Recent Research Progress of Red Phosphors for PDPs Applications

The commercial vacuum ultraviolet (VUV) red phosphor (Y, Gd)BO₃:Eu³⁺ has low luminous efficiency and poor color purity. Our work aims to overcome this drawback and we mainly devote to investigating the luminescence mechanism, improving the commercial red phosphor, and seeking for new red emitting VUV materials with high efficiency. Based on the investigation of the photoluminescence mechanism of VUV phosphors, both the luminous efficiency and the color purity of (Y, Gd)BO₃:Eu³⁺ are improved. Additionally, a series of novel VUV red phosphors have been developed, such as (Gd,Y)Al₃(BO₃)₄:Eu³⁺ and (La,Gd)P₃O₉:Eu³⁺. This presentation is a review about the recent research progress of red phosphors for plasma displays (PDPs) applications in our group.     

Waterproof Alkyl Phosphate Coated Fluoride Phosphors for Optoelectronic Materials

A facile approach for coating red fluoride phosphors with a moisture‐resistant alkyl phosphate layer with a thickness of 50–100 nm is reported. K₂SiF₆:Mn⁴⁺ particles were prepared by co‐precipitation and then coated by esterification of P₂O₅ with alcohols (methanol, ethanol, and isopropanol). This route was adopted to encapsulate the prepared phosphors using transition‐metal ions as cross‐linkers between the alkyl phosphate moieties. The coated phosphor particles exhibited a high water tolerance and retained approximately 87 % of their initial external quantum efficiency after aging under high‐humidity (85 %) and high‐temperature (85 °C) conditions for one month. Warm white‐light‐emitting diodes that consisted of blue InGaN chips, the prepared K₂SiF₆:Mn⁴⁺ phosphors, and either yellow Y₃Al₅O₁₂:Ce³⁺ phosphors or green β‐SiAlON: Eu²⁺ phosphors showed excellent color rendition.     

Strong f‐f Excitation and Bright Red Emission in Cd4Gd1‐xEuxO(BO3)3 (0≤x≤1): Near‐UV LED Pumped Red Phosphor with Low Thermal Quenching

Searching efficient red phosphors under near‐UV or blue light excitation is practically important to improve the current white light‐emitting diodes (WLEDs). Eu²⁺‐ and Mn⁴⁺‐based red phosphors have been extensively studied. Here we proposed that Eu³⁺ is also a promising activator when it resides on a noncentrosymmetric coordination site. We proved that Cd₄GdO(BO₃)₃ is a good host, which has a significantly distorted coordination for Eu³⁺. A careful crystallographic study was performed on the solid solutions of Cd₄Gd_1‐xEu_xO(BO₃)₃ (0≤x≤1) by Rietveld refinements. The as‐doped Eu³⁺ cations locate at the Gd³⁺ site and are well separated by CdO₈, CdO₆ and BO₃ groups; thus, only a slight concentration quenching was observed at ≈80 atom % Eu³⁺. Most importantly, the parity‐forbidden law of 4f‐4f transitions for Eu³⁺ are severely depressed, thus the absorptions at ≈393 and ≈465 nm are remarkable. Cd₄Gd_0.2Eu_0.8O(BO₃)₃ can be pumped by a 395 nm LED chip to give a bright red emission, and when mixed with other commercial blue and green phosphors, it can emit the proper white light (0.3657, 0.3613) with a suitable R_a≈87 and correlated colour temperature ≈4326 K. In‐situ photoluminescence study indicated the low thermal quenching of these borate phosphors, especially under 465 nm excitation. Our case proves the practicability to develop near‐UV excited red phosphors in rare‐earth‐containing borates.     

Synthesis,Structure, and Photoluminescence Properties of Novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+ Phosphors for White‐Light‐Emitting Diodes

A series of novel KBaSc₂(PO₄)₃:Ce³⁺/Eu²⁺/Tb³⁺phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce³⁺‐ and Eu²⁺‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc₂(PO₄)₃:Eu²⁺ and KBaSc₂(PO₄)₃:Ce³⁺ phosphors with Tb³⁺ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu²⁺ and Tb³⁺ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu²⁺→Tb³⁺ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc₂(PO₄)₃:Eu²⁺,Tb³⁺ and KBaSc₂(PO₄)₃:Ce³⁺,Tb³⁺ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.     

Controlled synthesis and luminescent properties of Eu(Eu), Dy-doped Sr3Al2O6 phosphors by hydrothermal treatment and postannealing approach

In this work, Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors have been prepared by hydrothermal treatment and subsequently postannealing approach, using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, and CO(NH₂)₂ as starting materials. The as-obtained phosphors were characterized by means of XRPD, FESEM, and PL techniques. In addition, many reaction parameters were studied in detail, including the initial mole ratios, hydrothermal reaction temperature, calcination temperature and calcination atmosphere. Remarkably, two scientific merits exist herein: Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors can be selectively obtained in a reducing atmosphere (H₂/Ar, 20%+80%) and in air, respectively; adding certain amount of sodium citrate can alter the shape and size of Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors in essence. Besides, the luminescent properties of Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors were studied by excitation spectra, emission spectra and decay curves.     

Site‐Selective Occupancy of Eu2+ Toward Blue‐Light‐Excited Red Emission in a Rb3YSi2O7:Eu Phosphor

Establishing an effective design principle in solid‐state materials for a blue‐light‐excited Eu²⁺‐doped red‐emitting oxide‐based phosphors remains one of the significant challenges for white light‐emitting diodes (WLEDs). Selective occupation of Eu²⁺ in inorganic polyhedra with small coordination numbers results in broad‐band red emission as a result of enhanced crystal‐field splitting of 5d levels. Rb₃YSi₂O₇:Eu exhibits a broad emission band at λ_max=622 nm under 450 nm excitation, and structural analysis and DFT calculations support the concept that Eu²⁺ ions preferably occupy RbO₆ and YO₆ polyhedra and show the characteristic red emission band of Eu²⁺. The excellent thermal quenching resistance, high color‐rendering index R_a (93), and low CCT (4013 K) of the WLEDs clearly demonstrate that site engineering of rare‐earth phosphors is an effective strategy to target tailored optical performance.     

Enhancing the Photocatalytic Activity of Sr4Al14O25: Eu2+, Dy3+ Persistent Phosphors by Codoping with Bi3+ Ions

The photocatalytic activity of Bismuth‐codoped Sr₄Al₁₄O₂₅: Eu²⁺, Dy³⁺ persistent phosphors is studied by monitoring the degradation of the blue methylene dye UV light irradiation. Powder phosphors are obtained by a combustion synthesis method and a postannealing process in reductive atmosphere. The XRD patterns show a single orthorhombic phase Sr₄Al₁₄O₂₅: Eu²⁺, Dy³⁺, Bi³⁺ phosphors even at high Bismuth dopant concentrations of 12 mol%, suggesting that Bi ions are well incorporated into the host lattice. SEM micrographs show irregular micrograins with sizes in the range of 0.5–20 μm. The samples present an intense greenish‐blue fluorescence and persistent emissions at 495 nm, attributed to the 5d–4f allowed transitions of Eu²⁺. The fluorescence decreases as Bi concentration increases; that suggest bismuth‐induced traps formation that in turn quench the luminescence. The photocatalytic evaluation of the powders was studied under both 365 nm UV and solar irradiations. Sample with 12 mol% of Bi presented the best MB degradation activity; 310 min of solar irradiation allow 100% MB degradation, whereas only 62.49% MB degradation is achieved under UV irradiation. Our results suggest that codoping the persistent phosphors with Bi³⁺ can be an alternative to enhance their photocatalytic activity.     

Ultra‐Narrow‐Band Blue‐Emitting Oxoberyllates AELi2[Be4O6]:Eu2+ (AE=Sr,Ba) Paving the Way to Efficient RGB pc‐LEDs

Highly efficient phosphor‐converted light‐emitting diodes (pc‐LEDs) are popular in lighting and high‐tech electronics applications. The main goals of present LED research are increasing light quality, preserving color point stability and reducing energy consumption. For those purposes excellent phosphors in all spectral regions are required. Here, we report on ultra‐narrow band blue emitting oxoberyllates AELi₂[Be₄O₆]:Eu²⁺ (AE=Sr,Ba) exhibiting a rigid covalent network isotypic to the nitridoalumosilicate BaLi₂[(Al₂Si₂)N₆]:Eu²⁺. The oxoberyllates’ extremely small Stokes shift and unprecedented ultra‐narrow band blue emission with fwhm ≈25 nm (≈1200 cm^?1) at λ_em=454–456 nm result from its rigid, highly condensed tetrahedra network. AELi₂[Be₄O₆]:Eu²⁺ allows for using short‐wavelength blue LEDs (λ_em<440 nm) for efficient excitation of the ultra‐narrow band blue phosphor, for application in violet pumped white RGB phosphor LEDs with improved color point stability, excellent color rendering, and high energy efficiency.     

Tuning Mixed‐Valent Eu2+/Eu3+ in Strontium Formate Frameworks for Multichannel Photoluminescence

Cooperative performance of mixed‐valent Eu²⁺/Eu³⁺ in single‐compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu²⁺ oxidation. Using the tunable nature of the metal‐ion nodes in metal–organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu²⁺/Eu³⁺ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic‐ and sensitized‐emissions of Eu²⁺ and Eu³⁺, and long‐lived luminescence from charge transfer. Color rendering can be easily achieved by fine‐tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu²⁺/Eu³⁺ emissions provides outstanding properties for applications as self‐calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb³⁺ into the MOFs results in white light, utilizing all Eu²⁺,Tb³⁺, and Eu³⁺ emissions in a single crystalline lattice.     

Investigation of Luminescence Properties of Eu3+, Dy3+ and Gd3+ Doped MgAl2Si2O8 Red‐emitting Phosphors

Rare‐earth‐doped aluminosilicates of alkaline earth MgAl₂Si₂O₈: Eu³⁺, Dy³⁺ and MgAl₂Si₂O₈: Eu³⁺, Gd³⁺ were synthesized by the solid state reaction method at 1300 ^oC. The phosphors were characterized by X‐ray powder diffraction (XRD), photoluminescence (PL), thermoluminescence (TL) and scanning electron microscopy (SEM). X‐ray powder diffraction studies show that the phosphors were crystallized in the triclinic crystal system. The phosphors show characteristic broad band phosphorescence of Eu³⁺. This broad band phosphorescence has red emission bands in the range of 580–705 nm corresponding to ⁵D₀ → ⁷F_j (j:0,2,3,4) transitions of Eu³⁺.     

Mechanistic Insight into Energy-Transfer Dynamics and Color Tunability of Na4CaSi3O9:Tb3+,Eu3+ for Warm White LEDs

In this work, a latent energy-transfer process in traditional Eu³⁺,Tb³⁺-doped phosphors is proposed and a new class of Eu³⁺,Tb³⁺-doped Na₄CaSi₃O₉ (NCSO) phosphors is presented which is enabled by luminescence decay dynamics that optimize the electron-transfer energy process. Relative to other Eu³⁺,Tb³⁺-doped phosphors, the as-synthesized Eu³⁺,Tb³⁺-doped NCSO phosphors show improved large-scale tunable emission color from green to red upon UV excitation, controlled by the Tb³⁺/Eu³⁺ doping ratio. Detailed spectroscopic measurements in the vacuum ultraviolet (VUV)/UV/Vis region were used to determine the Eu³⁺–O²⁻ charge-transfer energy, 4f–5d transition energies, and the energies of 4f excited multiplets of Eu³⁺ and Tb³⁺ with different 4f^N electronic configurations. The Tb³⁺→Eu³⁺ energy-transfer pathway in the co-doped sample was systematically investigated, by employing luminescence decay dynamics analysis to elucidate the relevant energy-transfer mechanism in combination with the appropriate model simulation. To demonstrate their application potential, a prototype white-light-emitting diode (WLED) device was successfully fabricated by using the yellow luminescence NCSO:0.03Tb³⁺, 0.05Eu³⁺ phosphor with high thermal stability and a BaMgAl₁₀O₁₇:Eu²⁺ phosphor in combination with a near-UV chip. These findings open up a new avenue to realize and develop multifunctional high-performance phosphors by manipulating the energy-transfer process for practical applications.     

Eu2+ & Mn2+‐Coactivated Ba3Gd(PO4)3 Orange‐Yellow‐Emitting Phosphor with Tunable Color Tone for UV‐Excited White LEDs

A novel orange‐yellow‐emitting Ba₃Gd(PO₄)₃:x Eu²⁺,y Mn²⁺ phosphor is prepared by high‐temperature solid‐state reaction. The crystal structure of Ba₃Gd(PO₄)₃:0.005 Eu²⁺,0.04 Mn²⁺ is determined by Rietveld refinement analysis on powder X‐ray diffraction data, which shows that the cations are disordered on a single crystallographic site and the oxygen atoms are distributed over two partially occupied sites. The photoluminescence excitation spectra show that the developed phosphor has an efficient broad absorption band ranging from 230 to 420 nm, perfectly matching the characteristic emission of UV‐light emitting diode (LED) chips. The emission spectra show that the obtained phosphors possess tunable color emissions from yellowish‐green through yellow and ultimately to reddish‐orange by simply adjusting the Mn²⁺ content (y) in Ba₃Gd(PO₄)₃:0.005 Eu²⁺,y Mn²⁺ host. The tunable color emissions origin from the change in intensity between the 4f–5d transitions in the Eu²⁺ ions and the ⁴T₁‐⁶A₁ transitions of the Mn²⁺ ions through the energy transfer from the Eu²⁺ to the Mn²⁺ ions. In addition, the mechanism of the energy transfer between the Eu²⁺ and Mn²⁺ ions are also studied in terms of the Inokuti–Hirayama theoretical model. The present results indicate that this novel orange‐yellow‐emitting phosphor can be used as a potential candidate for the application in white LEDs.     

Luminescence Properties of Ca2Ga2SiO7:RE Phosphors for UV White‐Light‐Emitting Diodes

A series of Eu²⁺‐, Ce³⁺‐, and Tb³⁺‐doped Ca₂Ga₂SiO₇ phosphors is synthesized by using a high‐temperature solid‐state reaction. The powder X‐ray diffraction and structure refinement data indicate that our prepared phosphors are single phased and the phosphor crystalizes in a tetrahedral system with the ${P\bar 42m}$ (113) space group. The Eu²⁺‐ and Ce³⁺‐doped phosphors both have broad excitation bands, which match well with the UV light‐emitting diodes chips. Under irradiation of λ=350 nm, Ca₂Ga₂SiO₇:Eu²⁺ and Ca₂Ga₂SiO₇:Ce³⁺, Li⁺ have green and blue emissions, respectively. Luminescence of Ca₂Ga₂SiO₇:Tb³⁺, Li⁺ phosphor varies with the different Tb³⁺ contents. The thermal stability and energy‐migration mechanism of Ca₂Ga₂SiO₇:Eu²⁺ are also studied. The investigation results indicate that the prepared Ca₂Ga₂SiO₇:Eu²⁺ and Ca₂Ga₂SiO₇:Ce³⁺, Li⁺ samples show potential as green and blue phosphors, respectively, for UV‐excited white‐light‐emitting diodes.     

Photoluminescence Properties of a Promising Red-emitting Phosphor CaNb2O6:EU3+for Trichromatic White Light Emitting Diodes Application

Motivated by the need for new phosphors of white light emitting diode (WLED) application, Ca_0.95Nb₂ O₆:Eu³⁺_0.05 phosphors were synthesized by high temperature solid‐state reaction. Increasing the content of doped‐Eu³⁺ and adding the co‐activator Bi³⁺ to improve the photoluminescence (PL) intensity of Ca_1?xNb₂ O₆Eu³⁺_x phosphors were investigated in detail. The effects of Eu³⁺ were better than that of Bi³⁺ on the PL intensity of Ca_1?xNb₂ O₆Eu³⁺_x phosphors. Compared with Y₂O₂ S:0.05Eu³⁺ the Ca_0.70Nb₂ O₆:Eu³⁺_0.03 phosphor could be excited efficiently by UV (395 nm) light and emit the red light at 614 nm with line spectra, which were coupled well with the characteristic emission from UV‐Near UV LED. The CIE (International Commission on Illumination) chromaticity coordinates (x?0.654, y?0.348) of Ca_0.70Nb₂O₆:Eu³⁺_0.03 were close to the NTSC (National Television Standard Committee) standard values. Therefore Ca_0.70Nb₂ O₆:Eu³⁺_0.03 might find application to UV‐Near UV InGaN chip‐based white light emitting diodes, which is further proved by the LED fabrication with the Ca_0.70Nb₂ O₆:Eu³⁺_0.03 phosphor.     

白光LED用Eu掺杂红色荧光粉

白光LED因亮度高、体积小、寿命长、高效节能、绿色环保等优点而引起人们的广泛关注,但是目前大部分白光LED用荧光粉的不足之处在于其发光效率较低,显色指数较差,色温较高,成本较高等等。红色荧光粉可明显改善白光LED的色温和显色指数,因此红色荧光粉在调制白光LED和改善其显色指数方面具有至关重要的作用。近年来红色荧光粉得到了深入研究,并有不少文献报道了新型的红色荧光粉。本文介绍了Eu³⁺掺杂的线状红光发射荧光粉、Eu²⁺掺杂的带状红光发射荧光粉并着重介绍了Eu²⁺掺杂的新型窄带红光发射荧光粉,以及目前Eu掺杂红色荧光粉发展的不足及其改善方法。     

Enhancement of the photoluminescence and long afterglow properties of Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphor by Dy<Superscript>3+</Superscript> co-doping

The Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ long afterglow phosphors were synthesized under a weak reducing atmosphere by the traditional high temperature solid state reaction method. The synthesized phosphors were characterized by powder X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) techniques. The luminescence properties were investigated using thermoluminescence (TL), photoluminescence (PL), long afterglow, mechanoluminescence (ML), and ML spectra techniques. The crystal structure of sintered phosphors was an akermanite type structure, which belongs to the tetragonal crystallography. TL properties of these phosphors were investigated, and the results were also compared. Under the ultraviolet excitation, the emission spectra of both prepared phosphors were composed of a broad band peaking at 535 nm, belonging to the broad emission band. When the Ca₂MgSi₂O₇:Eu²⁺ phosphor is co-doped with Dy³⁺, the PL, afterglow and ML intensity is strongly enhanced. The decay graph indicates that both the sintered phosphors contain fast decay and slow decay process. The ML intensities of Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were proportionally increased with the increase of impact velocity, which suggests that this phosphor can be used as sensors to detect the stress of an object.     

Synthesis,Persistent Luminescence,and Thermoluminescence Properties of Yellow Sr3SiO5:Eu2+,RE3+ (RE=Ce,Nd, Dy,Ho, Er,Tm, Yb) and Orange‐Red Sr3−xBaxSiO5:Eu2+, Dy3+ Phosphor

Sunlight‐excitable orange or red persistent oxide phosphors with excellent performance are still in great need. Herein, an intense orange‐red Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ persistent luminescence phosphor was successfully developed by a two‐step design strategy. The XRD patterns, photoluminescence excitation and emission spectra, and the thermoluminescence spectra were investigated in detail. By adding non‐equivalent trivalent rare earth co‐dopants to introduce foreign trapping centers, the persistent luminescence performance of Eu²⁺ in Sr₃SiO₅ was significantly modified. The yellow persistent emission intensity of Eu²⁺ was greatly enhanced by a factor of 4.5 in Sr₃SiO₅:Eu²⁺,Nd³⁺ compared with the previously reported Sr₃SiO₅:Eu²⁺, Dy³⁺. Furthermore, Sr ions were replaced with equivalent Ba to give Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ phosphor, which shows yellow‐to‐orange‐red tunable persistent emissions from λ=570 to 591 nm as x is increased from 0 to 0.6. Additionally, the persistent emission intensity of Eu²⁺ is significantly improved by a factor of 2.7 in Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ (x=0.2) compared with Sr₃SiO₅:Eu²⁺,Dy³⁺. A possible mechanism for enhanced and tunable persistent luminescence behavior of Eu²⁺ in Sr_3?xBa_xSiO₅:Eu²⁺,RE³⁺ (RE=rare earth) is also proposed and discussed.     

Improved Thermal and Chemical Stability of Oxynitride Phosphor from Facile Chemical Synthesis for Vehicle Cornering Lights

Orange Eu²⁺-doped phosphors are essential for light-emitting diodes for cornering lights to prevent fatal road accidents at night, but such phosphors require features of high thermal, chemical stability and facile synthesis. This study reports a series of yellow-orange-red emitting SrAl₂Si₃ON₆:Eu²⁺ oxynitride phosphors, derived from the SrAlSi₄N₇ nitride iso-structure by replacing Si⁴⁺−N³⁻ with Al³⁺−O²⁻. The introduction of a certain amount of oxygen enabled the facile synthesis under atmospheric pressure using the air-stable raw materials SrCO₃, Eu₂O₃, AlN and Si₃N₄. SrAl₂Si₃ON₆ has a smaller band gap and lower structure rigidity than SrAlSi₄N₇ (5.19 eV vs 5.50 eV, Debye temperature 719 K vs 760 K), but exhibits higher thermal stability with 100 % of room temperature intensity remaining at 150 °C compared to 85 % for SrAlSi₄N₇. Electron paramagnetic resonance, thermoluminescence and density functional theory revealed that the oxygen vacancy electron traps compensated the thermal loss. Additionally, no decrease in emission intensity was found after either being heated at 500 °C for 2 hours or being immersed in water for 20 days, implying both of the thermal and chemical stability of SrAl₂Si₃ON₆:Eu²⁺ phosphors. The strategy of oxynitride-introduction from nitride promotes the development of low-cost thermally and chemically stable luminescent materials.     

MgAl2O4:Eu3+ nanoplates and nanoparticles as red-emitting phosphors: Shape-controlled synthesis and photoluminescent properties

We demonstrate herein a facile hydrothermal synthesis followed by post-annealing approach to selectively prepare MgAl₂O₄:Eu³⁺ nanoplates and nanoparticles. Series of scientific techniques such as XRPD, FESEM, TEM, HRTEM, and PL were adopted to characterize the as-prepared MgAl₂O₄:Eu³⁺ phosphors. First, by altering the amount of hexamethylenetetramine (abbr. HMTA) in solution, MgAl₂O₄:Eu³⁺ nanoplates occurred. Next, MgAl₂O₄:Eu³⁺ nanoparticles were prepared by adding certain amounts of sodium citrate and sodium dodecylbenzenesulfonate (abbr. SDBS). In particular, the MgAl₂O₄:Eu³⁺ nanoplates have novel porous structures. Besides, the MgAl₂O₄:Eu³⁺ phosphors exhibit excellent red-emitting properties based upon the characteristic transitions of Eu³⁺ from ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, and 4).     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.