Luminescent characteristics of LiSrBO3:M (M = Eu, Sm, Tb, Ce, Dy) phosphor for white light-emitting diode

LiSrBO₃:M (M = Eu³⁺, Sm³⁺, Tb³⁺, Ce³⁺, Dy³⁺) phosphors which have been developed for white light-emitting diodes (LEDs) were synthesized by a normal solid-state reaction. The emission and excitation spectra indicate that these phosphors can be effectively excited by near-ultraviolet light-emitting diodes (UVLED), and exhibit satisfactory red, green and blue performances, respectively, nicely fitting in with the widely applied UV chip. Under the condition of doping charge compensation Li⁺, Na⁺ and K⁺, the luminescence intensities of these phosphors were increased.     

Effects of co-doped Li+ ions on luminescence of CaWO4:Sm3+ nanoparticles

CaWO₄, CaWO₄:Sm³⁺ and CaWO₄:(Sm³⁺, Li⁺) nanoparticles were synthesized by the precipitation method with addition of PEG 200. The X-ray diffraction patterns show that the obtained samples have a pure tetragonal phase. The CaWO₄ sample shows an emission peak at 418 nm originating from the charge-transfer transitions within the WO₄ ^2? complex. CaWO₄:Sm³⁺ and CaWO₄:(Sm³⁺, Li⁺) samples show emission peaks originating from the f–f forbidden transitions of the 4f electrons of Sm³⁺ ions. The charge compensator of Li⁺ can enhance the emission intensity effectively. It is found that the emission intensity of CaWO₄:(3 mol% Sm³⁺, 4 mol% Li⁺) phosphor is about double that of CaWO₄:3 mol% Sm³⁺ phosphor.     

Enhanced novel orange red emission in LiSr4−x (BO3)3:xSm3+ by K+

LiSr_4?x (BO₃)₃:xSm³⁺ and LiSr_3.985?x (BO₃)₃:0.015Sm³⁺, xK⁺ phosphors were prepared by solid-state reactions. The phases and luminescent properties of the obtained phosphors were characterized. The results demonstrate that the phosphors particles emit an intensive reddish orange light emission under excitation at 403 nm. LiSr_4?x (BO₃)₃:xSm³⁺ phosphor can be efficiently excited by ultraviolet and blue light, and the emission spectrum consists of three emission peaks at 564, 601 and 647 nm. The introduction of the charge compensator K⁺ into the LiSr_4?x (BO₃)₃:xSm³⁺ phosphor matrix promotes the increase of the emission intensity, as well as the decrease of the E _g value. Results suggest that LiSr_3.97(BO₃)₃:0.015Sm³⁺, 0.015 K⁺ is a promising orange–red emitting phosphor for UV LED applications.     

Electrospinning preparation and luminescence properties of one-dimensional SrWO4: Sm3+ nanofibers

One-dimensional Sm³⁺ doped SrWO₄ with or without different charge compensation approaches (co-doping Li⁺, Na⁺ and K⁺) nanofibers were prepared by electrospinning. The structure, morphology and luminescence properties of the obtained nanofiber phosphors were investigated. The X-ray diffraction, Fourier transformation infrared and thermogravimetric results show that the Sr_(1?x)WO₄: Sm _x ³⁺ samples crystallize at 700 °C. Scanning electron microscope results indicate that as prepared nanofibers before/after calcination present uniform fiberlike morphology. The luminescence results show that Sr_(1?x)WO₄: Sm _x ³⁺ phosphors can be excited efficiently by ultraviolet (UV) and near-UV light. The emission spectrum consists of three emission peaks at 561, 596 and 643 nm, corresponding to ⁴G_5/2 → ⁶H_5/2, ⁴G_5/2 → ⁶H_7/2 and ⁴G_5/2 → ⁶H_9/2 transitions of Sm³⁺, respectively. The optimal doping concentration of Sm³⁺ in SrWO₄ is experimentally ascertained to be 4 mol%. The introduction of charge compensator R⁺ (R = Li, Na and K) can enhance the emission intensity of phosphors significantly. The co-doping of Li⁺ has the best compensation effect. The present investigation indicates that Sm³⁺ doped SrWO₄ is a promising orange phosphor for light-emitting diode based on UV chip technology.     

Li doping effects on the upconversion luminescence of Yb3+/Er3+-doped ABO4 (A = Ca,Sr; B = W,Mo) phosphors

ABO₄ (A = Ca, Sr; B = W, Mo):Er³⁺/Yb³⁺/Li⁺ phosphors tri-doped with different concentrations of Li⁺ ion ranging from 0 to 22.5 mol% were prepared by using a solid-state reaction method. And their upconversion (UC) luminescence properties were in estimated under a 975 nm laser-diode excitation. The four kinds of phosphors (CaWO₄, CaMoO₄, SrWO₄, and SrMoO₄) tri-doped with Er³⁺, Yb³⁺ and Li⁺ ions showed strong green UC emission peaks at 530 nm and 550 nm and weak red UC emission. The intensity of green UC emission of Li⁺ doped samples was several higher than that of Li⁺ un-doped samples due to the reduction of lattice constant and the local crystal field distortion around rare-earth ions. The optimum doping concentration of Li⁺ ions was investigated and the effects of Li⁺ concentration for UC emission intensity were studied in detail.     

Deep red phosphors SrMgAl10O17:Mn4+, M (M = Li+, Na+, K+, Cl−) for warm white light emitting diodes

High-saturated red aluminate phosphors SrMgAl₁₀O₁₇ doped with Mn⁴⁺ ions were prepared by solid-state reaction at 1,400 °C. The crystal structure and particle morphology of SrMgAl₁₀O₁₇:Mn⁴⁺ phosphors were investigated by X-ray diffraction, scanning electron microscopy and their photoluminescence were studied by the excitation and emission spectra. The excitation spectrum of samples showed two broad absorption bands ranging from 250 to 480 nm, which indicated that SrMgAl₁₀O₁₇:Mn⁴⁺ could be effectively excited by both near-ultraviolet light and the commercially available blue light of light-emitting diode chips. Simultaneously, the emission spectrum exhibited two sharp peaks (651 and 662 nm) in the deep-red region. It was found that the quenching concentration of Mn⁴⁺ in phosphor was 1.5 mol%. In the end, the effects of doping ions, M (Li⁺, Na⁺, K⁺, Cl^?) ions, on the luminescent properties of SrMgAl₁₀O₁₇:Mn⁴⁺ were investigated, respectively. The results suggested that all of Li⁺, Na⁺, and Cl^? could significantly improve the luminescent properties of SrMgAl₁₀O₁₇:Mn⁴⁺, and the phosphor SrMgAl₁₀O₁₇:Mn⁴⁺, M (M = Li⁺, Na⁺, Cl^?) was expected to be used as a red phosphor in warm white light emitting diode.     

Enhanced red-emitting phosphor Na<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation

A series of novel red-emitting Na₂Ca_3???x Si₂O₈:xEu³⁺ phosphors were synthesized by solid state reactions. The phosphors can strongly absorb 395 nm light, and show red emission with a good color purity. The excitation and emission spectra properties of Na₂Ca₃Si₂O₈:Eu³⁺ were characterized. Na₂Ca₃Si₂O₈:Eu³⁺ with self-compensated and alkali metal ions charge compensated approaches (2Ca²⁺→Eu³⁺ + M⁺, M?=?Li⁺, Na⁺, K⁺) have investigated, which found that the red emission of luminescent intensity can be greatly enhanced, and shows superior luminescent property to the commercial Y₂0₃S:Eu³⁺. The present work implies that the efficient charge compensated phosphors are promising candidates as red-emitting phosphor for w-LEDs.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

A novel blue-emitting Sr3Al2O5Cl2:Ce,Li phosphor for near UV-excited white-light-emitting diodes

A novel blue-emitting Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ phosphor has been synthesized by solid state reaction. The excitation spectrum shows a broad band extending from 300 to 400 nm, and the emission spectrum shows a broad blue band peaking at 450 nm with a half width of about 100 nm. The emission intensity at 250 °C remains at about 50% of that at room temperature. The decay curve at the emission peak consists of fast and slow components. The Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ should be a promising blue phosphor for near ultraviolet-based white-light-emitting diodes.     

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu3+

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

Enhanced red emission in ZnB2O4:Eu by charge compensation

Eu³⁺ doped ZnB₂O₄ without or with different charge compensation (CC) approaches (co-doping Li⁺, Na⁺, K, decreasing the content of Zn²⁺) were prepared by solid state reactions. The phosphors can strongly absorb 393 nm ultraviolet (UV) light which is coupled well with the emission of currently used InGaN-based near UV light emitting diodes (LEDs) and emit red light with a good color purity. The luminescent intensity of phosphors can be remarkably enhanced with any of CC methods. However, the shape and position of excitation and emission spectra keep unchanged. The introduction of Li⁺ can enhance the red emission intensity of Eu³⁺ by ∼4 times with the optimal effect. Red emission of Eu³⁺ can also be enhanced with the other three CC approaches but the effects are not as good as Li⁺ because the volume unbalance in Li⁺ compensation approach is the smallest while net positive charge was offset. The results of this work suggest that volume compensation and equilibrium of mole number should also be taken into account when a CC approaches is selected.     

Double-perovskite Ca3TeO6:Sm3+, Na+ orange–red-emitting phosphors for UV-based white light-emitting diodes

A series of double-perovskite orange–red-emitting Ca_(3?2x)Sm_xNa_xTeO₆ (x?=?0.01–0.25) phosphors have been synthesized via high-temperature method. The single-phase and orthorhombic structure of Ca₃TeO₆:Sm³⁺, Na⁺ phosphors was confirmed by X-ray powder diffraction. Under 405 nm excitation, Ca₃TeO₆:Sm³⁺, Na⁺ phosphors emitted a series of orange–red emission due to the transition of Sm³⁺ from ⁴G_5/2 to ⁶H_J/2 (J?=?5, 7, 9, and 11). The optimal Sm³⁺-doping concentration of Ca_(3?2x)Sm_xNa_xTeO₆ (x?=?0.01–0.25) was x?=?0.10. The thermal-quenching temperature of Ca₃TeO₆:0.10Sm³⁺, 0.10Na⁺ phosphor was above 480 K. A white light-emitting diode (w-LED) based on 410 nm UV chip was successfully fabricated, and it presented a good correlated color temperature and a high color-rendering index (R_a). Therefore, orange–red-emitting Ca₃TeO₆:Sm³⁺, Na⁺ phosphors have potential applications in UV-based w-LEDs.

     

Effects of Li+ ions on the enhancement of up-conversion emission in Ho3+-Yb3+ co-doped transparent glass–ceramics containing Ba2LaF7 nanocrystals

The up-conversion (UC) emission of Ho³⁺-Yb³⁺ and Li⁺ co-doped transparent glass ceramics 45SiO₂-15Al₂O₃-12Na₂CO₃-21BaF₂-7LaF₃-0.2HoF₃-1YbF₃-xLi₂CO₃ (x = 0, 0.5, 1, 2, 4 and 6 mol%) containing Ba₂LaF₇ nanocrystals were investigated. These glass ceramics samples were prepared using the conventional quenching techniques. The Ba₂LaF₇ nanocrystals precipitated from the glass matrix was confirmed by X-ray diffraction (XRD). Compared with the glass ceramics sample without Li⁺, the UC emission intensity of glass ceramics samples with Li⁺ were enhanced. It can be proved that the Li⁺ can affect the enhancement up-conversion (UC) emission. Particularly, the green UC emission intensity band centered at 546 nm was strongly increased twice with the concentration of Li⁺ increasing up to 4 mol%. Through the comparison and analysis of the energy graph, it was shown that the ⁵F₄/⁵S₂→⁵I₈ transition of Ho³⁺ ion obtained the green (546 nm) light. There are two weak fluorescences in the red (657 nm) region and near infrared (753 nm) region of spectrum, which is the ⁵F₄/⁵S₂→⁵I₇ and ⁵F₅→⁵I₈ transition of Ho³⁺. Therefore, the emission results showed that the incorporation of Li⁺ ions into the Ba₂LaF₇:Eu³⁺ lattice could induce a remarkable change of the emission intensity in red region (R = I_ED/I_MD) with 393 nm excitation wavelength. It was indicated that the symmetry of the lattice was destroyed by Li⁺ in glass ceramics. The possible mechanism responsible for the enhancement of UC emission in Ho-Yb co-doped was discussed.     

Green emission enhancement of Ba2SiO4:Eu2+ phosphor via Gd co-doping and charge compensation

A series of new green-emitting Ba_2?x?2ySiO₄:xEu²⁺, yGd³⁺, yR⁺ (R = Li, Na or K) phosphors were synthesized by the solid-reaction method. X-ray diffraction (XRD) and fluorescence spectrophotometer are utilized to characterize the crystal structure and luminescence properties of the as-synthesized phosphors, respectively. The XRD patterns reveal that the doping of Gd³⁺, Eu²⁺ and R⁺ ions have no significant influence on the Ba₂SiO₄ phase. The green emission of Eu²⁺ ion associated with 4f⁶5d¹ → 4f⁷ can be obtained by 396 nm UV excitation source, which match well with the emission wavelength of UV-LEDs chip (380–420 nm). Moreover, the effect of charge compensator ions (Li⁺, Na⁺ or K⁺) on the luminescence intensity of (Ba, Gd)₂SiO₄:Eu²⁺ phosphors were also investigated. When introducing the Li⁺ ions into the (Ba, Gd)₂SiO₄ host lattices, the as-prepared phosphors show the strongest emission. The emission intensity of Ba_1.95SiO₄:0.04Eu²⁺, 0.005Gd³⁺, 0.005Li⁺ is about 1.39 times than that of Ba_1.96SiO₄:0.04Eu²⁺. Furthermore, the mechanism of energy transfer and concentration quenching of Ba_1.982?xSiO₄:xEu²⁺, 0.009Gd³⁺, 0.009Li⁺ phosphors are also discussed.     

Synthesis and luminescence properties of Na+, Li+ compensated Er3+ doped CaAl4O7 phosphors

Here the green-emitting highly luminescent Er³⁺ doped, Er³⁺-Li⁺ co-doped, Er³⁺-Na⁺ co-doped CaAl₄O₇ is synthesized by Pechini method at 1000^°C. Photoluminescence (PL) of CaAl₄O₇: Er³⁺ studies have been compared with Li⁺ co-doped CaAl₄O₇: Er³⁺ and Na⁺ co-doped CaAl₄O₇: Er³⁺. Na⁺ co-doped CaAl₄O₇:Er³⁺ shows increases in luminescence intensity compared to Li⁺ co-doped CaAl₄O₇: Er³⁺ and Er³⁺ doped CaAl₄O_7. The results suggest that CaAl₄O₇:Er³⁺ phosphor can be used as efficient green-emitting phosphor in white LED. The resultant phosphor emits green color peaking at 549 nm upon 378 nm excitation. Powder X-ray diffraction (PXRD) and photoluminescence (PL) techniques have been studied to characterize the synthesized microparticles. Further, this phosphor has good thermal stability that implies its potential to act as green phosphor in white light-emitting diodes. The effect of activator (Er³⁺), Na⁺ co-doped CaAl₄O₇:Er³⁺, and Li⁺ co-doped CaAl₄O₇:Er³⁺ phosphors luminescence spectra as well as photoluminescence life time studies were studied in detail. The results show that as the concentration of Er³⁺ in CaAl₄O₇ increases, the symmetry around the Er³⁺ ion decreases due to the creation of lattice defects in the crystal. Addition of Na⁺ and Li⁺ ions in CaAl₄O₇: Er³⁺leads to a small distortion in the local symmetry of Er³⁺ ions, thereby significantly enhancing its luminescence property. Analysis of photoluminescence life time studies of the prepared samples shows a smaller concentration quenching of Er³⁺ luminescence in charge compensated Na⁺ and Li⁺ CaAl₄O₇ phosphor.

     

Determination of optical and structural properties of lithium silicate ceramics with different ratios of Sm doped

In this study, the synthesis and luminescence characterization of Samarium (Sm³⁺) doped lithium metasilicate (Li₂SiO₃) phosphor ceramic were investigated. It was presented and discussed the results obtained on the luminescence and other optical studies such as X-ray diffraction (XRD), optical absorption and luminescence properties of Li₂SiO₃:Sm³⁺ phosphor ceramic. The Li₂SiO₃ compound was shown a characteristic phase in XRD. The doping in the lithium compound was not having a significant effect on the basic crystal structure of the material. The maximum photoluminescence (PL) emission for Sm³⁺ doped Li₂SiO₃ was observed at 554, 583, 641, 725 nm and bore resemblance to the visible region of the spectrum. The glow curves of all synthesized materials have a complex peak structure after being irradiated with a ⁹⁰Sr–⁹⁰Y beta source. In addition, the peak between 400 and 600 nm was seen in the radioluminescence (RL) spectrum because of a wide peak thought to be caused by silicate.     

A novel red emitting phosphor CaIn2O4:Eu, Sm with a broadened near-ultraviolet absorption band for solid-state lighting

Red phosphor of CaIn₂O₄:Eu³⁺, Sm³⁺ is synthesized by solid state reaction. The ⁵D₀ → ⁷F₂ transition of Eu³⁺ is dominantly observed in the photoluminescence spectrum, leading to a red emission of the phosphor. The doped Sm³⁺ is found to be efficient to sensitize the emission of Eu³⁺ and be effective to extend and strengthen the absorption of near-UV light with wavelength of 400-405 nm, and the energy transfer from Sm³⁺ to Eu³⁺ occurs and is discussed. The effect of the molar concentration of Sm³⁺ on the emission intensities of the phosphor CaIn₂O₄:Eu³⁺, Sm³⁺ is investigated. The temperature quenching effect is also measured from room temperature to 425 K, and the emission intensity of the phosphor at 425 K shows about 85% of that at room temperature. Furthermore, the chromaticity coordinates, the emission intensities and the conversion efficiencies of CaIn₂O₄:Eu³⁺, Sm³⁺ are compared to those of the conventional red phosphor of Y₂O₂S:Eu³⁺.     

Lithium solubility limit in ZnGa2O4:Bi0.0013+,Li+ phosphor

The lithium solubility limit, photoluminescence (PL) and photoluminescence excitation (PLE) properties of lithium ion co-activated ZnGa₂O₄:Bi³⁺,Li⁺ phosphor have been investigated. A LiGaO₂ second phase began to appear from 3 mol% Li⁺ ion co-activated ZnGa₂O₄:Bi³⁺,Li⁺ phosphor. The enhanced brightness of blue (λ_ex = 254 nm) and white (λ_ex = 315 nm) colors of bismuth ions doped ZnGa₂O₄:Bi³⁺,Li⁺ phosphor was assigned to the formation of LiGaO₂. Bi³⁺ activated lithium zinc gallate phosphor showed a more enhanced PLE peak around 315 nm than that of lithium zinc gallate phosphor when λ_em = 520 nm. Thus, we observed that the PL intensity of ZnGa₂O₄:Bi³⁺,Li⁺ phosphor with λ_em = 520 nm was much greater than that of ZnGa₂O₄:Li⁺ phosphor. Also, ZnGa₂O₄:Bi³⁺,Li⁺ phosphor exhibited a shorter decay time than that of ZnGa₂O₄:Li⁺ phosphor by about a factor of about 2.     

Enhanced luminescence by charge compensation in red-emitting Eu-activated Ca3Sr3(VO4)4

The effects of charge compensation on the luminescence behavior of a red-emitting phosphor, Ca₃Sr₃(VO₄)₄:Eu³⁺, were investigated. It has been observed that charge compensated by monovalent ions, especially Na⁺, shows greatly enhanced red emission under ultraviolet excitation. It is found that Na₂CO₃ addition acts as a fluxing agent and plays a role in charge compensation, which clearly improves the emission intensity of Eu³⁺-activated Ca₃Sr₃(VO₄)₄. Enhanced emission intensity of the corresponding charge compensated phosphors under ultraviolet radiation may find application in the production of red phosphors for white light-emitting diodes.     

A novel green emitting phosphor Ca2GeO4:Tb3+

A novel green emitting phosphor, Tb³⁺-doped Ca₂GeO₄ was prepared for the first time by a solid-state reaction. The phosphor showed prominent luminescence in green due to the magnetic dipole transition of ⁵D₄ → ⁷F₅. Structural characterization of the luminescent material was carried out with X-ray powder diffraction (XRD) analysis and field emission scanning electron microscopy (FE-SEM). Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. Photoluminescence measurements indicated that the phosphor exhibited bright green emission at about 541 and 550 nm under UV excitation. In addition, Al³⁺ or Li⁺ co-doping enhances the green emission from Ca₂GeO₄:Tb³⁺ by about 18 and 4 times, respectively, under UV excitation. The excellent luminescence properties make it a possible candidate for flat panel display application.