Luminescent properties of long lasting phosphor Ca2MgSi2O7:Eu

Long afterglow phosphors (Ca_1−xEu_x)₂MgSi₂O₇ (0.002 ≤ x ≤ 0.02) were prepared by solid-state reactions under a weak reductive atmosphere. X-ray diffraction pattern, photoluminescence spectra, decay curve, afterglow spectra and thermoluminescence curves were investigated. The phosphors showed two emission peaks when they were excited by 343 nm, due to two types of Eu²⁺ centers existing in the Ca₂MgSi₂O₇ lattice. However, only one emission peak can be found in their afterglow spectra. Energy transfer between Eu²⁺ ions in inequivalent sites was found. A possible mechanism was presented and discussed. The afterglow decay time of Ca_1.998MgSi₂O₇:Eu_0.002 was nearly 12.5 h which means it was a good long lasting phosphor.     

Energy transfer and luminescence studies of Pr, Yb co-doped lead borate glass

Lead borate glass samples doped with the tripositive lanthanide ions Pr³⁺ and Yb³⁺ were synthesized by the conventional melting-quenching method. The luminescence properties and energy transfer process from Pr³⁺ to Yb³⁺ were investigated. Upon ultraviolet excitation, the room temperature luminescence decay curve of a sample containing only a low concentration of Pr³⁺ exhibited monoexponential decay from ¹D₂ with the lifetime 37 μs, without emission from ³P₀. The room temperature Pr³⁺ emission intensity decreased with the increase of Yb³⁺ mole ratio in the glass. Under the excitation of 454.5 nm at 10 K, a broad red emission band centered at 605 nm, and an NIR emission band at 995 nm were observed in the co-doped lead borate glass, originating from Pr³⁺ and Yb³⁺ ions, respectively. The decay curves of the ¹D₂ emission from Pr³⁺ with addition of Yb³⁺ in lead borate glass show non-monoexponential character, and are best described by a stretched exponential function. The average ¹D₂ decay time decreases considerably with the addition of Yb³⁺ in the glass. Decay curve fitting using a modified Inokuti-Hirayama expression indicates dipole-dipole energy transfer from Pr³⁺ to Yb³⁺, which is consistent with the expected cross-relaxation scheme. There is a good agreement of the estimated overall energy transfer efficiency obtained from the integrals under the normalized decay curves, or from the lifetimes fitted by the stretched exponential function, or from the average decay times.     

Crystal growth and spectral properties of Pr:La2(WO4)3

Pr³⁺-doped La₂(WO₄)₃ single crystal with dimensions up to Ø 20 mm × 35 mm has been grown by the Czochralski method. The structure of the Pr³⁺:La₂(WO₄)₃ crystal was determined by the X-ray powder diffraction and the Pr³⁺ concentration in this crystal was determined. The absorption and fluorescence spectra of Pr³⁺:La₂(WO₄)₃ crystal were measured at room temperature, and the fluorescence lifetime of main emission multiplets were estimated from the recorded decay curves. The spectral properties related to laser performance of the crystal were evaluated.     

White-light long-lasting phosphor Sr2SiO4:Pr

A white-emitting phosphor Sr₂SiO₄: Pr³⁺ was synthesized through a solid-state reaction, and characterized by XRD, scanning electron microscopy (SEM), fluorescence spectrophotometer and thermo luminescence (TL) meter. Its emission spectra is composed of bluish purple (peaking at 390 nm), green (peaking at 535 nm) and red (peaking at 604 nm) light emission. They originate from the transitions of 4f → 5d, ³P₀ → ³H₅ and ¹D₂ → ³H₄ of Pr³⁺. The afterglow emission spectrum is similar to the emission spectra. And the afterglow can last over 40 min in darkness. The TL curve shows that there is only one thermo luminescence band peak at about 376.480 K, which is responsible for the long-lasting emission.     

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.     

Observation on long afterglow of Tb in CaWO4

The Tb³⁺ doped CaWO₄ phosphors are synthesized via high temperature solid state reaction. The X-ray diffraction shows that small amount of Tb³⁺ does not have a significant influence on the structure of CaWO₄. A broad absorption band of the WO₄²⁻ group is observed from photoluminescence and the energy transfer from WO₄²⁻ group to Tb³⁺ ions induces the f-f transition. The cross-relaxation between two adjacent Tb³⁺ ions weakens ⁵D₃-⁷F_j transitions and enhances the ⁵D₄-⁷F_j transitions, leading to a green long afterglow of the phosphors. The thermoluminescence curves centered around 75 °C reveal the trap depth for afterglow generation is about 0.74-0.77 eV. The optimum Tb³⁺ concentration for afterglow properties is about 1%. A deep hole trap is induced when Tb³⁺ concentration exceeds 1% and it suppresses the thermoluminescence and the decay properties.     

Sol–gel synthesis of long-lasting phosphors CdSiO3: Mn2+, RE3+ (RE = Tb,Eu, Nd) and luminescence mechanism research

Mn²⁺ and RE³⁺ (RE = Tb, Eu, Nd) co-doped CdSiO₃ orange phosphors were prepared at 1050 °C by a sol–gel method. The phase and crystallinity of the synthesized materials were investigated by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The luminescence characteristics were analyzed using photoluminescence (PL) spectra, afterglow decay curves, long-lasting phosphorescence spectra, and thermoluminescence (TL) spectra. Due to the difference in co-doped rare earth ionic radii, it varied greatly in trap density and trap depth caused by the different defects deriving from RE³⁺ ions co-doping into the CdSiO₃: Mn²⁺ host. The afterglow intensity and time for these samples increased as follows: CdSiO₃: Mn²⁺0.2%, Nd³⁺0.8% < CdSiO₃: Mn²⁺0.4%, Tb³⁺0.8% < CdSiO₃: Mn²⁺0.4%, Eu³⁺0.3%. CdSiO₃: Mn²⁺0.4%, Eu³⁺0.3% had the best afterglow properties, which could be due to the proper traps formed by Eu³⁺ ions co-doping into the host. The role of RE³⁺ co-doped into the CdSiO₃: Mn²⁺ matrix and the possible long-lasting phosphorescence process was also discussed in this paper.     

High pressure and time resolved luminescence spectra of Gd3Ga5O12:Pr crystal

Luminescence spectra and time resolved luminescence spectra of GGG crystal doped with Pr³⁺ were measured at high hydrostatic pressure from ambient to 220 kbar. Effect of pressure results in the red shift of all luminescence lines related to Pr³⁺ ion emission equals from −0.32 to −1.02 cm⁻¹/kbar and in the diminishing of the luminescence lifetimes. The luminescence decay related to emission from ³P₀ state was single-exponential and diminished with pressure from 23 μs at ambient pressure to 6.5 μs at 165 kbar. Luminescence decay related to transition form ¹D₂ state was two-exponential with longer decay equal to 162 μs at ambient pressure and 120 μs at 165 kbar. We discussed effect of pressure on the ¹D₂ → ³H₄ luminescence and emission from ³P₀ state in the context of non-radiative processes that depopulate the ³P₀ and populate the ¹D₂ state, considering mainly multiphonon relaxation processes and depopulation via the praseodymium trapped exciton state.     

Preparation of PrxZn1 − xO nanopowder with UV-visible light response

We prepared Pr_xZn_1 − xO nanopowder using a combustion method. The sample was characterized by XRD, TEM, XPS, UV-visible and PL spectroscopy. The prepared Pr_xZn_1 − xO nanopowder had a good photon absorption performance in the range of 200-800 nm wavelength. Moreover, the 4f² electronic configuration of trivalent Pr³⁺ ions was revealed from the diffuse reflectance spectra. The single crystalline particle size was about 20-70 nm based on the TEM observation. A quantum size effect of the Pr_xZn_1 − xO nanopowder was also noted.     

Enhanced green emission from Tb-Bi co-doped GdAlO3 nanophosphors

Bi³⁺ and Tb³⁺ ions co-doped GdAlO₃ (GAP) nanophosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GAP phosphor confirms their orthorhombic phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of GAP:Tb³⁺, Bi³⁺ phosphors consist of a broad band in the shorter wavelength region due to the 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with the 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and some sharp peaks in the longer wavelength region due to f → f transitions of Tb³⁺ ions. The present phosphors exhibit green color due to strong ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions. The emission intensity was enhanced by co-doping with Bi³⁺ ions under 292 nm excitation, which indicate that the efficient energy transfer occurred from Bi³⁺ to Tb³⁺ ions.     

Synthesis, characterization and photoluminescence properties of (Gd0.99,Pr0.01)2O2S sub-microphosphor by homogeneous precipitation method

Homogeneous precipitation method for synthesizing (Gd_0.99,Pr_0.01)₂O₂S sub-microphosphor was developed, using the commercially available Gd₂O₃, Pr₆O₁₁, H₂SO₄ and (NH₂)₂CO (urea) as the starting materials. It was found that the as-synthesized precursor is mainly composed of (Gd_0.99,Pr_0.01)₂(OH)₂(CO₃)(SO₄)·nH₂O. Pure quasi-spherical shaped (Gd_0.99,Pr_0.01)₂O₂S particles can be synthesized by calcining the precursor at a temperature higher than 700 °C for 1 h in flowing hydrogen. The (Gd_0.99,Pr_0.01)₂O₂S particles have a narrow size distribution with a mean grain size of about 300-400 nm. Photoluminescence spectra of (Gd_0.99,Pr_0.01)₂O₂S under 303 nm UV excitation show a green emission at 515 nm as the most prominent peak, which corresponds to the ³P₀ → ³H₄ transition of Pr³⁺ ions. Decay study reveals that the ³P₀ → ³H₄ transition of Pr³⁺ ions in Gd₂O₂S host lattice has a single exponential decay behavior.     

Luminescence quenching processes in Gd2O2S:Pr,Ce scintillating ceramics

Temperature dependent radioluminescence under X-ray excitation (XRL) and luminescence decay time measurements following 430 nm laser excitation have been performed in the 10-775 K range on Gd₂O₂S:Pr³⁺,Ce³⁺ scintillating ceramics. From 200 K to both low and high temperature, XRL light yield decreases by 60%. High temperature luminescence quenching has been revisited. Temperature dependent lifetime measurements imply non-radiative de-excitation mechanism at electronic defects spatially correlated to Pr³⁺ emitting ions. At low temperatures, decreasing XRL light yield with irradiation time is linked to very intense thermoluminescence (TL) peak around 120 K ascribed to sulfur vacancies. These traps cause efficient electron trapping which competes with the prompt recombination mechanism.     

Fast d-f emission in Ce, Pr and Nd activated RbCl

In the search for new scintillator materials, Ce³⁺ doped chlorides are a promising class of materials, combining a high efficiency and fast response time. Even shorter response times may be achieved by replacing Ce³⁺ by Pr³⁺ or Nd³⁺ as the lifetime of the d-f emission is substantially shorter for these ions. Here we report on the luminescence properties of Ce³⁺, Pr³⁺ and Nd³⁺ in RbCl and investigate the potential as a scintillator material. Under UV excitation Ce³⁺ shows d-f emission between 325 and 425 nm. The emission originates from multiple (differently charge compensated) Ce³⁺ sites. The luminescence lifetime varies with wavelength and is ∼40 ns for the longer wavelength emission. For RbCl:Pr³⁺ three d-f emission band are observed between 250 and 350 nm which can be assigned to transitions from the lowest energy fd state to different ³H_J (J = 4-6) states within the 4f² configuration of Pr³⁺. The decay time is ∼17 ns. For the Nd³⁺ activated sample a weak emission band around 220 nm is observed only at 8 K which may be due to d-f emission. The very short lifetime (4 ns) is faster than the radiative lifetime, indicating that the d-f emission is quenched by relaxation to lower lying 4f³ states or by the process of photoionization. Under VUV excitation at wavelengths below 175 nm (the bandgap of RbCl) the d-f emission is very weak for Ce³⁺, Pr³⁺ and Nd³⁺ doped RbCl and the emission spectra are dominated by defect related emission. This indicates that energy transfer from the host lattice to the fd states is inefficient which prevents application as a scintillator material.     

Influence of Zn2+ and Si4+ codoping on luminescence properties of CaWO4:Eu3+ phosphor

The red afterglow phosphors of CaWO₄ doped with Eu³⁺, Zn²⁺ or (and) Si⁴⁺ were prepared by solid state reaction. All crystalline phases were identified by the X-ray powder diffraction (XRD). The photoluminescence spectra and decay curves as well as thermoluminecence (TL) curves of all samples were also investigated. In comparison to CaWO₄:Eu³⁺ phosphor, the luminescence and afterglow properties could be improved greatly after being doped with Zn²⁺ or (and) Si⁴⁺ ions.     

Optical properties of Mn-doped ZnS semiconductor nanoclusters synthesized by a hydrothermal process

Undoped and Mn-doped ZnS nanoclusters have been synthesized by a hydrothermal approach. Various samples of the ZnS:Mn with 0.5, 1, 3, 10 and 20 at.% Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-ray, high resolution electron microscopy, UV-vis diffusion reflection, photoluminescence (PL) and photoluminescence excitation (PLE) measurements. All the prepared ZnS nanoclusters possess cubic sphalerite crystal structure with lattice constant a = 5.408 ± 0.011 ?. The PL spectra of Mn-doped ZnS nanoclusters at room temperature exhibit both the 495 nm blue defect-related emission and the 587 nm orange Mn²⁺ emission. Furthermore, the blue emission is dominant at low temperatures; meanwhile the orange emission is dominant at room temperature. The Mn²⁺ ion-related PL can be excited both at energies near the band-edge of ZnS host (the UV region) and at energies corresponding to the Mn²⁺ ion own excited states (the visible region). An energy schema for the Mn-doped ZnS nanoclusters is proposed to interpret the photoluminescence behaviour.     

Absorption and circular-dichroism spectra of LaBGeO5 crystal doped with Pr and Ho ions

Absorption and circular-dichroism spectra of LaBGeO₅ crystal doped with Pr³⁺ and Ho³⁺ ions were investigated at 8 K in the range 300-900 nm. Electronic transitions of these ions, which substitute La³⁺ ions in positions with a local symmetry C₁ are observed in the spectra. All transitions are active in both absorption and circular-dichroism spectra. Values of the dipole strengths D_om, rotation strengths R_om and anisotropy factors g are calculated for some well-separated bands.     

Enhanced luminescence properties of YBO3:Eu phosphors by Li-doping

Different concentrations of Li-doped YBO₃:Eu³⁺ phosphors have been prepared by the conventional solid state reaction method and were characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence excitation and emission measurements. An intense reddish orange emission is observed under UV excitation and the emitted radiation was dominated by an orange peak at 594 nm resulted from the ⁵D₀ → ⁷F₁ transitions of Eu³⁺ ions. The brightness of the YBO₃:Eu³⁺ phosphor was found greatly improved with Li-doping accompanied by slight improvement in the purity of the color which might be attributed to improvement in crystallinity, grain sizes and creation of oxygen vacancies with Li-doping. The observed results have been discussed in comparison with similar reported works.     

Optical characterization of Bi doped SrS nanophosphors

Optical properties of Bi³⁺ doped SrS nanophosphors synthesized by solid state diffusion method in the presence of sodium thiosulfate as a flux have been reported. UV-vis absorption and photoluminescence (PL) spectra of SrS phosphors doped with trivalent Bi³⁺ ions either alone or in combination with charge compensating ions, were also studied. These studies reflect that the incorporation of Bi³⁺ into host lattice is facilitated by the charge compensating Na⁺ ions. PL emission for SrS:Bi shows a peak at 481 nm at an excitation wavelength of 430 nm, which is attributed to the transition from the ³P₁ to ¹S₀ states of Bi³⁺. We have also investigated the effect of different dopant concentrations on PL emission intensity.     

Synthesis and photoluminescence of Eu-doped ZnO microrods prepared by hydrothermal method

Eu-doped ZnO microrods, with wurtzite structure and [0 0 0 1] growth direction have been successfully synthesized on Si (1 0 0) substrates by a simple hydrothermal method. The samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), lifetime decay curves, photoluminescence (PL) and photoluminescence excitation (PLE) spectra, respectively. These results indicate that Eu³⁺ ions are located in the distorted lattice sites near the surface of the ZnO microrods. Additionally, it is also suggested that the surface defects may act as a step in the process of energy transfer from ZnO to Eu³⁺ ions.     

Solvothermal synthesis of SrMoO4:Ln (Ln = Eu, Tb, Dy) nanoparticles and its photoluminescence properties at room temperature

Rare-earth ions (Eu³⁺, Tb³⁺, Dy³⁺) doped SrMoO₄ nanoparticles were prepared by solvothermal route using oleic acid as surfactant to control the particle shape and size. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), photoluminescence spectra (PL) and the kinetic decay times were applied to characterize the obtained samples. The XRD patterns reveal that all the doped samples are assigned to the scheelite-type tetragonal structure of SrMoO₄ phase. In addition, the as-synthesized SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) particles are high purity well crystallized and with the average size of 30-50 nm. The possible formation process of SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) nanoparticles have been discussed as well. Upon excitation by ultraviolet radiation, the as-synthesized SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) nanoparticles exhibit the characteristic emission lines of corresponding Eu³⁺, Tb³⁺, Dy³⁺, respectively.