Luminescence properties of novel Eu3+-doped tantalate NaCaTiTaO6 red-emitting phosphors for solid-state lighting

A novel tantalate red-emitting phosphors NaCa_1-xEu_xTiTaO₆ (x = 0.02-0.50) is synthesized via the traditional solid-state reaction sintering. The photoluminescence properties, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal stability are characterized in detail. Photoluminescence spectra show strong red emission monitored at 614 nm at λ_ex = 395 nm. The spectral properties exhibit excellent color purity and chromaticity coordinate (CIE) characteristics. White light-emitting diodes (w-LEDs) device are fabricated by the prepared phosphors and show high quality of color-rendering index. The investigated results suggest that the Eu³⁺-doped NaCaTiTaO₆ phosphors can be as potential substitute red phosphors for w-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.     

Broadband excited Na3Tb(PO4)2:Ce3+/Eu2+ green/yellow-emitting phosphors with high color purity for LED-based application

To enhance the display quality of light-emitting diodes (LEDs), it is of great significance to exploit green/yellow-emitting phosphors with narrow emission band, high quantum yield, and excellent color purity to satisfy the application. Herein, orthophosphate-based green/yellow-emitting Na₃Tb(PO₄)₂:Ce³⁺/Eu²⁺ (NTPO:Ce³⁺/Eu²⁺) phosphors have been successfully synthesized by a facile solid-state reaction method. The absorption band of NTPO samples was extended to the near-ultraviolet region and the absorption efficiency was significantly improved owing to a highly efficient energy transfer from Ce³⁺/Eu²⁺ ion to Tb³⁺ ion in NTPO host certified by time-resolved PL spectra. Upon 300 nm excitation, the NTPO:Ce³⁺ is characterized by ultra-narrow-band green emission of Tb³⁺ with an absolute quantum yield of 94.5%. Unexpectedly, NTPO:Eu²⁺ emits bright yellow light with a color purity of 73% as a result of the blending of green light emission from Tb³⁺ and red light emission from Eu³⁺. The thermal stability has been improved by controlling the stoichiometric ratio of Na⁺. The prototype white LED used yellow-emitting NTPO:Eu²⁺ phosphor has higher color-rendering index (Ra = 83.5), lower correlated color temperature (CCT = 5206 K), and closer CIE color coordinates (0.338, 0.3187) to the standard white point at (0.333, 0.333) than that used green-emitting NTPO:Ce³⁺ phosphor, indicating the addition of the yellow light component improved the Ra of the trichromatic (RGB) materials.     

Site-selective occupation and luminescence property investigation of Ca18Na3Y(PO4)14:Eu2+ phosphor for full-spectrum LED

Cyan-emitting phosphors have attracted widespread attention as an integral part to realize full-spectrum lighting. Understanding the site occupation of luminescence centers is of great importance to design and clarify the luminescent mechanism for new cyan-emitting phosphors. Here, we report a cyan-emitting phosphor Ca₁₈Na₃Y(PO₄)₁₄:Eu²⁺ synthesized by the high-temperature solid-state method. The crystal structure is characterized by X-ray diffraction and refined by the Rietveld method. The diffuse reflectance spectra, excitation/emission spectra, fluorescence decay curves, thermal stability, and related mechanism are systematically studied. The results show that Ca₁₈Na₃Y(PO₄)₁₄:Eu²⁺ crystallizes in a trigonal crystal system with space group R3c. Under excitation at 350 nm, a broadband cyan emission can be obtained at 500 nm with a half-width of about 120 nm, which is caused by Eu²⁺ occupying five different sites in host, namely, Na2O₁₂ (450 nm), (Ca3/Na1)O₈ (485 nm), Ca2O₈ (515 nm), Ca1O₇ (565 nm), and (Ca4/Y)O₆ (640 nm), respectively. Moreover, crystal structure, room and low temperature spectroscopy, and luminescence decay time are used to skillfully verify the site-selective occupation of Eu²⁺. Finally, a full-spectrum light-emitting diode (LED) lamp is fabricated with an improved color rendering index (∼90.3), CCT (∼5492 K), and CIE coordinates (0.332, 0.318). The results show that Ca₁₈Na₃Y(PO₄)₁₄:Eu²⁺ has the potential to act as a cyan emission phosphor for full-spectrum white LEDs.     

Excitation-dependent energy transfer and color tunability in Dy3+/Eu3+ co-doped multi-component borophosphate glasses

Using the melt-quench technique, potassium zinc borophosphate (KZnBP) glasses incorporated with Dy³⁺, Eu³⁺, and Dy³⁺/Eu³⁺ ions individually and combinedly were prepared, and their photoluminescence (PL)-related features were investigated. The KZnBP glass containing an optimized content of Dy³⁺ (0.5 mol%) is co-doped with Eu³⁺ in various contents, and the energy transfer (ET) process between them was studied at λ_exci = 349, 364, 387 (Dy³⁺), and 394 nm (Eu³⁺). The Dy³⁺/Eu³⁺ co-doped system, when excited with Dy³⁺ excitations has resulted in a significant decrease in the intensity of Dy³⁺ peaks observed at 480 nm (⁴F_9/2→⁶H_15/2, blue) and 574 nm (⁴F_9/2→⁶H_13/2, yellow), with simultaneous enhancement of the intensity of Eu³⁺ peaks at 591 nm (⁵D₀→⁷F₁, orange) and 617 nm (⁵D₀→⁷F₂, red). This trend is due to the efficient energy transfer from Dy³⁺ to Eu³⁺, indicating that Eu³⁺ ions were sensitized by Dy³⁺ ions. Dexter's theory and the Inokuti–Hirayama (I–H) model revealed that the dipole–dipole interaction is accountable for the energy transfer from Dy³⁺ to Eu³⁺ through energy-transfer channels [⁴F_9/2(Dy³⁺)+⁷F_1,2(Eu³⁺)→⁶H_15/2(Dy³⁺)+⁵D₂(Eu³⁺)] and [⁴F_9/2(Dy³⁺)+⁷F₀(Eu³⁺)→⁶H_13/2(Dy³⁺)+⁵D₀(Eu³⁺)]. The color coordinates of the Dy³⁺/Eu³⁺ co-doped glasses under various excitations fall within the white light emission spectrum, indicating their potential application in warm white LEDs.     

Synthesis and luminescence properties of single‐component Ca5(PO4)3F:Dy3+, Eu3+ white‐emitting phosphors

A series of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors was synthesized by a solid‐state reaction method. The XRD results show that all as‐prepared Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ samples match well with the standard Ca₅(PO₄)₃F structure and the doped Dy³⁺ and Eu³⁺ ions have no effect on the crystal structure. Under near‐ultraviolet excitation, Dy³⁺ doped Ca₅(PO₄)₃F phosphor shows blue (486 nm) and yellow (579 nm) emissions, which correspond to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions respectively. Eu³⁺ co‐doped Ca₅(PO₄)₃F:Dy³⁺ phosphor shows the additional red emission of Eu³⁺ at 631 nm, and an improved color rendering index. The chromaticity coordinates of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors also indicate the excellent warm white emission characteristics and low correlated color temperature. Overall, these results suggest that the Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors have potential applications in warm white light‐emitting diodes as single‐component phosphor.     

Eu3+在LiSrPO4中的发光及浓度猝灭机理

采用高温固相法合成了白光发光二极管用LiSrPO4:Eu3+红色荧光粉.测量了LiSrPO4:Eu3+的激发和发射光谱,结果显示材料的发射光谱为一系列尖峰,主峰位于616 nm,具有很强的红光发射;激发光谱中O2-→Eu3+的电荷迁移态CTS (220～310 nm)非常低,Eu3+的f→f (310～500 nm)跃迁吸收很强,主峰位于393 nm,与InGaN(350～410 nm)管芯匹配.比较了LiSrPO4:Eu3+与LiCaPO4:Eu3+、LiBaPO4:Eu3+发射光谱的差异,这三种晶体中Eu3+占据的格位对称性按Ca、Sr、Ba顺序逐渐增加.根据Dexter理论判定Eu3+在LiSrPO4中的浓度猝灭机理为电四极-电四极(q-q)相互作用.加入电荷补偿剂Li+、Na+和Cl 均提高了LiSrPO4:Eu3+材料的发射强度.LiSrPO4: Eu3+是一种适合白光发光二极管激发的红色荧光粉.     

红色荧光粉YAl3(BO3)4:Eu3+的制备及发光性能研究

以稀土氧化物、硝酸铝和硼酸为原料,高温固相反应制备了单相红色荧光粉YAl3(BO3)4:Eu3+,用X射线衍射和发射光谱对荧光粉末的结构和发光性能进行了分析.研究了煅烧温度、Eu3+掺杂量对其发光性能的影响.结果表明,反应物在1 250 ℃下煅烧可制得单相YAl3(BO3)4:Eu3+晶体,在YAl3(BO3)4:Eu3+晶体中,Eu3+取代了YAl3(BO3)4晶体中Y3+,占据了非对称中心格位.在394 nm的紫外光激发下,YAl3(BO3)4:Eu3+荧光粉具有很强的发光性能,与(Y,Gd)BO3:Eu3+荧光粉相比,最强发射线波长由596 nm变为618 nm,由橙红色光变为红色光,色纯度有了很大提高.Eu3+的最佳掺杂量为8%(物质的量分数).     

Preparation,luminescence properties and energy transfer of Ca9Y(PO4)7: Eu2+‐Tb3+ phosphors

Tb³⁺‐doped and Eu²⁺, Tb³⁺ co‐doped Ca₉Y(PO₄)₇ phosphors were synthesized by conventional solid‐state method. Additionally, the luminescence properties, decay behavior and energy transfer mechanism have already been investigated in detail. The green emission intensity of Tb³⁺ ions under NUV excitation is weak due to its spin‐forbidden f‐f transition. While Eu²⁺ can efficiently absorb NUV light and yield broad blue emission, most of which can be absorbed by Tb³⁺ ions. Thus, the emission color can be easily tuned from cyan to green through the energy transfer of Eu²⁺→Tb³⁺ in Ca₉Y(PO₄)₇:Eu²⁺,Tb³⁺ phosphor. In this work, the phenomenon of cross‐relaxation between ⁵D₃ and ⁵D₄ are also mentioned. The energy transfer is confirmed to be resulted from a quadrupole‐quadrupole mechanism.     

Eu~(3+)掺杂浓度对NaYF_4:Eu~(3+)晶体荧光强度的影响

在乙醇和乙二醇的混合溶剂中,用溶剂热法,150℃,反应12 h,成功合成了NaYF4:Eu3+晶体。室温下,用X射线衍射对材料的组成进行了表征,JCPDS号为16-0334。荧光光谱分析表明,在395 nm(7F0→5L4)紫外光激发下,其发射峰在476 nm、540~578 nm、718 nm分别对应着Eu3+的5DJ(J=0,1,2,3)→7FJ(J=1,2,3,4)能级跃迁。并讨论了离子Y3+:Eu3+不同浓度掺杂比对荧光性质的影响。结果表明,Eu3+的最佳掺杂浓度比为5%,当掺杂浓度为10%时,出现荧光猝灭。     

Crystal structure and luminescence mechanism of novel Fe3+-doped Mg0.752Al2.165O4 deep red-emitting phosphors

Nonstoichiometric alumina-rich spinel provides diverse and changeable local environments for transition-metal dopants. In this contribution, novel Mg_0.752Al_2.165−xO₄:xFe³⁺ deep red-emitting phosphors were designed and prepared by the solid-state reaction method. The red emission presents an unexpected shift from 735 to 770 nm by comparing with Fe³⁺-doped MgAl₂O₄. The excitation spectrum of Mg_0.752Al_2.165−xO₄:xFe³⁺ is broadened in the UV region with a new strong peak at 320 nm. The crystal structure refinement and NMR spectra fitting reveal that the cation vacancies and disorder increase with excess Al³⁺ entering the spinel crystal lattice. According to the results of EPR, NMR, and PL/PLE measurements, it was proposed that the Fe³⁺ ions locate at the distorted octahedral coordination. The changes of the local structure of Fe³⁺ ions promote the doublet state's involvement in the d−d transition. It was proposed that the new excitation peak at 320 nm in Mg_0.752Al_2.165−xO₄:xFe³⁺ is associated with the transitions from the ground state ⁶A_1g(⁶S) to the ⁴A_2g(⁴F)/T_1g(⁴P) and doublet states. The transition between the lower energy excited state of ²T_2g(²I) and ⁶A_1g(⁶S) mainly contributes to the deep red emission and the red-shifting effect.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

High-recoverable energy-storage density and dielectric tunability in Eu3+-doped NBT-xSTO binary solid solution films

The Eu³⁺-doped (1 − x)Na_0.5Bi_0.5TiO₃-xSrTiO₃ (Eu-NBT-xSTO) thin films were prepared on Pt/Ti/SiO₂/Si substrates. Raman analysis reveals that the phase structure may undergo a phase evolution of rhombohedral → rhombohedral + tetragonal (morphotropic phase boundary) → tetragonal with increasing content of STO. The scanning electron microscopy images show that the uniformity and high density of Eu-NBT-xSTO films were increased by adding STO, resulting in a pronounced effect on energy storage properties. The ɛ-T curves confirm that a high phase transition diffuseness of γ = 2.02 ± 0.03 and 1.98 ± 0.03 was achieved in Eu-NBT-0.24STO and Eu-NBT-0.3STO films, respectively. Furthermore, a large recoverable energy storage density of 31.5 J cm⁻³ with an efficiency of 64% was obtained in Eu-NBT-0.3STO film, which also exhibited good thermal stability in the temperature range between −60°C and 80°C as well as long-term stability up to 1 × 10⁸ switching cycles. These results suggest that the Eu-NBT-xSTO films may be used in the novel and advanced energy storage capacitors.     

Plant habitat-conscious phosphors: Tuneable luminescence properties of Dy3+-doped Ca8ZnY(PO4)7 phosphors by co-dopants Mg2+ and B3+

Outdoor lighting and other lighting systems can disrupt natural plant growth habits. Thus, LED lighting that is not detrimental to plant growth is required. In our study, Dy³⁺-doped Ca₈ZnY(PO₄)₇:Dy³⁺ phosphor with enhanced luminescence properties caused by the co-dopants Mg²⁺ and B³⁺ were synthesised. The samples had multiple excitation peaks, indicating they are excited by either near-ultraviolet (n-UV) or blue chips. All samples exhibited bright narrow yellow and blue emission corresponding to the transitions of Dy³⁺ ions with ⁴F_9/2→⁶H_13/2 and ⁴F_9/2→⁶H_13/2, respectively. Moreover, doping with Mg²⁺ and B³⁺ enhanced the luminescence intensity, reaching 113.6 and 119.7%, respectively. In addition, the luminescence emission intensity at 150 °C was maintained at approximately 95% of the initial value at 25 °C, and its thermal stability increased by 123%. Devices assembled with an n-UV chip (388 nm) and the as-obtained CZMYP:Dy³⁺ phosphor emitted a bright warm white light and simulated outdoor dark lighting for tobacco cultivation, indicating that the as-prepared phosphor is an excellent candidate material for plant habitat-conscious phosphors.     

Versatile Ca2LnSbO6:Eu3+/Mn4+ (Ln = La,Y, Gd,and Lu) phosphors for temperature sensing and plant growth LED

A multifunctional double-perovskite-type Ca₂LnSbO₆ (Ln = La, Y, Gd, and Lu) phosphors with Eu³⁺ and Mn⁴⁺ co-doped were successfully synthesized and designed to simultaneously apply to temperature sensing and plant growth LED. With temperature varying from 303 to 523 K, the integrated intensity of Mn⁴⁺ ions (²E_g → ⁴A_2g) markedly decline swifter comparing to Eu³⁺ ions (⁵D₀ → ⁷F₂) due to the thermal quenching effect. It implies that Mn⁴⁺ is susceptive to the temperature in this work. Eu³⁺ exhibits high heat resistance, which can be selected as a calibration parameter for the fluorescence intensity ratio temperature sensor. The maximum relative sensitivity (S_r) values of Ca₂LnSbO₆:1%Eu³⁺, 0.5%Mn⁴⁺ (Ln = La, Y, and Gd) phosphor are estimated as 2.19% K⁻¹ at 443 K, 1.68% K⁻¹ at 503 K, and 1.80% K⁻¹ at 483 K, respectively. They are superior to many recent emerging phosphors. Moreover, upon 365 nm excitation, Ca₂LnSbO₆:1%Eu, 0.5%Mn (Ln = La, Y, Gd, and Lu) phosphors display a wide red emission peaking at 696, 680, 677, and 684 nm, respectively. They come from the overlapped of ²E_g–⁴A_2g of Mn⁴⁺ and ⁵D₀–⁷F₄ transition of Eu³⁺. Their full widths at half maximum are 34, 35, 35, and 29 nm, respectively. They are all perfectly overlapping the absorption curves of chlorophyll a and chlorophyll b, and their fabricated red phosphor-converted light-emitting diode device ulteriorly corroborated the promising applications for plant growth. Markedly, the systematic analysis of their crystal chemistry and site preferentially occupancy is first reported and discussed by the bond valence theory.     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

Achieving highly efficient far-red emission from luminescence-ignorable Ca2MgTeO6:Mn4+ to Ca2-zLnzMgTe1-yWyO6:Mn4+ (Ln = La,Y, Gd) phosphors via solid solution and impurity doping strategies

The Mn⁴⁺-doped Ca2MgTeO6 (CMTO) far-red emitting phosphors with double perovskite-type structure were successfully synthesized. Upon near-ultraviolet (n-UV, 300 nm) light excitation, the as-prepared phosphors showed far-red light at 700 nm attributed to the ²E_g→⁴A_2g transition of Mn⁴⁺ ion. The doping concentration of the CMTO:xMn⁴⁺ samples was optimized to be 0.8 mol%. The relevant mechanism of concentration quenching was demonstrated as the dipole-dipole interaction. Furthermore, solid solution and impurity doping strategies were adopted to improve the far-red emission of the luminescence-ignorable CMTO:Mn⁴⁺ phosphor. Series of Ca₂MgTe_(1−y)W_yO₆:0.8 mol%Mn⁴⁺ (y = 0–100 mol%) solid solution and Ca_2−zLn_zMgTe_0.6W_0.4O₆:Mn⁴⁺ (Ln = La, Y, and Gd, z = 10 mol%) phosphors were synthesized through the above two strategies. The luminescence intensity of the optimal Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was 13.7 times that of the CMTO:Mn⁴⁺ phosphor and 2.51 times that of red commercial phosphor K₂SiF₆:Mn⁴⁺. Notably, both CMTO:Mn⁴⁺ and Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphors exhibited remarkable thermal stability compared with most Mn⁴⁺-doped phosphors. Finally, the highly efficient Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was successfully applied in fabricating the warm white light diode (w-LED). This working along both lines strategy exhibited great potential for luminescence optimization of Mn⁴⁺-doped oxide phosphors.     

Luminescence and temperature-sensing properties of Y4GeO8:Bi3+,Eu3+ phosphor

In this paper, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor with dual emission centers was elaborated via conventional solid-state reaction technology. Thorough research on the structure, morphology, and luminous properties of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor, the potential applications in optical thermometry were investigated by means of fluorescence intensity ratio and thermochromic techniques. Under 290 and 347 nm excitation, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor presents broadband emission from ³P₁ → ¹S₀ transition of Bi³⁺ ions and characteristic emission peaks from 4f–4f transition of Eu³⁺ ions. Outstanding temperature-sensing capabilities are acquired from Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor. The maximum relative sensitivity (S_r) can attain 1.51% K⁻¹ (λ_ex = 290 nm). With temperature raising (303–513 K), the emitted color of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor (λ_ex = 290 nm) shifts from faint yellow to red with a high chromaticity shift (0.180), which can be distinguished by the unaided eye clearly. Our results indicate that Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor has potential applications in optical temperature measurement and high-temperature safety marker.     

高效红色荧光粉Li1-xAlSiO4+x:xEu3+的制备与发光性能研究

以碳酸锂、氧化铝、二氧化硅、Eu2O3为原料，采用传统高温固相法在较低温度下制备Eu3+离子掺杂LiAlSiO4红色荧光粉，并通过XRD、SEM和光致发光光谱分别对其晶体结构，粉体形貌和发光性能进行表征。结果表明：Eu3+离子掺杂浓度低于15%时，样品为单一基质；样品可以被近紫外350~420nm波段高效激发，最强激发峰位置位于394nm，发射光谱呈现出Eu3+的特征峰，谱带峰值位置在593 nm、616 nm，分别对应于Eu3+的5D0→7F1、5D0→7F2特征跃迁。最强发射对应的掺杂摩尔百分含量为12%，浓度猝灭的发生主要是因为四极-四极（q-q）相互作用，CIE坐标为（0.6464，0.3526），可应用于近紫外芯片激发LED用红色荧光粉。     

Effect of A+ (A = Li,Na and K) co-doping on enhancing the luminescence of Ca5(PO4)2SiO4:Eu3+ red-emitting phosphors as charge compensator

A series of Ca_5-x(PO₄)₂SiO₄:xEu³⁺ red-emitting phosphors were synthesized through solid-state reaction, and alkali metal ions A⁺ (A = Li, Na and K) were co-doped in Ca₅(PO₄)₂SiO₄:Eu³⁺ to improve its luminescence property. The impacts of synthesis temperature, luminescence center Eu³⁺ concentration and charge compensator A⁺ on the structure and luminescence property of samples were studied in detail. X-ray diffraction results indicated that prepared Ca₅(PO₄)₂SiO₄:Eu³⁺, A⁺ had a standard Ca₅(PO₄)₂SiO₄ structure with space group P6₃/m. Under the excitation of 392 nm, Ca₅(PO₄)₂SiO₄:Eu³⁺ phosphors showed a red emission consisting of several emission peaks at 593 nm, 616 nm and 656 nm, relevant to ⁵D₀→⁷F₁, ⁵D₀→⁷F₂ and ⁵D₀→⁷F₄ electron transitions of Eu³⁺ ions, respectively. Luminescence intensity and lifetime of Ca₅(PO₄)₂SiO₄:Eu³⁺ can be significantly enhanced through co-doping alkali metal ion A⁺, which play an important role as charge compensator. The results suggest that Ca₅(PO₄)₂SiO₄:Eu³⁺, A⁺ red phosphors with excellent luminescence property are expectantly served as red component for white light-emitting diodes excited by near-ultraviolet.