Dopant Site Environment and Spectrum Blue Shift of Yellow‐Emitting Solid Solution Phosphor Ba2−xSrxMg(PO4)2:Eu2+

An unexpected spectrum blue shift of the yellow emission was observed for solid solution phosphors Ba_2?xSr_xMg(PO₄)₂:Eu²⁺ (x = 0–1.5), when bigger ions Ba²⁺ were substituted by smaller ions Sr²⁺ in Ba₂Mg(PO₄)₂ lattices. The solid solution phosphors were prepared by a solid‐state reaction to clarify the local sites environment of activators Eu²⁺ and tune the anomalous long‐wavelength yellow emission. BaSrMg(PO₄)₂ phase was identified to be isostructural with Ba₂Mg(PO₄)₂ by Rietveld refinements. DFT calculation and photoluminescence show that the activator ions Eu²⁺ in BaSrMg(PO₄)₂ occupy Sr²⁺ and Ba²⁺ sites at an equal probability and both generate an anomalous yellow emission. The yellow emission from Ba_2?xSr_xMg(PO₄)₂:Eu²⁺ was gradually blue shift with increasing Sr²⁺ substitution concentration x from 0.1 to 1. Such unusual blue shift is interpreted based on the evolution of crystal structure parameters due to Sr²⁺ substitution, and subsequently, a site environmental expansion mechanism is proposed. The proposed mechanism could serve as a general model to reveal the underlying factors for spectrum shift caused by cation substitution and contribute to design new solid solution phosphors.     

Phase Identification and Dopant Site Occupancy of Yellow‐Emitting Phosphor BaSrMg(PO4)2:Eu2+

Substitution is widely employed to design single‐host phosphor with multiple sites for one activator, which could emit more than one band. BaSrMg(PO₄)₂:Eu²⁺ was reported as a potential single‐host white light‐emitting phosphor for white LEDs, possessing multiple sites for Eu²⁺ doping. However, different emission spectra were observed in this paper for the sample with same nominal formula. Therefore, XRD and Rietveld refinements were employed to investigate the crystal structure in detail and the results indicated that the sample contains Sr₂P₂O₇ coexisting with the main phase BaSrMg(PO₄)₂. Meanwhile, BaSrMg(PO₄)₂ phase was identified to be isostructural with Ba₂Mg(PO₄)₂ and was confirmed by TEM. Photoluminescence of the phosphor sintered at 900°C shows two emission bands peaking at 424 and 585 nm. Hence, different from the literature, the blue band was assigned to the 4f⁶5d¹→4f⁷ transition of Eu²⁺ occupying the Sr²⁺ sites in Sr₂P₂O₇ and the yellow band to the Eu²⁺ occupying Sr²⁺ and Ba²⁺ sites in BaSrMg(PO₄)₂. The relative intensity ratio of yellow/blue bands is consistent with the content ratio of two phases in the samples with different synthesis temperatures, which is further proof for the original of the blue band. The results of the thermal quenching data demonstrated that the Sr²⁺‐substituted phosphor was better than Ba₂Mg(PO₄)₂.     

Preparation and Luminescence Properties of Blue‐emitting Phosphor Ba2Ca(PO4)2:Eu2+

Using the conventional high temperature solid‐state reaction method Ba₂Ca(PO₄)₂:Eu²⁺ phosphors were prepared. The phase structure, photoluminescence (PL) properties, and the PL thermal stability of the samples were investigated, respectively. Under the excitation at 365 nm, the phosphor exhibited an asymmetric broad‐band blue emission with peak at 454 nm, which is ascribed to the 4f–5d transition of Eu²⁺. It was further proved that the dipole–dipole interactions results in the concentration quenching of Eu²⁺ in Ba₂Ca_1?x (PO₄)₂:xEu²⁺ phosphors. When the temperature turned up to 150°C, the emission intensity of Ba₂Ca_0.99(PO₄)₂:0.01Eu²⁺ phosphor was 59.07% of the initial value at room temperature. The activation energy ΔE was calculated to be 0.30 eV, which proved the good thermal stability of the sample. All the properties indicated that the blue‐emitting Ba₂Ca(PO₄)₂:Eu²⁺ phosphor has potential application in white LEDs.     

Effect of Sr and Ca substitution of Ba on the photoluminescence properties of the Eu2+ activated Ba2MgSi2O7 phosphor

The effects of Sr and Ca substitution of Ba on the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties have been investigated. The physical mechanisms for the photoluminescence variations are discussed. With Rietveld refinement method, the crystal structure of Ba_1.98MgSi₂O₇:0.02Eu²⁺ and the lattice parameters of Sr and Ca substituted phosphors were refined. The emission band shift, the photoluminescence intensity variation, the phosphor chromaticity evolution, the Eu²⁺ lifetime distribution and the thermal stability elevation were investigated. With Sr and Ca substitution, the cell is shrinks. The cell shrinkage is resulting in the increase of the Eu²⁺ 5d electron crystal field splitting intensity, which is the reason for the emission band shift towards the long wavelength band. The photoluminescence intensity is increased firstly and then decreased. The intensity variation is the competitive result between the increase of the crystal structure rigidity and the rise of the lattice defect. The correlated color temperature can be cut down and the color purity can be adjusted. The photoluminescence life time of Eu²⁺ is raised firstly and then decreased. For Sr and Ca substitution, the thermal stability can be elevated. With the forbidden band gap calculation, the reason for the thermal stability elevation was investigated that for the substituted phosphors the forbidden band gap is enlarged and then limits the Eu²⁺ 5d self-ionization from the splitting levels to the conduction band. This work reveals that the Sr and Ca substitution of Ba can elevate the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties and improve the applications for the White Light Emitting Diode.     

The doping concentration dependent tunable yellow luminescence of Sr5(PO4)2(SiO4):Eu

Color tunable yellow-emitting phosphors of Sr_5−5xEu_5x(PO₄)₂SiO₄ (x = 0.05-0.15) were prepared by conventional solid-state reaction method. The X-ray powder diffraction patterns, the photoluminescence excitation and emission spectra were measured. The main excitation bands of the phosphors locate at a broad band extending from 300 to 500 nm, which can match the emission of ultraviolet- and blue-emitting diode chips. The tunable luminescence color was realized by the changing Eu²⁺ doping in Sr₅(PO₄)₂SiO₄. The structure and luminescence properties were investigated. Sr_5−5x(PO₄)₂SiO₄:Eu_5x displays two typical luminescence centers, which originate from two different Sr²⁺ (Eu²⁺) sites in the host. The site-occupation, the luminescence intensity and energy transfer between the Eu²⁺ ions occupying two different crystallographic Sr²⁺ sites were discussed on the base of the luminescence spectra and crystal structure. This is helpful to improve this phosphor for a potential application as a white light emitting diode phosphor.     

Eu‐Doped β‐SiAlON Phosphors: Template‐Assistant Low Temperature Synthesis,Dual Band Emission,and High‐Thermal Stability

A hard template route has been successfully developed for synthesis of β‐SiAlON:Eu phosphors at low temperatures. The synthesis utilizes mesoporous silica (SBA‐15) skeleton as an active Si source, combined with the carbothermal reduction and nitridation method. It has been shown that the additional driving force from high surface area and porosity of SBA‐15 enables β‐SiAlON:Eu (with compositions of Si_6?zAl_z?xO_z+xN_8?z?x: xEu, x = 0.010–0.200 and z = 1.000) phosphors to be formed as a dominant phase at low temperature of 1400°C. The resultant β‐SiAlON:Eu phosphor powders exhibit a typical rod‐like morphology and a well dispersed state. By tailoring the Eu²⁺ concentration in the phosphors, a continuous change in emission band can be realized, that is a blue emission dominated for low Eu²⁺ concentrations and a green emission dominated for high Eu²⁺ doping concentrations. Furthermore, the resultant phosphors exhibit a small thermal quenching up to high temperature of 250°C. Therefore, the developed method is beneficial to synthesize LED phosphors of oxynitride systems at lower temperatures.     

Synthesis,structural characterization,and photoluminescence properties of Eu3+‐doped Mg3‐xEux(BO3)2 phosphor

Eu³⁺‐doped Mg_3‐xEu_x(BO₃)₂ (x = 0.000, 0.005, 0.010, 0.020, 0.050, and 0.100) phosphors were synthesized for the first time by solution combustion synthesis method, which is a fast synthesis method for obtaining nano‐sized borate powders. The optimization of the synthesis conditions of phosphor materials was performed by TG/DTA method. These phosphors were characterized by XRD, FTIR, SEM‐EDX, and photoluminescence, PL analysis. The XRD analysis exhibited that all of the prepared ceramic compounds have been crystallized in orthorhombic structure with space group Pnnm. Also, the influence of europium dopant ions on unit cell parameters of host material was analyzed using Jana2006 program and the crystalline size was determined by Debye‐Scherrer's formula. The luminescence properties of all Eu³⁺‐doped samples were investigated by excitation and emission spectra. The excitation spectra of Mg_3‐xEu_x(BO₃)₂ phosphors show characteristic peak at 420 nm in addition to other characteristic peaks of Eu³⁺ under emission at 613 nm. The emission spectra of Eu³⁺‐doped samples indicated most intensive red emission band dominated at 630 nm belonging to ⁵D₀→⁷F₂ magnetic dipole transition. Furthermore, the optimum or quenching concentration of Eu³⁺ ion has been determined as x = 0.010 showed the maximum emission intensity when it was excited at 394 nm.     

Synthesis,Structure, and Tunable Luminescence Properties of Novel Ba3NaLa(PO4)3F:Eu2+,Mn2+ Phosphors

A series of luminescent emission‐tunable phosphors Ba₃NaLa(PO₄)₃F:Eu²⁺,Mn²⁺ have been prepared by a high‐temperature solid‐state reaction. The Rietveld refinement analysis confirms that the obtained phosphors possess pure apatite crystalline phase and the sites' occupancy of dopant has been also discussed. Upon the excitation of 355 nm, the emission spectra of Ba₃NaLa(PO₄)₃F:Eu²⁺,Mn²⁺ consist of two broad bands assigned to 5d–4f transition of Eu²⁺ and ⁴T₁ (⁴G)–⁶A¹ (⁶S) transitions of Mn²⁺, respectively. Energy transfer (ET) occurs in Eu²⁺, Mn²⁺ codoped Ba₃NaLa(PO₄)₃F host. On the basis of the thorough analysis and comparison upon their excitation, emission properties, and the decay behaviors, it is demonstrated that the ET mechanism between Eu²⁺ and Mn²⁺ is ascribed to the exchange interaction, and the tunable emission color in the novel apatite host can be realized.     

Sr-induced color-tunable and thermal stability enhancing in the phosphor (Ba1-xSrx)9Lu2Si6O24:Eu2+ for solid-state lighting

Rare earth ions’ site occupation is significant for studying luminescence properties by changing the host composition. The (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ (x = 0-0.4) tunable-color phosphors were synthesized via a high temperature solid-state reaction. With the Sr²⁺ ions concentration increase, the luminescent color could be tuned from blue to green. This phenomenon is discussed in detail through the ions occupation in the host lattice. More importantly, the temperature-dependent luminescence of (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphors was investigated and exhibited excellent thermal stability. Furthermore, white LED device has been fabricated using (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphor mixed with commercial red phosphor Sr₂Si₅N₈:Eu³⁺ combined with a 370 nm UV-chip. This device showed correlated color temperature (CCT) of 5125 K and high color render index (CRI) of 91. This phosphor will be a promising candidate as a tunable-color phosphor for UV-based white LEDs.     

Photostimulated and Long Persistent Luminescence Properties from Different Crystallographic Sites of β‐Sr2SiO4: Eu2+, R3+ (R = Tm,Gd)

Sintered ceramics of β‐Sr₂SiO₄: Eu²⁺, R³⁺(R=Tm, Gd) were prepared and their spectroscopic properties were evaluated. A large enhancement of green photostimulated luminescence (PSL) was observed from β‐Sr₂SiO₄:Eu²⁺ codoping with Tm³⁺ at a recognizable intensity level, and the most efficient PSL was obtained when the codoping concentration of Tm³⁺ was 0.002. It was proved that the introduction of Tm³⁺ created a large number of oxygen vacancies which serve as traps for electrons excited by UV irradiation. In addition, a distinguishable difference between the photoluminescence (PL) and PSL spectra of β‐Sr₂SiO₄: Eu²⁺, Tm³⁺ was observed, namely the PSL spectrum exhibits only a symmetric emission band peaked at about 540 nm while both 470 and 540 nm peaks were detected in the PL spectrum. It is safe to say that PSL only derives from one emission center of Eu2 in the crystallographic Sr2 sites, which could be ascribed to the different distribution of trap centers for two crystallographic Sr sites .     

Light‐induced electrons suppressed by Eu3+ ions doped in Ca11.94−xSrxAl14O33 caged phosphors for LED and FEDs

Control of light‐induced electron generation is of vital importance for the application of caged phosphors. For Eu‐doped Ca_11.94?xSr_xAl₁₄O₃₃ caged phosphors, the suppressed effect of strontium doping on the light‐induced electrons is observed compared to the europium‐free Ca_11.94?xSr_xAl₁₄O₃₃ phosphors. In the presence of europium ions, Sr doping will promote the reduction of Eu³⁺ to Eu²⁺. The Rietveld refinement suggests that unit cell volumes of the Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 samples are expanded when Ca²⁺ ions are replaced by Sr²⁺ ions. The absorption and FTIR transmittance spectra confirm that the competitive reaction of encaged O^2? anions with H₂ is suppressed. For the sample (x=0.48), the higher thermal activation energy (~0.40 eV) for luminescence quenching can be attributed to the more rigid framework structure after Sr doping. For Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 phosphors, their emission colours are tuned from red to purple upon 254 nm excitation and from pink to blue under electron beam excitation through Sr substitution. The insight gained from this work may have a significant guiding to design new phosphors for LED and FEDs and novel nanocaged mutifunctional materials.     

Optical Energy Storage Properties of (Ca1−xSrx)2Si5N8: Eu2+, Tm3+ Solid Solutions

While the reddish‐orange emitting phosphors M₂Si₅N₈:Eu²⁺(M = Ca, Sr) have been intensively investigated as potential materials for white‐light‐emitting diodes, in this study, optical energy storage properties of (Ca_1?xSr_x)₂Si₅N₈: Eu²⁺, Tm³⁺ (x = 0–1) solid solutions were tuned by cation substitution, which was commonly used to tune color point for improving w‐LEDs. Partial substitution of either Ca by Sr or Sr by Ca resulted in a redshifted Eu²⁺ emission which had a demarcation point at x = 0.5. Furthermore, the (Ca_1?xSr_x)₂Si₅N₈: Eu²⁺, Tm³⁺ materials exhibited similar persistent‐ and photostimulated luminescence behaviors with a maximum intensity at about x = 0.2. Such optical energy storage characters of the samples were attributed to the more appropriate trap depths (322–333 K) and higher density of energy level traps indicated by the thermoluminescence analysis.     

Sr3Lu (VO4)3: Eu3+ red-emitting phosphors for warm white LEDs

A series of novel red emission phosphors Sr₃Lu_1-x(VO₄)₃:xEu³⁺(x = 0.007, 0.009, 0.02, 0.04, 0.06) were synthesized successfully by traditional high-temperature solid-state reaction. The results of X-ray diffraction (XRD) reveal the doped Eu³⁺ ions have replaced the lattice sites of Lu³⁺ ions. The diffuse reflectance spectra illustrate the energy gap of Sr₃Lu(VO₄)₃ host is 3.61 eV. The room-temperature steady-state fluorescence spectra show that these phosphors can be effectively pumped by the charge-transfer band (CTB) of the host in near ultraviolet (NUV) spectral region and then produce strong and pure red emission at 615 nm originated from ⁵D₀ → ⁷F₂ electric dipole transition of Eu³⁺. The Commission Internationale de L’Eclairage (CIE) coordinates of Sr₃Lu_0.96(VO₄)₃:0.04Eu³⁺ are (x = 0.65, y = 0.35), which are very close to the red standard of National Television Standards Committee NTSC (0.67, 0.33). The fabricated warm white-light-emitting diodes (LED) demonstrate high color-rendering index Ra as 93. The results imply the red-emitting Sr₃Lu(VO₄)₃:Eu³⁺ phosphors could be potentially utilized in the fields of solid-state lighting.     

Partial cation substitution of tunable blue-cyan-emitting Ba2B2O5:Ce3+ for near-UV white LEDs

In this study, Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ ions act to tune the emission band to the blue-cyan region in Ba_xSr_yB₂O₅:Ce³⁺ (BSBO), Ba_xCa_zB₂O₅:Ce³⁺ (BCBO), Ba_xZn_uB₂O₅:Ce³⁺ (BZBO), and Ba_xMg_vB₂O₅:Ce³⁺ (BMBO) phosphors. A red shift occurs with the increase of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ concentration, and a blue shift occurs when the concentrations of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ exceed the critical value. The emission color can be tuned from deep blue (0.15, 0.12) to cyan (0.16, 0.27) upon 365 nm UV lamp excitation due to the crystal field splitting and centroid shifts. The excitation band shift to long wavelength by introducing ions, so that the synthesized phosphor can be better matched with the n-UV chip. The emission intensity slowly decreases with the temperature increasing. Therefore, the BMBO:Ce³⁺, BZBO:Ce³⁺, BCBO:Ce³⁺, and BSBO:Ce³⁺ phosphors with relatively good thermal stability were synthesized, which could have potential applications in the n-UV white LEDs.     

Synthesis and luminescent properties of Sr4−xSi3O8Cl4: xEu3+ red phosphor by hydrothermal method

Sr_4‐xSi₃O₈Cl₄:xEu³⁺ (SSOC:Eu³⁺) phosphors were successfully synthesized by hydrothermal method. The crystallization of this phosphor was analyzed by means of X‐ray diffraction patterns. The size and morphology were recorded using SEM patterns of samples. And the PLE and PL spectra were characterized by a PL spectrophotometer. Excited by 394 nm UV light, the intense red emission is recognized in SSOC:Eu³⁺ phosphor and the main emission peak located at 620 nm. The influences of Eu³⁺ concentration, pH value of reaction solution, and charge compensator on PL spectra of SSOC:Eu³⁺ phosphors were investigated. The results revealed that this red phosphor had potential applications for white LEDs.     

Fabrication and Characterization of Transparent (Y0.98−xTb0.02Eux)2O3 Ceramics with Color‐Tailorable Emission

Transparent (Y_0.98?xTb_0.02Eu_x)₂O₃ (x = 0–0.04) ceramics with color‐tailorable emission have been successfully fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h. These ceramics have the in‐line transmittances of ~73%–76% at 613 nm, the wavelength of Eu³⁺ emission (the ⁵D₀→⁷F₂ transition). Thermodynamic calculation indicates that the Tb⁴⁺ ions in the starting oxide powder can essentially be reduced to Tb³⁺ under ~10^?3 Pa (the pressure for vacuum sintering) when the temperature is above ~394°C. The photoluminescence excitation (PLE) spectra of the transparent (Y_0.98?xTb_0.02Eu_x)₂O₃ ceramics exhibit one spin‐forbidden (high‐spin, HS) band at ~323 nm and two spin‐allowed (low‐spin, LS) bands at ~303 and 281 nm. Improved emissions were observed for both Eu³⁺ and Tb³⁺ by varying the excitation wavelength from 270 to 323 nm, without notably changing the color coordinates of the whole emission. The transparent (Y_0.98Tb_0.02)₂O₃ ceramic exhibits the typical green emission of Tb³⁺ at 544 nm (the ⁵D₄→⁷F₅ transition). With increasing Eu³⁺ incorporation, the emission color of the (Y_0.98?xTb_0.02Eu_x)₂O₃ ceramics can be precisely tailored from yellowish‐green to reddish‐orange via the effective energy transfer from Tb³⁺ to Eu³⁺ under the excitation with the peak wavelength of the HS band. At the maximum Eu³⁺ emission intensity (x = 0.02), the ceramic shows a high energy‐transfer efficiency of ~85.3%. The fluorescence lifetimes of both the 544 nm Tb³⁺ and 613 nm Eu³⁺ emissions were found to decrease with increasing Eu³⁺ concentration.     

Preparation of Sr1−xCaxLiAl3N4:Eu2+ Solid Solutions and Their Photoluminescence Properties

A series of quaternary nitride solid solutions with a general formula of Sr_1?xCa_xLiAl₃N₄:0.5%Eu²⁺ was synthesized by a solid‐state reaction method. The experimental results showed that a proper amount of Ca‐doping can improve the crystallinity and the photoluminescence properties of the produced phosphors. Rietveld refinement showed that the volume of the unit cell shrank with the increase of Ca substitution for Sr, which resulted in a red shift of the emission spectra from 654 to 665 nm under blue excitation at 475 nm. Rietveld refinement and CASTPE calculations suggested that Ca²⁺ ions prefer to occupy the smaller Sr(I) sites in the crystal lattice, which increases the amount of Eu²⁺ ions in Sr(II) sites and enables the tuning of the chromaticity coordinates of the obtained phosphors. The thermal stability of the produced phosphors is better than that of commercial Sr₂Si₅N₈:Eu²⁺ phosphor. The experimental results qualify the solid‐solution Sr_1?xCa_xLiAl₃N₄:0.5%Eu²⁺ for consideration as a potential candidate for application in white LEDs.     

Efficient,stable, broadband cyan-emitting Ca-substituted Ba9Lu2Si6O24:Eu2+ with multisite luminescence for NUV-wLEDs

In order to develop an efficient and stable broadband cyan phosphor for full spectrum white lighting emitting diodes (wLEDs), novel Ba₉Lu₂Si₆O₂₄:Eu²⁺, xCa²⁺ is designed and synthesized. Ca-substitution induces Eu²⁺ ions into Lu³⁺ crystallographic site, which achieve rare nonequivalent cation substitution of Eu²⁺. Effects of Ca-substitution on crystal structure of matrix and phosphor are investigated by X-ray photoelectron spectroscopy, X-ray powder diffraction, transmission electron microscopy, and density functional thoery (DFT). Ba₉Lu₂Si₆O₂₄:Eu²⁺, xCa²⁺ can be effectively excited by with near-ultraviolet (NUV) and exhibit broadband cyan emission with full width at half maximum (FWHM) of 119.7 nm at x = 0.2, due to the multisite luminescence centers. For the sample x = 0.2, the internal quantum efficiency is 92.61%, and the luminous intensity at 423 K remains 89% of that measured at room temperature. The rigid structure of [SiO4]-[LuO6]-[SiO4] doped with Eu2+ ion makes Ca-substituted samples exhibit excellent luminescence efficiency and thermal stability. Our work develops a significant strategy based on multisite cation regulation to explore NUV-excited broadband cyan phosphors for full spectrum wLEDs.     

High luminescent brightness and thermal stability of red emitting Li3Ba2Y3(WO4)8:Eu3+ phosphor

A series of Li₃Ba₂Y_3−x(WO₄)₈:xEu³⁺ (x=0.1, 1, 1.5, 2 and 2.8) phosphors were synthesized by a high temperature solid-state reaction method. Under the excitation of near ultraviolet (NUV) light, the as-prepared phosphor exhibits intense red luminescence originating from the characteristic transitions of Eu³⁺ ions, which is 1.8 times as strong as the commercial Y₂O₂S:Eu³⁺ phosphor. The optimal doping concentration of Eu³⁺ ions here is confirmed as x=1.5. The electric dipole-quadrupole (D-Q) interaction is deduced to be responsible for concentration quenching of Eu³⁺ ions in the Li₃Ba₂Y₃(WO₄)₈ phosphor. The analysis of optical transition and Huang-Rhys factor reveals a weak electron-phonon coupling interaction. The temperature-dependent emission spectra also indicate that the as-prepared Li₃Ba₂Y₃(WO₄)₈:Eu³⁺ phosphor has better thermal stability than that of the commercial Y₂O₂S:Eu³⁺ phosphor. Therefore, our results show that the as-prepared Li₃Ba₂Y₃(WO₄)₈:Eu³⁺ phosphor is a promising candidate as red emitting component for white light emitting diodes (LEDs).     

Cation vacancy repair towards a new yellow Ca7Sr3Na(PO4)7:Eu2+ phosphor

Cationic substitution is a prevalent strategy to tune the luminescence spectra of phosphors. In this work, we reported a series of Eu²⁺-activated whitlockite type Ca₇Sr_3.5-0.5xA_x(PO₄)₇ (CSPA; A =Li, Na, K) (x = 0–1.00) phosphors. The substitution by Na⁺ for both half occupied/vacant M(4) site was verified via Raman spectra, Reitveld refinement and HR-TEM, whereas a similar accommodation of K⁺ into the Ca₂Sr(PO₄)₂ (CSP) host cannot be realized due to the significant size mismatch. A continuous increase of Na⁺ contents led to the progressively structural contraction, promoting the migration of Eu²⁺ activator from looser M(4) to other sites, and regulating the luminescence behaviors. Consequently, the gradual red-shift of emission band terminated at a new yellow phosphor Ca₇Sr₃Na(PO₄)₇:0.04Eu²⁺. The cation vacancy repair developed in this work can not only migrate the Eu²⁺ activator among different cation sites, but also serves as a new strategy for tuning the luminescence properties of phosphor.