Photoluminescence properties of thenardite activated with Eu

Na₂SO₄:Eu phosphors were prepared by heating pure natural thenardite with EuF₃ at 900 °C for 20 min in air. The photoluminescence (PL) and excitation spectra of as-prepared and γ-ray-irradiated phosphors were observed at 300 K. The PL spectrum under 394 nm excitation consisted of strong narrow bands with peaks at 579, 592, 616, 652, 697 and 741 nm, assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, …, 5) transitions, respectively, within Eu³⁺. The PL spectrum under 340 nm excitation consisted of a broad Eu²⁺ band with a peak at 435 nm. The excitation spectrum obtained by monitoring the violet luminescence consisted of a weak band with a peak at approximately 261 nm and a broad Eu²⁺ band with a peak at approximately 338 nm. The relative efficiency of the violet luminescence of the γ-ray-irradiated phosphor at the exposure of 46 kGy increased up to 3.0 times that of the unirradiated phosphor. The enhancement of violet luminescence by γ-ray irradiation was ascribed to the conversion of Eu³⁺ to Eu²⁺ in Na₂SO₄.     

Fluorescence features of Sm ions in Na2SO4-MO-P2O5 glass system—Influence of modifier oxide

Na₂SO₄-P₂O₅:Sm³⁺ glasses mixed with three different alkaline earth modifier oxides viz., MgO, CaO and BaO were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature; the Judd-Ofelt theory was successfully applied to characterize these spectra. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r, for various emission levels in the spectra of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies in the change of scenario for modifying oxides in the glass network.     

Photoluminescence characterization of Ce and Dy doped Li2CaGeO4 phosphors

Ce³⁺ and Dy³⁺ activated Li₂CaGeO₄ phosphors were prepared by a solid-state reaction method, and characterized by XRD (X-ray diffraction) and photoluminescence techniques. The characteristic emission bands of Dy³⁺ due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions were detected in the emission spectra of Li₂CaGeO₄:Dy³⁺. Ce³⁺ broad band emission was observed in Li₂CaGeO₄:Ce³⁺ phosphors at 372 and 400 nm due to 5d→4f transition when excited at 353 nm. Co-doping of Ce³⁺ enhanced the luminescence of Dy³⁺ significantly and concentration quenching occurs when Dy³⁺ is beyond 0.04 mol%. White-light with different hues can be realized by tuning Dy³⁺ concentration in the phosphors.     

Luminescence properties of Ba2NaNb5O15 crystals activated with Sm, Eu, Tb or Dy ions

Single crystals of Ba₂NaNb₅O₁₅ (BNN) singly doped with Sm³⁺, Eu³⁺, Tb³⁺ or Dy³⁺ have been grown by means of the flux growth method. Their visible emission and excitation spectra and the decay profiles of the luminescence have been measured at room temperature. All spectral features are significantly inhomogeneously broadened in consequence of the structural disorder of the host and of the doping mechanisms. The analysis of the observed spectra allows formulating an hypothesis about the site occupancy of the active ions in the BNN lattice.     

Monochromatic blue-green and red emission of rare-earth ions in MgGa2O4 spinel

Pr³⁺-activated blue-green phosphor and Eu³⁺-activated red phosphor hosted in MgGa₂O₄ spinel have been prepared by a gel-assisted high-temperature calcination process, respectively. Both anion and cation vacancies in the host were formed by decreasing the Mg concentration in the reaction source. The induced vacancies provide possibility of the accommodation of the doped rare-earth ions with larger atomic size in the highly symmetrical spinel structure. Due to the efficient energy transfer from the spinel host to the sole 4f sub-level of the doped rare earths, monochromatic emissions with high efficiency can be obtained to allow the phosphors to find applications in solid-state laser device and other phosphors excited under low energy. The corresponding spectroscopic transition mechanism has been proposed in this work.     

The luminescence of CaYBO4:RE (REEu, Gd, Tb, Ce) in VUV-visible region

Phosphors CaYBO₄:RE³⁺ (RE=Eu, Gd, Tb, Ce) were synthesized with the method of solid-state reaction at high temperature, and their vacuum ultraviolet (VUV)-visible luminescent properties in VUV-visible region were studied at 20 K. In CaYBO₄, it is confirmed that there are two types of lattice sites that can be substituted by rare-earth ions. The host excitation and emission peaks of undoped CaYBO₄ are very weak, which locate at about 175 and 350-360 nm, respectively. The existence of Gd³⁺ can efficiently enhance the utilization of host absorption energy and result in a strong emission line at 314 nm. In CaYBO₄, Eu³⁺ has typical red emission with the strongest peak at 610 nm; Tb³⁺ shows characteristic green emission, of which the maximum emission peak is located at 542 nm. The charge transfer band of CaYBO₄:Eu³⁺ was observed at 228 nm; the co-doping of Gd³⁺ and Eu³⁺ can obviously sensitize the red emission of Eu³⁺. The fluorescent spectra of CaYBO₄:Ce³⁺ is very weak due to photoionization; the co-addition of Ce³⁺-Tb³⁺ can obviously quench the luminescence of Tb³⁺.     

Photoluminescence study of disordering in the cation sublattice of Cu2ZnSnS4

In this study we investigated the influence of the degree of disordering in the cation sublattice on low temperature photoluminescence (PL) properties of Cu₂ZnSnS₄ (CZTS) polycrystals. The degree of disordering was changed by using different cooling rates after post-annealing at elevated temperatures. The results suggest that in the case of higher degree of cation sublattice disorder radiative recombination involving defect clusters dominates at T = 10 K. These defect clusters induce local band gap energy decrease in CZTS. The concentration of defect clusters can be reduced by giving more time for establishing ordering in the crystal lattice. As a result, radiative recombination mechanism changes and band-to-impurity recombination involving deep acceptor defect with ionization energy of about 200 meV starts to dominate in the low temperature PL spectra of CZTS polycrystals.     

Luminescent properties of RE-activated CaAl2B2O7 (RE=Tb, Ce) in VUV-visible region

RE³⁺-activated α- and β-CaAl₂B₂O₇ (RE=Tb, Ce) were synthesized with the method of high-temperature solid-state reaction. Their VUV excitation and VUV-excited emission spectra are measured and discussed in the present article. The charge transfer band of Tb³⁺ and Ce³⁺ is respectively calculated to be at 151±2 and 159±3 nm. All the samples show an activator-independent excitation peak at about 175 nm and an emission peak at 350-360 nm ascribed to the host absorption and emission band, respectively.     

Low temperature quenching and high efficiency Tm, La or Tb co-doped CaSc2O4:Ce phosphors for light-emitting diodes

Low temperature quenching and high efficiency CaSc₂O₄:Ce³⁺ (CSO:Ce³⁺) phosphors co-doped with Tm³⁺, La³⁺ and Tb³⁺ ions were prepared by a solid state method and the phase-forming, morphology, luminescence and application properties of these phosphors were investigated. The results showed that co-doping of Tm³⁺, La³⁺ and Tb³⁺ ions can improve the luminescence properties and decrease temperature quenching of CSO:Ce³⁺ phosphor remarkably. High efficiency green-light-emitting diodes were fabricated with the prepared phosphors and InGaN blue-emitting (∼460 nm) chips. The good performances of the green-light-emitting LEDs made from co-doped CSO:Ce³⁺ phosphors confirm the luminescence enhancement and indicate that Tm³⁺, La³⁺ and Tb³⁺ co-doped CSO:Ce³⁺ phosphors are suitable candidates for the fabrication of high efficiency white LEDs.     

Photoluminescence of SrGa2S4:Sn,Re(=Ce, Gd) phosphors

The photoluminescence (PL) spectra, PL excitation spectra, color coordinates, and X-ray diffraction spectra are reported for SrGa₂S₄:Sn,Re(=Ce and Gd, respectively) phosphors. By mixing SrGa₂S₄:Sn,Ce phosphors with different Ce³⁺ concentrations, white emissions can be obtained under the excitation of a 340-nm UV LED. Emissions in the green to yellow color range can be obtained from SrGa₂S₄:Sn,Gd phosphors. The rare earth ions enhance the green emission band, which peaks at 534 nm, instead of the yellow one. The origin of this enhancement is discussed. The resonant energy transfer rates are estimated in the cases from Ce³⁺ to the green and yellow centers of Sn²⁺ and between the yellow centers and the green centers.     

TSL, OSL and ESR studies in ZnAl2O4:Tb phosphor

ZnAl₂O₄:Tb phosphor was prepared by combustion synthesis. ZnAl₂O₄:Tb exhibits three thermally stimulated luminescence (TSL) peaks around 150, 275 and 350 °C. ZnAl₂O₄:Tb exhibits optically stimulated luminescence (OSL) when stimulated with 470 nm light.Electron spin resonance (ESR) studies were carried out to identify defect centres responsible for TSL peaks observed in ZnAl₂O₄:Tb. Two defect centres are identified in irradiated ZnAl₂O₄:Tb phosphor and these centres are assigned to V and F⁺ centres. V centre appears to correlate with the 150 °C TSL peak, while F⁺ centre could not be associated with the observed TSL peaks.     

Photoluminescence of colloidal YVO4:Eu/SiO2 core/shell nanocrystals

YVO₄:Eu, and YVO₄:Eu/SiO₂ nanocrystals (NCs) were prepared by hydrothermal method with citrate as capping ligands. Their morphologies, structures, components, and photoluminescence properties were investigated and presented in this paper. A remarkable fluorescence enhancement up to 2.17 times was observed in colloidal YVO₄:Eu/SiO₂ NCs, compared to that of colloidal YVO₄:Eu NCs. This is mainly attributed to the formation of the outer protecting layers of biocompatible SiO₂ shells; which shield the Eu³⁺ ions effectively from water and thus reduces the deleterious effects of water on the luminescence. Meanwhile, on the basis of laser selective excitation, two kinds of luminescent centers were confirmed in the NCs, namely, inner Eu³⁺ ions and surface Eu³⁺ ions. The surface modifications for YVO₄:Eu NCs effectively reduced the surface defects and accordingly enhanced the luminescence. The core/shell NCs exhibited long fluorescence lifetime and high photostability under ultraviolet radiation.     

Influence of Li dopants on thermoluminescence spectra of CaSO4 doped with Dy or Tm

Thermoluminescence emission spectra are presented for lithium doped variants of CaSO₄:Dy or CaSO₄:Tm dosimetry material. All three dopants (Li, Dy and Tm) variously introduce different changes in both the glow peak temperatures and the luminescence efficiency. In every case the emission signals display the line emission characteristic of the rare earth ions. At temperatures below ∼50 K the relative peak intensities differ for Dy and Tm doped samples, and there are small temperature shifts between the Dy:Li and Tm:Li co-doped materials. Above room temperature the rare earth ions do not show peak temperature movements when co-doped with lithium. However they do influence the peak temperature by ∼5 °C when they are the sole dopant. Inclusion of lithium dramatically moves the high temperature glow peak from ∼200 °C down to 120 °C. All these changes are consistent with a single defect model in which the trapping sites and luminescence occur within the complexes formed of the rare earth ion, an intrinsic sulphate defect and lithium. The evidence and rationale for such a model are presented. There is discussion which suggests that such defect complexes are the norm in thermoluminescence.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

EPR study of some rare-earth ions (Dy3+, Tb3+, and Nd3+) in YBa2Cu3O6-compound

We investigate the low temperature X-band electron paramagnetic resonance (EPR) of YBa(2)Cu(3)O(x) compounds with x congruent with 6.0 doped with Dy(3+), Tb(3+), and Nd(3). The EPR spectra of Dy(3+) and Tb(3+) have been identified. The EPR of Tb(3+) is used also to study the effect of suppression of high T(c) superconductivity by doping with Tb(3+). The EPR of Nd(3+) is probably masked by the intense resonance of Cu(2+). All experimental EPR results compare well with theoretical estimations.     

Photoluminescence and thermoluminescence of Ce and Eu in Ca2Al2SiO7 matrix

The Ca₂Al₂SiO₇ samples doped with Ce³⁺ and Eu²⁺ are synthesized via a high temperature solid-state reaction. Ca₂Al₂SiO₇: Ce³⁺ emits a strong UV-violet emission while Ca₂Al₂SiO₇: Eu²⁺ emits a blue-green emission. The Stokes shift of the latter is greater due to a stronger crystal repulsion from ligands to Eu²⁺ ions. Ca₂Al₂SiO₇: Ce³⁺ exhibits a stronger initial intensity and longer duration of afterglow due to the higher liberated probability of the trapped carriers. The thermoluminescence curves reveal that at least three traps exist in the phosphors. Ca²⁺ vacancies may enhance the electron trapping and then lead to a stronger afterglow. A possible explanation will be provided.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

A nuclear magnetic resonance study of the structural properties and molecular motions of Li2KH(SO4)2 and LiKSO4 single crystals

The structural properties and relaxation mechanisms of Li₂KH(SO₄)₂ crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T₁) of their ¹H, ⁷Li, and ³⁹K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO₄ crystals. The substitution of the potassium ions with protons in the LiKSO₄ crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The ⁷Li T₁ for the Li₂KH(SO₄)₂ crystals was much shorter than the ⁷Li T₁ for the LiKSO₄ crystals, and these findings indicate that the presence of the protons in Li₂KH(SO₄)₂ causes the Li ions to move with greater freedom.     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.