photoluminescent properties of Ce³⁺ and Tb³⁺ co-doped BaAl₂B₂O₇ phosphors were investigated by using the photoluminescence emission and excitation spectra. Under the excitation of near ultraviolet (n-UV) light, BaAl₂B₂O₇:Ce³⁺,Tb³⁺ phosphors exhibited blue emission corresponding to the f–d transition of Ce³⁺ ions and green emission bands corresponding to the f–f transition of Tb³⁺ ions, respectively. Effective energy transfer occurred from Ce³⁺ to Tb³⁺ in BaAl₂B₂O₇ host due to the observed spectra overlap between the emission spectrum of Ce³⁺ ion and the excitation spectrum of Tb³⁺ ion. The energy transfer efficiency from Ce³⁺ ion to Tb³⁺ ion was also calculated to be 71%. Furthermore, the concentration quenching and critical distance of BaAl₂B₂O₇:Ce³⁺,Tb³⁺ phosphors were also discussed. The energy transfer from Ce³⁺ to Tb³⁺ in BaAl₂B₂O₇ host was demonstrated to be resonant type via a dipole–dipole interaction mechanism with the energy transfer critical distance of 16.13 Å.     

Characterization of Micro‐ and Nanoscale LuPO4:Pr3+,Nd3+ with Strong UV‐C Emission to Reduce X‐Ray Doses in Radiation Therapy

UV‐C emitting nanoscale scintillators can be used to sensitize cancer cells selectively against X‐rays during radiation therapy, due to the lethal DNA lesions caused by UV‐C photons. Unfortunately, nanoscale particles (NPs) show decreased UV‐C emission intensity. In this paper, the influence of different Nd³⁺ concentrations on the UV‐C emission of micro‐ and nanoscale LuPO₄:Pr³⁺ is investigated upon X‐ray irradiation and vacuum UV excitation (160 nm). Co‐doped LuPO₄ results in increased UV‐C emission independent of excitation source due to energy transfer from Nd³⁺ to Pr³⁺. The highest UV‐C emission intensity is observed for LuPO₄:Pr³⁺,Nd³⁺(1%,2.5%) upon X‐ray irradiation. Finally, LuPO₄ NPs co‐doped with different dopant concentrations are synthesized, and the biological efficacy of the combined approach (X‐rays and UV‐C) is assessed using the colony formation assay. Cell culture experiments confirm increased cell death compared to X‐rays alone due to the formation of UV‐specific DNA damages, supporting the feasibility of this approach.     

Investigation of crystal/electronic structure effects on the photoluminescence properties in the BaO–SiO2:Eu2+ systems

BaO–SiO₂:Eu²⁺ phosphors with different Ba/Si mole ratio were prepared using a solid-state reaction method, and their crystal structure dependent-photoluminescence properties were investigated. The prepared phosphor powders were characterized using X-ray diffraction (XRD), field-emission electron microscopy (FE-SEM) and fluorescence spectroscopy. The emission band of the Eu²⁺ activator varied from orange to blue with varying crystal structure of the host materials, which was related to the crystal field splitting of the Eu 5d orbitals. These emission color changes were examined by calculating the electronic band structure properties such as the density of the state. Moreover, the host material with Ba/Si=1 (BaSiO₃) for Eu²⁺, which exhibited a yellow emission when excited with near UV light, was further characterized for enhancing its emission intensity.     

Yellow-orange light emission from Mn2+-doped ZnS nanoparticles

ZnS nanoparticles with Mn²⁺ doping (1–2.5%) have been prepared through a simple soft chemical route, namely the chemical precipitation method. The nanostructures of the prepared undoped ZnS and Mn²⁺-doped ZnS:Mn nanoparticles have been analyzed using X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–vis spectrophotometer. The size of the particles is found to be in 2–3 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample only exhibits a blue-light emission peaked at ∼365 nm under UV excitation. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn^{2+ 4}T₁–⁶A₁ transition is observed along with the blue emission. The prepared 2.5% Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission at ∼580 nm with the blue emission suppressed.     

Interplay of spin-allowed and spin-forbidden 5d–4f luminescence from rare earth ions

The conditions for co-existence of emissions from spin-allowed and spin-forbidden 5d–4f transitions in rare earth ions and for thermal quenching of these emissions have been analyzed by taking Tm³⁺ 5d–4f luminescence in LiYF₄:Tm³⁺ and Lu³⁺ 5d–4f luminescence in LuF₃ as examples. It is shown that temperature behavior of 5d–4f luminescence agrees with the common trends in decreasing energy splitting between the lowest high-spin and low-spin 5d levels as well as decreasing energy gap between the lowest 5d level and the bottom of the conduction band of the host crystal towards heavier rare earth ions (from Er³⁺ to Lu³⁺).     

Photoluminescence properties of blue-emitting Li4SrCa(SiO4)2:Eu2+ phosphor for solid-state lighting

Blue-emitting Li₄SrCa(SiO₄)₂:Eu²⁺ phosphors have been synthesized by solid-state reaction. The photoluminescence (PL) excitation spectrum shows broad-band absorption and matches well with the emission of a near-UV (n-UV) chip. The PL emission spectrum exhibits a broad-band emission peaking at 430 nm, which is the characteristic emission of the f–d transition of the Eu²⁺ ion. The diffuse reflection spectra, temperature-dependent emission spectra, fluorescence decay, and mechanism of concentration quenching are also studied in detail. Li₄SrCa(SiO₄)₂:Eu²⁺ is a candidate blue phosphor for n-UV excited solid-state lighting.     

Effect of composition on the spontaneous emission probabilities, stimulated emission cross-sections and local environment of Tm in TeO2-WO3 glass

Effect of composition on the structure, spontaneous and stimulated emission probabilities of various 1.0 mol% Tm₂O₃ doped (1−x)TeO₂+(x)WO₃ glasses were investigated using Raman spectroscopy, ultraviolet-visible-near-infrared (UV/VIS/NIR) absorption and luminescence measurements.Absorption measurements in the UV/VIS/NIR region were used to determine spontaneous emission probabilities for the 4f-4f transitions of Tm³⁺ ions. Six absorption bands corresponding to the absorption of the ¹G₄, ³F₂, ³F₃ and ³F₄, ³H₅ and ³H₄ levels from the ³H₆ ground level were observed. Integrated absorption cross-section of each band except that of ³H₅ level was found to vary with the glass composition. Luminescence spectra of the samples were measured upon 457.9 nm excitation. Three emission bands centered at 476 nm (¹G₄→³H₆ transition), 651 nm (¹G₄→³H₄ transition) and 800 nm (¹G₄→³H₅ transition) were observed. Spontaneous emission cross-sections together with the luminescence spectra measured upon 457.9 nm excitation were used to determine the stimulated emission cross-sections of these emissions.The effect of glass composition on the Judd-Ofelt parameters and therefore on the spontaneous and the stimulated emission cross-sections for the metastable levels of Tm³⁺ ions were discussed in detail. The effect of temperature on the stimulated emission cross-sections for the emissions observed upon 457.9 nm excitation was also discussed.