Enhanced red emission in LiAl5O8:Fe phosphor by B doping

Fe³⁺, B³⁺ co-doping LiAl₅O₈ phosphor has been successfully synthesized by a solid-state reaction method assisted with wet chemical mixing route. Photoluminescence emission peak is observed at around 672 nm excited at both 290 nm ultraviolet and 565 nm green light. With introduction of a small amount of boric acid, the red emission intensity can be enhanced by 2.62 times under 290 nm excitation and 2.31 times under 565 nm excitation, respectively. It is believed that the substitution of B³⁺ ions for Al³⁺ sites decreases the symmetry of the luminescence center, intensifying the red emission.     

Photoluminescence and energy transfer studies on Eu and Ce co-doped SrCaSiO4 for white light-emitting-diodes

The luminescence of SrCaSiO₄:Eu²⁺, Ce³⁺ is studied as a potential ultraviolet light-emitting diodes (UV-LEDs) phosphor that is capable of converting the ultraviolet emission of a UV-LED into green light with good luminosity. There are two emissions peaks peaking at 420 and 500 nm, respectively. The two emissions come from d-f transitions of Ce³⁺ and Eu²⁺, respectively. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped SrCaSiO₄ due to a part of spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺. The Ce³⁺/Eu²⁺ energy transfer, thoroughly investigated by the diffuse reflection emission and excitation spectra, photoluminescence decay curves, is demonstrated to be in the mechanism of electric dipole-dipole interaction.     

Synthesis and phosphorescence properties of Mn, La and Ho in MgAl2Si2O8

Mn⁴⁺, La³⁺ and Ho³⁺ doped MgAl₂Si₂O₈-based phosphors were first synthesized by solid state reaction. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The phosphors were obtained at about 1300 °C. They showed broad red and fuchsia-pink emission bands in the range of 610-715 nm and had a different maximum intensity when activated by UV illumination. Such a fuchsia-pink emission can be attributed to the intrinsic d-d transitions of Mn⁴⁺.     

Low-voltage cathodoluminescence properties of green-emitting ZnAl2O4:Mn nanophosphors for field emission display

A low-cost ZnAl₂O₄:Mn²⁺ green nanophosphor for field emission display (FED) was successfully synthesized by the coprecipitation method and a two-step firing, firstly calcining at 1200 °C for 2 h in air and then annealing at 900 °C for 3 h in flowing NH₃ gas. The effects of the preparation process and the Mn²⁺ concentration on optical properties of ZnAl₂O₄:Mn²⁺ were investigated. The phase composition, particle morphology, photoluminescence (PL) spectra of the ZnAl₂O₄:Mn²⁺ phosphor as well as low-voltage field emission properties of the FED device prepared by using the synthesized ZnAl₂O₄:Mn²⁺ phosphor were examined. Similar to ZnGa₂O₄:Mn²⁺, Mn²⁺-doped ZnAl₂O₄ showed two green emission bands centered at 508 and 517 nm, respectively, which originate from ⁴T₁(⁴G)→⁶A₁(⁶S) transitions of Mn²⁺ on T_d and O_h sites. The PL intensity reached the maximum at 0.5 at.% Mn²⁺. Under the low-voltage excitation, the FED device exhibited bright green emission, high voltage brightness saturation, and high color purity.     

Luminescence studies of Ba1−xMg2−y(PO4)2:xEu, yMn phosphor

The phosphors BaMg₂(PO₄)₂ doped with Eu²⁺ and Mn²⁺ solely or doubly were prepared by solid state reaction, and their luminescent properties were also investigated. Under the excitation of 322 nm, it has been observed a broad blue emission band centered at 417 nm and a red emission band centered at about 665 nm, resulting from Eu²⁺ and Mn²⁺, respectively. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the emission spectra of Eu²⁺ and the excitation spectra of Mn²⁺. According to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission, efficiencies of energy transfer were calculated. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

Nanocrystallization and photoluminescence of Ce/Dy/Eu-doped fluorosilicate glass ceramics

Ce³⁺-Eu²⁺-Dy³⁺-Eu³⁺-doped fluorosilicate glass ceramics containing orthorhombic CaCeOF₃ nanocrystals were prepared by annealing the precursor glass above 640 °C, along with the reduction of Eu³⁺ → Eu²⁺. Under near ultraviolet excitation, the emission bands of Eu²⁺ or Dy³⁺ were enhanced by several ten or hundred times, owing to energy transfers from Ce³⁺ to Eu²⁺ or Dy³⁺. The glass and glass ceramics emitted warm white light deriving from the blue, yellow and red emission from Eu²⁺, Dy³⁺ and Eu³⁺. Tuning the annealing temperature, the Eu²⁺/Eu³⁺ ratio and the warm white Commission Internationale de I’Eclairage (CIE) coordinates can be adjusted. Thus, the present materials can be applied on warm white high power light-emitting-diodes for indoor illumination application.     

Synthesis and luminescence properties of clew-like CaMoO4:Sm, Eu

Eu³⁺ and Sm³⁺ co-doped CaMoO₄ microclews have been successfully synthesized via a facile hydrothermal method directly in surfactant-free environment. The as-prepared phosphor present clew-like agglomerates composed of 40 nm nanosheets under the moderated reaction temperature. The red phosphor CaMoO₄:Eu³⁺, Sm³⁺ can generate a strong absorption line at 405 nm, originating from ⁶H_5/2 → ⁶P_5/2 transition of Sm³⁺, which is suitable for the emission of the near-ultraviolet light-emitting diodes (∼400 nm). Energy transfer between Sm³⁺ and Eu³⁺ is detected from the varied photoluminescence spectra with different Eu³⁺ concentrations and the energy transfer mechanism is clarified via the photoluminescence spectra. When Sm³⁺ is excited (405 nm), the electron is excited from ⁶H_5/2 to ⁶P_5/2, and then relaxed to ⁴G_5/2. It jumps from ⁴G_5/2 to the lower levels corresponding to the emissions of Sm³⁺; meanwhile, the transfers from ⁴G_5/2 state of Sm³⁺ ion to ⁵D₀ state of Eu³⁺ ion come out. The transition of ⁵D₁ → ⁷F_J (J = 0, 1, 2) does not appear indicating that the transfer from ⁴G_5/2 state of Sm³⁺ to ⁵D₀ state rather than ⁵D₁ state of Eu³⁺ is the energy transfer pathway.     

Photoluminescence and energy transfer of Ce and Tb doped oxyfluoride aluminosilicate glasses

The transmission and photoluminescence (PL) properties of Ce³⁺ or Tb³⁺ doped and Tb³⁺/Ce³⁺ codoped oxyfluoride aluminosilicate glasses were reported. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were applied to confirm the structure and thermal stability of samples. PL spectra revealed a bright and broad violet-blue emission derived from Ce³⁺ [5d (²D) → ²F_5/2,7/2] and an intense sharp green emission (543 nm) derived from Tb³⁺ (⁵D₄ → ⁷F₅) in the Ce³⁺ and Tb³⁺ doped glasses, respectively. Concentration quenching is not observed even the mole ratio of Tb³⁺ is up to 8% in Tb³⁺ doped glass. This indicates that the as-made host glass provides a good distribution of Tb³⁺ activators in glass matrix. For Tb³⁺/Ce³⁺ codoped glasses, a strong green emission corresponding to Tb³⁺ (⁵D₄ → ⁷F₅) and an energy transfer phenomenon from Ce³⁺ to Tb³⁺ were observed upon excitation with an UV wavelength (289 nm). It was also observed that their PL intensity depends on the concentration of Ce³⁺ when the concentration of Tb³⁺ is fixed. The mechanism involved in the energy transfer between Ce³⁺ and Tb³⁺ was explained with an energy level diagram.     

Growth of Mn, Co and Ni-doped near-stoichiometric LiNbO3 by Bridgman method using K2O flux

The near-stoichiometric LiNbO₃ (SLN) single crystals doped Mn²⁺, Co²⁺ and Ni²⁺ in 0.5 mol% concentration in the raw compositions were grown by the Bridgman method under the conditions of taking K₂O as flux, a high temperature gradient (90–100 °C/cm) for solid–liquid interface. The XRD, absorption spectra, excitation spectra and emission spectra have been carried out. From the absorption edges of Mn²⁺, Co²⁺ and Ni²⁺-doped SLN crystals, the molar ratio of [Li⁺]/[Nb⁵⁺] are estimated to be about 0.977. The absorption spectra of Mn²⁺:SLN have shown a broad absorption band centered at 571 nm (⁶A_1g(⁶S) → ⁴T_1g(⁴G)), three absorption peaks at 520, 549 and 612 nm (overlapping of the ⁴T₁(F)–⁴A₂(F), ⁴T₁(F)–⁴T₁(P)), and a wide absorption band at 1400 nm (⁴T₁(F) → ⁴T₂(F)) of Co²⁺:SLN, Ni²⁺:SLN, and five absorption peaks at 381 nm (³A_2g(F) → ³T_1g(P)), 733 nm (³A_2g(F) → ³T_1g(F)), 1280 nm (³A_2g(F) → ³T_2g(F)), 430 nm (³A_2g(F) → ¹T_2g(D)), and 840 nm (³A_2g(F) → ¹E(D)) of Ni²⁺:SLN were observed. A red emission at 612 nm (⁴T_1g(⁴G) → ⁶A_1g(⁶S)) for Mn²⁺:SLN, a red emission at 775 nm (⁴T₁(P) → ⁴T₁(F)) for Co²⁺:SLN, and a green emission at 577 nm (¹T_2g(D) → ³A_2g(F)) and a red emission at 820 nm (¹T_2g(D) → ³T_2g(F)) for Ni²⁺:SLN were observed under excited by 416, 520 and 550 nm lights, respectively. The concentration distribution of Mn²⁺, Co²⁺and Ni²⁺ ion in SLN crystals was investigated primarily from the absorption and emission spectra for various parts. The effective distribution coefficient for Mn²⁺ was less than 1. While, for Co²⁺ and Ni²⁺ were more than 1.     

Synthesis and characterization of YNbTiO6:Dy phosphor

A novel yellow phosphor of Dy³⁺ activated YNbTiO₆ has been prepared by high temperature solid-state reaction, and its luminescence properties have been investigated. The excitation spectra monitored at 575 nm have several strong peaks from 350 to 480 nm. Under 365 nm excitation, the emission spectra of composition-optimized (Y_0.9Dy_0.1)NbTiO₆ phosphor exhibit a dominant peak located at about 575 nm with the Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of (0.385, 0.411). The energy transfer between Dy³⁺ is found to be through exchange interaction.     

Reddish orange long afterglow phosphor Ca2SnO4:Smprepared by sol-gel method

A reddish orange light emissive long afterglow phosphor, Ca₂SnO₄:Sm³⁺ was prepared by sol-gel method at lower temperature. The synthesized phosphors were characterized by X-ray diffraction, scanning electron micrograph images, photoluminescence spectra, afterglow decay curves and thermoluminescence spectra. Three emission peaks locate at 565 nm, 609 nm and 655 nm corresponding to CIE chromaticity coordinates of x = 0.53 and y = 0.47, which indicates the reddish orange light emitting. The fluorescent intensity and the afterglow characteristic depends on the concentration of Sm³⁺ and the optimized concentration is 1.5 mol%. The afterglow decay curves are well fitted with triple-exponential decay models. The thermoluminescence glow curves show that the Sm³⁺ induces suitable trap depth and result in the long afterglow phenomenon, and the corresponding increase or decrease in afterglow is associated with trap concentration, nearly no change in trap depth. The 1.5 mol% Sm³⁺-doped Ca₂SnO₄ sample has the biggest trap concentration and exhibit the best afterglow characteristic, its’ afterglow time is about 1 h. The phosphorescence mechanism of this long afterglow phosphor was discussed.     

Luminescence and energy transfer of Mn and Tb in Y3Al5O12 phosphors

Mn²⁺ is an excellent luminescent ion with variable color from green, yellow to red in different hosts and has been widely utilized in recent years. The luminescent intensity of Mn²⁺ in many hosts is so low that the correlative application is restricted. In the present paper, two methods, i.e. employing a charge compensator and introducing a sensitizer, were adopted to enhance the luminescence of Mn²⁺ in Y₃Al₅O₁₂ (YAG). By employing Si⁴⁺ as a charge compensator, the doping content of Mn²⁺ (x) in Y₃Mn_xAl_5−2xSi_xO₁₂ can be lifted up to 0.4. Mn²⁺ in YAG emits orange light in a broad band. The peak wavelength shifts from 586 to 593 nm with the increasing x. The luminescent intensity of Mn²⁺ reaches its maximum when x = 0.1. Co-doping Tb³⁺ into Mn²⁺ doped YAG, the sensitization effect of Tb³⁺ on Mn²⁺ was observed clearly. The resonance energy transfer from Tb³⁺ to Mn²⁺ occurs because there is a well overlapping between emission spectrum of Tb³⁺ and excitation spectrum of Mn²⁺. A reasonable explanation for the sensitization effect of Tb³⁺ on the luminescence of Mn²⁺ was brought forward.     

Effects of Ce concentration, beam voltage and current on the cathodoluminescence intensity of SiO2:Pr-Ce nanophosphor

SiO₂:Pr³⁺-Ce³⁺ phosphor powders were successfully prepared using a sol-gel process. The concentration of Pr³⁺ was fixed at 0.2 mol% while that of Ce³⁺ was varied in the range of 0.2-2 mol%. High resolution transmission electron microscopy (HRTEM) clearly showed nanoclusters of Pr and Ce present in the amorphous SiO₂ matrix, field emission scanning electron microscopy (FE-SEM) indicated that SiO₂ clustered nanoparticles from 20 to 120 nm were obtained. Si-O-Si asymmetric stretching was measured with Fourier transform-IR (FT-IR) spectroscopy and it was also realized that this band increased with incorporation of the activator ions into the SiO₂ matrix. The broad blue emission from the Ce³⁺ ions attributed to the 5d¹-4f¹ transition was observed from the SiO₂:0.2 mol% Pr³⁺-1 mol% Ce³⁺ phosphor. This emission was slightly enhanced compared to that of the singly doped SiO₂:1 mol%Ce³⁺ phosphor. Further investigations were conducted where the CL intensity was measured at different beam voltages and currents from 1 to 5 kV and 8.5 to 30 μA, respectively, in order to study their effects on the CL intensity of SiO₂:0.2 mol% Pr³⁺-1 mol% Ce³⁺. The electron-beam dissociated the SiO₂ and as a result an oxygen-deficient surface dead or non-luminescent layer of SiO_x, where x < 2 on the surface, was formed.     

Synthesis and luminescence properties of Bi-doped YVO4 phosphors

YVO₄:Bi³⁺ phosphors have been prepared by a convenient high-temperature solid-state method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) technologies are used to study the luminescence properties of YVO₄:Bi³⁺ phosphors. The emission and excitation spectra of Bi³⁺ in the YVO₄ lattice have been investigated at room temperature. The excitation band peaks at 330 nm in a region among 250-400 nm, and the emission spectrum exhibits an intense yellowish-white broad emission centered at about 543 nm covering from 400 nm to 800 nm. The full width at half maximum (FWHM) is about 144 nm. The color coordinates of the as-synthesized YVO₄:Bi³⁺ phosphors are in a range of x = 0.358-0.374, y = 0.482-0.496. The dependence of the luminescence intensity on Bi³⁺ concentrations and heat treatment condition has also been discussed. In addition, we found that a little amount of flux NH₄Cl could enhance the Bi³⁺ luminescence intensity.     

Preparation and luminescent properties of Eu doped Sr3La(PO4)3 phosphor

Eu²⁺-doped Sr₃La(PO₄)₃ phosphors were synthesized by solid-state reaction method. Their luminescent properties were investigated. The phosphor could be excited by ultraviolet light effectively. The emission spectra exhibit two emission peaks located at 418 nm and 500 nm, respectively. These two peaks originated from two different luminescent centers, respectively. One is nine-coordinated Eu(I) center, other is six-coordinated Eu(II) center. It was found that the doping concentration of Eu²⁺ ions affected the shape of emission spectra. As the doping concentration increasing, Eu²⁺ ions are more likely to form Eu(I) luminescent centers and emit purple light.     

Photoluminescent properties of LiSrxBa1−xPO4:RE (RE = Sm, Eu) f-f transition phosphors

Rare-earth ions (Sm³⁺ or Eu³⁺) doped LiSr_xBa_1−xPO₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) f-f transition phosphor powders were prepared by a high temperature solid-state reaction. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the phase structure of the sample changes from LiBaPO₄ to LiSrPO₄ when x changes from 0 to 1.0. The excitation spectra indicate that only direct excitation of rare earth ions (Sm³⁺ or Eu³⁺) can be observed. The doped rare earth ions show their characteristic emission in LiSr_xBa_1−xPO₄, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Sm³⁺⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, 11/2), respectively. The dependence of the emission intensities of the LiSr_xBa_1−xPO₄:Sm³⁺ and LiSr_xBa_1−xPO₄:Eu³⁺ phosphors on the x value and Ln³⁺ (Ln³⁺ = Sm³⁺, Eu³⁺) concentration is also investigated.     

Combustion synthesis of CaSc2O4:Ce nano-phosphors in a closed system

The CaSc₂O₄:Ce³⁺ nano-phosphors were successfully prepared by a single-step combustion method at an ignition temperature as low as 200 °C in a closed autoclave using glycine as a fuel and PEG4000 as a dispersant. The samples were characterized by X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscope (TEM). The results revealed that CaSc₂O₄:Ce³⁺ nano-phosphors can be conveniently prepared at an ignition temperature as low as 200 °C, which was much lower than that in the ordinary combustion methods. The optimized ignition temperature was 220 °C. The CaSc₂O₄:Ce³⁺ nano-phosphors give a uniform particle size in the range of 15-20 nm. The low ignition temperature and the addition of PEG4000 dispersant play important roles in the formation of small sized nanoparticles. The as-prepared nano-phosphors were incompact aggregates, but highly dispersed nano-phosphors can be obtained after further ultrasonic treatment. The CaSc₂O₄:Ce³⁺ nano-phosphors give satisfactory luminescence characteristic benefiting from the closed circumstance, in which cerium atoms can be isolated from the oxidizing atmosphere and non-fluorescent Ce⁴⁺ ions can be ruled out. The present highly dispersed CaSc₂O₄:Ce³⁺ nano-phosphors with efficient fluorescence are promising in the field of biological labeling, and the present low temperature combustion method is facile and convenient and can be applied as a universal process for preparing non-aggregate oxide nano-phosphors, especially those being sensitive to air at high temperature.     

Vacuum ultraviolet spectroscopic properties of KSrPO4:Tb

KSrPO₄:Tb³⁺ phosphors were prepared by a solid-state method and their photoluminescence properties were investigated under vacuum ultraviolet excitation. In the excitation spectrum monitoring at 544 nm, the band in the region of 120-162 nm can be attributed to be the overlap of host absorption and charge transfer transition of O²⁻ → Tb³⁺, and the band ranging from 162 to 300 nm was assigned to the f-d transition of Tb³⁺. The photoluminescence spectrum shows that the phosphors exhibited a strong green emission around 544 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺ under the excitation of 147 nm. Optimal emission intensity was obtained when x = 7% in KSr_1-xPO₄:xTb³⁺ and the luminescent chromaticity coordinates were calculated to be (x = 0.317, y = 0.522) for KSr_0.93PO₄:7%Tb³⁺.     

Synthesis and photoluminescence properties of color-tunable BaLa2WO7:Eu phosphor

Color-tunable phosphors BaLa_2−xEu_xWO₇ were synthesized via a solid-state reaction. The absorption, excitation, emission and decay curves were obtained to study the luminescence properties. The experimental results indicate that BaLa_2−xEu_xWO₇ phosphors have two regions in the excitation spectra: one is assigned to the charge-transfer state (CTS) band at about 338 nm, and the other is assigned to the intra-4f transitions at 360-600 nm. The emission spectra of BaLa_2−xEu_xWO₇ phosphors excited at 395 nm exhibit a series of sharp peaks, which are attributed to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions. Luminescence from higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed at low Eu³⁺ concentration. The optimal emission intensity of ⁵D₀ → ⁷F₂ red emission is at x = 0.4 (BaLa_1.6Eu_0.4WO₇). The chromaticity coordinates of BaLa_2−xEu_xWO₇ phosphors vary with Eu³⁺ content from white, orange-red, to red, making it a candidate for a white-light-emitting phosphor in UV-LEDs.     

Eu/Sm ions co-doped white light luminescence SrSiO3 glass-ceramics phosphor for White LED

Eu²⁺/Sm³⁺ co-doped silicate glass was prepared by high temperature melting under reducing atmosphere and the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics were obtained after heat-treatment. X-ray diffraction (XRD) and Raman spectra confirmed the formation of SrSiO₃ nano-crystals in the glass matrix. The photoluminescence excitation (PLE) spectra and photoluminescence (PL) spectra of the samples were measured. A broad emission band from 400 nm to 550 nm due to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ was observed, as well as several sharp emission peaks at 563 nm, 600 nm, 646 nm and 713 nm ascribed to the 4f → 4f transitions of Sm³⁺. The luminescence properties of the glass ceramics with different molar ratio of Eu²⁺/Sm³⁺ were studied and the corresponding chromaticity coordinates were calculated. The ultraviolet light-emitting diode (UV-LED) excitable glass-ceramics emitting white light were obtained by tuning the relative emission intensity of Eu²⁺ and Sm³⁺. The results indicate that the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics can be used as a potential matrix material for White LED under UV-LED excitation.