Site occupation and energy transfer in full color emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+

White light-emitting diodes (WLEDs) fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting. The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor. Here, we report a high quality white light-emitting phosphor Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ with spectral distribution covering whole visible region. Blue light emission originates from Ce³⁺ ions occupying preferentially Ba²⁺ site by controlling synthesis conditions. Green and red lights are obtained from Eu²⁺ occupying Ba²⁺ (and Ca²⁺) site and Mn²⁺ occupying Ca²⁺ site, respectively. In this triple-doped phosphor, strong red emission with a low concentration of Mn²⁺ is realized by the efficient energy transfer from Ce³⁺ and Eu²⁺ to Mn²⁺. Furthermore, high quality white light is accomplished by properly tuning the relative doping amount of Ce³⁺(K⁺)/Eu²⁺/Mn²⁺ based on efficient simultaneous energy transfer. The results indicate that Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ is a promising white light-emitting phosphor in WLEDs application.     

Synthesis and luminescence enhancement of red-emitting Sr9Y(PO4)7:Eu3+ phosphor through Gd3+ co-doping for white light-emitting diodes

A series of Sr₉Y(PO₄)₇:Eu³⁺ and Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphors were prepared via a high-temperature solid-state method, Gd³⁺ ion was co-doped in Sr₉Y(PO₄)₇:Eu³⁺ as sensitizer to enhance the luminescence property. The X-ray diffraction results verify that the structure of the as-prepared samples is consistent with the standard Sr₉Y(PO₄)₇ phase. All the Sr₉Y(PO₄)₇:Eu³⁺ samples show both characteristic emission peaks at 594 nm and 614 nm under near-ultraviolet excitation of 394 nm. The co-doping of Gd³⁺ significantly improves the luminescence intensity of the Sr₉Y(PO₄)₇:Eu³⁺ phosphors due to the crystal field environment effect and energy transfer of Gd³⁺→Eu³⁺ caused by the introduction of Gd³⁺, especially Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺, which emission intensity is higher than that of Sr₉Y(PO₄)₇:0.11Eu³⁺ by 1.21 times. The color purity and lifetime of Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺ phosphor are 88.26% and 3.7615 ms, respectively. A w-LED device was packaged via coating the as-prepared phosphor on n-UV chip of 395 nm with commercial phosphors. These results exhibit that the Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphor can be used as a red component in the w-LEDs application.     

Enhancement of oxygen/pressure sensing performance of Eu3+-doped YSZ phosphors via Bi3+ sensitization

The effects of the incorporation of a Bi³⁺ sensitizer on the phosphorescence properties and oxygen partial pressure sensitivity of the Eu³⁺ doped yttria stabilized zirconia (YSZ) phosphors were studied using a lifetime-based optical measurement system. Two series of YSZ: Eu phosphors were investigated in this work: Eu_0.01Bi_xY_0.07-xZr_0.92O_1.96 substitutional series and Eu_0.01Bi_xY_0.07Zr_0.92-xO_1.96-0.5x additive series. The phosphorescence intensity of the additive-series phosphors was enhanced by 47% excited at 405 nm with a Bi³⁺ concentration of 2 mol% due to the energy transfer between Bi³⁺ and Eu³⁺. In contrast, the phosphorescence intensity of the substitutional-series phosphors decreased as the Bi³⁺ concentration increased. The phosphorescence lifetimes for both series phosphors were highly sensitive to oxygen partial pressure at elevated temperatures. With increasing Bi³⁺ concentration, the oxygen sensitivities of both series were enhanced initially, which was related to the increment of concentration dependent non-radiative decay via cross-relaxation between Bi³⁺ and Eu³⁺. With 1 mol% Bi³⁺ doping, the oxygen sensitivity was enhanced by 28% and 12% for substitutional-series and additive-series phosphors, respectively. As the Bi³⁺ concentration further increased, the oxygen sensitivities of both series declined, which was attributed to the energy transfer between Bi³⁺, the formation of Bi³⁺ aggregates as well as the increase of the Eu³⁺ site symmetry. The results of this study not only provided valuable references for phosphor thermometry, but also offered new ideas for developing high-temperature non-contact pressure sensors.     

Improving the luminescence properties and powder morphologies of red-emitting Sr0.8Ca0.19AlSiN3:0.01Eu2+ phosphors for high CRIs white LEDs by adding fluxes

Red-emitting Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphor with halide fluxes for use in the production of white light-emitting diodes (white LEDs) with high-colour rendering indices (CRIs) was prepared through the high-temperature solid-state method. Fluoride (NaF, SrF₂, BaF₂, CaF₂, AlF₃·3H₂O and CeF₃), chloride (NH₄Cl, BaCl₂, MgCl₂, NaCl and LiCl) and composite fluxes (NaF + SrF₂, SrF₂+NH₄Cl and NaF + NH₄Cl) were applied in the phosphors. NaF, SrF₂, NH₄Cl and NaF + SrF₂ fluxes had prominent effects on the characteristics of Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphors. Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphors with various powder morphologies can be obtained through the addition of fluxes, which are conducive for phosphor formation. The powder morphologies of phosphors incorporated with NaF + SrF₂ were preferable to those of powders incorporated with other fluxes. This result indicated that the incorporation of NaF + SrF₂ into Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ yielded phosphors with high luminescent intensity and quantum efficiency, excellent thermal stability, narrow full widths at half-maximum (FWHM, 75.2 nm), uniform rod-like morphologies with large particle sizes (D₅₀ = 16.99 μm) and good particle dispersion. White LEDs with high CRIs were obtained by combining prepared phosphors (NaF + SrF₂ additive) with the commercial green-emitting phosphors Y₃(Al,Ga)₅O₁₂:Ce³⁺ and (Sr,Ba)₂SiO₄:Eu²⁺. White LEDs with Y₃(Al,Ga)₅O₁₂:Ce³⁺ and (Sr,Ba)₂SiO₄:Eu²⁺ phosphors had correlated colour temperatures (CCTs) of 3064 and 3023 K, respectively, and CRIs of 81.8 and 92.4, respectively. Therefore, NaF + SrF₂ can be used as a favourable flux for the production of Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺.     

Y4.67Si3O13-based phosphors: Structure,morphology and upconversion luminescence for optical thermometry

How to improve the sensitivity of the temperature-sensing luminescent materials is one of the most important objects currently. In this work, to obtain high sensitivity and learn the corresponding mechanism, the rare earth (RE) ions doped Y_4.67Si₃O₁₃ (YS) phosphors were developed by solid-state reaction. The phase purity, structure, morphology and luminescence characteristics were evaluated by XRD, TEM, emission spectra, etc. The change of the optical bandgaps between the host and RE-doped phosphors was found, agreeing with the calculation results based on density-functional theory. The temperature-dependence of the upconversion (UC) luminescence revealed that a linear relationship exists between the fluorescence intensity ratio of Ho³⁺ and temperature. The theoretical resolution was evaluated. High absolute (0.083 K⁻¹) and relative (3.53% K⁻¹ at 293 K) sensitivities have been gained in the YS:1%Ho³⁺, 10%Yb³⁺. The effect of the Yb³⁺ doping concentration and pump power on the sensitivities was discussed. The pump-power–dependence of the UC luminescence indicated the main mechanism for high sensitivities in the YS:1%Ho³⁺, 10%Yb³⁺. Moreover, the decay-lifetime based temperature sensing was also evaluated. The above results imply that the present phosphors could be promising candidates for temperature sensors, and the proposed strategies are instructive in exploring other new temperature sensing luminescent materials.     

Photoluminescence enhancement in a Na5Y(MoO4)4:Dy3+ white-emitting phosphor by partial replacement of MoO42− with WO42− or VO43−

A series of Na₅Y(MoO₄)_4-yA_y:Dy³⁺ (A = WO₄^2?, VO₄^3?; y = 0–0.05) phosphors were synthesized by the combustion method. Some of the MoO₄^2? sites were occupied by WO₄^2? and VO₄^3? anions, which enhanced the luminescence property of Dy³⁺-doped Na₅Y(MoO₄)₄. XRD results show that the crystal structures of the samples were consistent with the standard Na₅Y(MoO₄)₄ phase. Under excitation at 352 nm, the Na₅Y(MoO₄)_4-yA_y:Dy³⁺ phosphors exhibited a characteristic blue emission at 485 nm and a yellow emission at 577 nm, which originated from the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions, respectively. White light can be achieved by combining these blue and yellow emissions. After replacing MoO₄^2? with WO₄^2? and VO₄^3? anions in Na₅Y(MoO₄)₄:Dy³⁺, the luminescence intensity of Dy³⁺ was significantly improved due to the crystal field effect. The results indicate that Na₅Y(MoO₄)_3.97(WO₄)_0.03:Dy³⁺ and Na₅Y(MoO₄)_3.97(VO₄)_0.03:Dy³⁺ phosphors have good prospects for application in n-UV-excited w-LEDs.     

Alkali metal ion substitution induced luminescence enhancement of NaLaMgWO6:Eu3+ red phosphor for white light-emitting diodes

Alkali metal ion substitution is an effective strategy to improve the luminescence properties of phosphors. In this work, a series of red-emitting phosphors Na_1-xLi_x/2K_x/2La_0.6Eu_0.4MgWO₆ were prepared by a traditional high-temperature solid-state reaction. Their phase structure, microstructure, luminescence properties and potential application in phosphor-converted white light-emitting diodes (pc-WLEDs) were investigated in detail. X-ray diffraction (XRD) result revealed the formation of a solid solution when x?≤?0.3, which kept monoclinic structure of NaLaMgWO₆. Photoluminescence investigation indicated that the partial substitution of Li⁺/K⁺ ions for Na⁺ ions improved largely the red emission of Eu³⁺. Based on the optimized Na_0.7Li_0.15K_0.15La_0.6Eu_0.4MgWO₆ sample with relatively good thermal stability, a WLED device was fabricated by combining a near-ultraviolet (NUV) chip (~400?nm) with the phosphor mixture of commercial green/blue phosphors and the optimized red phosphor. The results indicated that the optimized red phosphor in this work could be a potential candidate for WLEDs pumped by NUV chips.     

Preparation and characterization of multilayer Gd2O2S:Tb phosphor screen for X-ray detection application

Gd2O2S:Tb (GOS) phosphor screen, generally with a multilayer structure, has been widely used in digital X-ray imaging. GOS phosphor screen is fabricated via a slip casting route, which is an effective method to obtain multilayer composites with good strength. The GOS slurry was prepared using the menhaden oil, polyvinyl butyral and PEG-400 as dispersant, binder and plasticizer, respectively, and slip casted on a support layer. After the GOS scintillation layer is formed, a transparent polyethylene terephthalate film is covered on it as a protective layer. The X-ray excited emission spectra of the obtained GOS phosphor screen is well match to the spectral response of a-Si:H photodiode, and the spatial resolution was close to 3.7 LP/mm, which could meet the request of the commercial application.     

Biomineralization,strength and cytocompatibility improvement of bredigite scaffolds through doping/coating

Coprecipitation-derived, sacrificial polymeric (urethane) foam-fabricated bredigite (Ca₇MgSi₄O₁₆) scaffolds were processed by individual and combined treatments of fluoride doping and poly (lactic-co-glycolic acid) (PLGA) coating and then studied in terms of structure, mechanical strength, bioactivity and cell biocompatibility in vitro. According to scanning electron microscopy and Archimedes porosimetry, the geometrical characteristics of pores for all the scaffolds are in the appropriate range for hard tissue regeneration applications. The apatite-formation ability of the samples immersed in a simulated body fluid is improved by doping for both the bare and coated conditions, based on microscopic and energy-dispersive X-ray spectroscopic analyses. Both the treatments advantageously buffer physiological pH changes imposed due to the fast bioresorption of the ceramic. Also, the biodegradable PLGA coating typically enhances the compressive strength of the scaffolds, which is critical for bone tissue engineering. In accordance with the MTT assay on osteoblast-like cells (MG-63) cultures, both the processes individually enhance the cell viability, while the highest improvement is obtained for the combined application of them. It is finally concluded that fluoride doping and PLGA coating are impressive approaches to improve the bioperformance of bredigite-based scaffolds.