Photoluminescence Properties of Color‐Tunable Ca3La6(SiO4)6: Ce3+, Tb3+ Phosphors

A series of newly developed color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors were successfully prepared in this study. The crystal structures of the prepared phosphors were revealed to be hexagonal with space group P6₃/m, and the lattice parameters were evaluated via utilizing the Rietveld refinement method. Upon excitation at 288 nm, the emission spectra of Ce³⁺and Tb³⁺ ions co‐doped Ca₃La₆(SiO₄)₆ phosphors included a blue emission band and several emission lines. The blue emission band with a peak at 420 nm originated in the f–d transitions of Ce³⁺ ions, and the emission lines in the range of 450–650 nm were assigned to the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. Increasing the doping content of Tb³⁺ ions considerably strengthened Tb³⁺ emission and reduced Ce³⁺ emission owing to the energy transfer from Ce³⁺ to Tb³⁺ ions. The mechanism of the energy transfer was confirmed to be a dipole–dipole interaction. The effective energy transfer from Ce³⁺ to Tb³⁺ ions caused a color shift from purplish‐blue to yellowish‐green. Color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors have the potential to be utilized in light‐emitting diodes with proper modulation of the amount of Tb³⁺ ions.     

Cyan-emitting Ba0.45Ca2.5La6(SiO4)6: 0.05 Eu2+ and Ba1.45Ca1.5La6(SiO4)6:0.05 Eu2+ solid-solution phosphors for white light-emitting diodes

Two cyan-emitting phosphors with different bandwidths were successfully synthesized through the high-temperature solid-state method in a reducing atmosphere. The crystal structures, morphologies, and luminescence properties of the as-prepared phosphors were investigated. The Rietveld refinements of the powder X-ray diffraction (XRD) data demonstrated the single phase of the samples, and two crystallographic sites of La³⁺ were observed in the crystal structure. Under the excitation of UV light, both Ba_0.45Ca_2.5La₆(SiO₄)₆: 0.05 Eu²⁺ and Ba_1.45Ca_1.5La₆(SiO₄)₆: 0.05 Eu²⁺ phosphors emitted cyan light due to the 4f⁶5 d¹→4f⁷ transitions of the Eu²⁺ ion. The emission spectra could be well fitted by two component Gaussian peaks corresponding to two different coordination environments of the Eu²⁺ ions. The temperature-dependent photoluminescence spectra show a large difference on the thermal stability between the two phosphors. The two phosphors exhibit effective absorption of near-UV light and their internal quantum efficiencies (IQEs) were calculated as 31.5% and 42.4% under 295 nm UV-light excitation. The experimental results indicate that the novel cyan phosphors might have potential applications in white light-emitting diodes (LEDs) based on the near-UV LED chip.     

Ca2Na2La6(SiO4)4(PO4)2O: Eu2+/Eu3+: A visual dual-emitting fluorescent ratiometric temperature sensor

A novel apatite-based UV-excited dual-emitting Ca₂Na₂La₆(SiO₄)₄(PO₄)₂O: Eu²⁺/Eu³⁺ phosphor (CNL: Eu²⁺/Eu³⁺) was designed and successfully synthesized by a solid-state reaction. Compared with previous reports on this family of materials, a structural study based on DFT calculation exhibited a new consequence that the monovalent ions in this system are more inclined to occupy the seven-coordinate cationic sites rather than the nine-coordinate sites. This result was confirmed by the structural refinement and high-resolution transmission electron microscopy (HRTEM) data. Due to the coexistence of Eu²⁺ and Eu³⁺ dopants in the material, under 345 or 392 nm excitation, CNL: 0.02Eu²⁺/Eu³⁺ exhibited a green Eu²⁺ emission band (528 nm) and red Eu³⁺ emission peaks (around 618 nm). The application potential of CNL:0.02Eu²⁺/Eu³⁺ in luminescent thermometry was studied by exploiting the temperature sensitivity of the fluorescent intensity ratio (green/red) at different temperatures. It was found that, under 345 nm excitation, the fluorescent intensity ratio of CNL: 0.02Eu²⁺/Eu³⁺ displayed linear correlation over the temperature range of 298 to 473 K with a high sensitivity of 2.82%K⁻¹. Additionally, the emission color of the CNL: 0.02Eu²⁺/Eu³⁺ sample under UV lamp (254 and 365 nm) excitation showed an obvious change (from green to red) as the temperature increased from 298 to 473 K (from green to red). These results indicated that CNL: Eu²⁺/Eu³⁺ can serve as an excellent visual luminescent ratiometric thermometer. Furthermore, this work provides a novel reference for developing high-performance luminescence temperature-sensing materials.     

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.     

Impact of Eu3+ Dopants on Optical Spectroscopy of Ce3+: Y3Al5O12‐Embedded Transparent Glass‐Ceramics

Transparent glass‐ceramics containing Ce³⁺: Y₃Al₅O₁₂ phosphors and Eu³⁺ ions were successfully fabricated by a low‐temperature co‐sintering technique to explore their potential application in white light‐emitting diodes (WLEDs). Microstructure of the sample was studied using a scanning electron microscope equipped with an energy dispersive X‐ray spectroscopy. The impact of co‐sintering temperature, Ce³⁺: Y₃Al₅O₁₂ crystal content and Eu³⁺ doping content on optical properties of glass‐ceramics were systematically studied by emission, excitation spectra, and decay curves. Notably, the spatial separation of these two different activators in the present glass‐ceramics, where Ce³⁺ ions located in YAG crystalline phase while the Eu³⁺ ones stayed in glass matrix, is advantageous to the realization of both intense yellow emission assigned to Ce³⁺: 5d→4f transition and red luminescence originating from Eu³⁺: 4f→4f transitions. As a result, the quantum yield of the glass‐ceramic reached as high as 93%, and the constructed WLEDs exhibited an optimal luminous efficacy of 122 lm/W, correlated color temperature of 6532 K and color rendering index of 75.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Tunable Color of Eu2+/Mn2+ Coactivated Na5Ca2Al(PO4)4 via Energy Transfer

Eu²⁺ and Eu²⁺/Mn²⁺‐activated Na₅Ca₂Al(PO₄)₄ phosphors have been synthesized by the combustion method. X‐ray powder diffraction profiles, luminescence spectra, chromaticity variation, and energy transfer of Na₅Ca₂Al(PO₄)₄:Eu²⁺, Mn²⁺ were investigated as a function of the Eu²⁺ and Mn²⁺ concentrations in Na₅Ca₂Al(PO₄)₄. The Na₅Ca₂Al(PO₄)₄:Eu²⁺,Mn²⁺ phosphors can be effectively excited at wavelength ranging from 300 to 430 nm, which matches well with that for near‐ultraviolet (UV) light‐emitting diode (LED) chips. Under excitation at 354 nm, Na₅Ca₂Al(PO₄)₄:Eu²⁺,Mn²⁺ not only exhibits blue‐green emission band attributed to 4f⁶5d¹→4f⁷ of Eu²⁺ but also gives an orange emission band attributed to ⁴T₁→⁶A₁ of Mn²⁺. The emission color of the phosphor can be systematically tuned from blue‐green through white and eventually to orange by adjusting the relative content of Eu²⁺ and Mn²⁺ through the principle of energy transfer. The results indicated that Na₅Ca₂Al(PO₄)₄:Eu²⁺, Mn²⁺ may serve as a potential color‐tunable phosphor for near UV white‐light LED.     

Synthesis and Photoluminescence of a New Chlorogermanate Phosphor Ca8Mg(GeO4)4Cl2:Eu2+

A new chlorogermanate compound Ca₈Mg(GeO₄)₄Cl₂ (CMGC) was synthesized via high‐temperature solid‐state reaction for the first time. The crystal structure of CMGC had been refined and determined from the XRD profiles by Rietveld refinement method, which belong to space group Fd‐3m with the lattice constants a = b = c = 15.1760(25) Å. Photoluminescence properties of CMGC:Eu²⁺ phosphors were investigated by absorption spectra, excitation, and emission spectra. The occupy situation and energy transfer were investigated by decay lifetimes and emission spectra under different excitation wavelengths. Thermal stability was also measured. The results show that the absorption spectra of CMGC:Eu²⁺ phosphors cover from 250 to 500 nm. Under 365 and 435 nm excitation, the emission spectra of CMGC:Eu²⁺ phosphors show blue‐green (centered at 425 and 510 nm) and green (centered at 510 nm) emission, respectively, which attributed to Eu²⁺ ions occupying different crystal sites. Our results indicated that CMGC:Eu²⁺ phosphors had a potential application use for white light‐emitting diodes.     

A comparison study on the substitution of Y3+−Al3+ by M2+−Si4+(M = Ba,Sr, Ca,Mg) in Y3Al5O12: Ce3+ phosphor

Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ (M = Ba, Sr, Ca, Mg) phosphors were successfully prepared through a classic solid-state reaction method. The crystal structures, photoluminescence spectra, quantum yields, and thermal stabilities of the phosphors were investigated in detail. The results indicate that all Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ phosphors maintain the crystal structure of garnets. The emission peaks of Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ (M = Ba, Sr, Ca, Mg) phosphors are located at 537, 538, 554, and 565 nm, respectively. A red-shift trend of emission peak is observed with decreasing M radius, which can be ascribed to the increase in the crystal-field splitting in the Ce³⁺ 5d level owing to the co-doping of M²⁺−Si⁴⁺. Under 460 nm excitation, the luminescence quantum yields and thermal stabilities of the Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ phosphors decreased with the decrease of M radius. The IQE of the Y_1.94BaAl₄SiO₁₂:0.06Ce³⁺ phosphor is 92.89%, and the resistance to thermal quenching is improved to be 93.32% at 150°C. In addition, the color shifts of Y_1.94MAl₄SiO₁₂: 0.06Ce³⁺ phosphors with increasing temperature are all tiny, which also demonstrates good resistance to thermal quenching of luminescence. The linear shrinkage of Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ phosphors is significantly improved compared with that of YAG: Ce³⁺, which is expected to generate Y_1.94MAl₄SiO₁₂:0.06Ce³⁺ transparent/translucent ceramics and fabricate high-powder w-LEDs for high-quality solid-state lighting in the future.     

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.     

Photoluminescent properties and site occupation preference in Bi3+, Eu3+ doped CaY4(SiO4)3O phosphor

Bi³⁺, Eu³⁺ doped CaY₄(SiO₄)₃O phosphors were synthesized through high temperature solid state reaction. Their photoluminescent properties were investigated and site occupation preference of Bi³⁺ in cationic sites was analyzed. The structure of CaY₄(SiO₄)₃O is characterized by three non-equivalent cationic sites with different coordination and cation-oxygen distances. By means of dielectric theory of the chemical bond for complex crystals, several kinds of chemical bond parameters like fractional covalence of CaY₄(SiO₄)₃O were calculated and integrated to yield environmental factor h_e. According to quantitative equations between the transition energy of Bi³⁺ and environmental factor h_e, the excitation bands at 308 and 226 nm were assigned to ¹S₀→³P₁ transition of Bi³⁺ in Y(6h) and Y(4f) site, respectively. Another excitation band centered at 210 nm should be the overlap of Bi³⁺ A-band in Ca site and C-band in Y(6h) site. Optical band gap of pure CYSO was calculated using Kubelka–Munk method from diffuse reflectance spectra. Red emission can be realized in CaY₄(SiO₄)₃O:Bi³⁺, Eu³⁺ under UV light excitation because of efficient energy transfer from Bi³⁺ to Eu³⁺ and decay behaviors of Bi³⁺ and Eu³⁺ emission were investigated. Without optimization, the internal quantum efficiency of CYSO:2%Bi³⁺, 7%Eu³⁺ at 310 and 393 nm excitations were 31.563%, 74.252%, respectively.     

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.     

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.     

Controllable hydrothermal synthesis and photoluminescence properties of CaGd2(WO4)4:Eu3+ red-emitting phosphor

CaGd₂(WO₄)₄:Eu³⁺ phosphors with controllable morphology were synthesized via the hydrothermal method. The influences of pH value, reaction time and Eu³⁺ concentration on the crystal structure, morphology, and photoluminescence properties of CaGd₂(WO₄)₄:Eu³⁺ were studied. The pure tetragonal structure CaGd₂(WO₄)₄ is obtained when the pH value is 8 and 9. Furthermore, by altering the pH value of the reaction solution, the morphologies of the CaGd₂(WO₄)₄:Eu³⁺ phosphors evolve from spindle-shaped grains to tetragonal plate-like grains and finally to aggregated bulk particles. Under the 394 nm excitation, the phosphors display a bright red emission corresponding to the characteristic 4f-4f transitions of Eu³⁺, and the intensity of emission peaks depends mainly on the pH value, the reaction time, and the Eu³⁺ concentration. The optimum photoluminescence performance is achieved for CaGd_2-x(WO₄)₄:xEu³⁺ (x = 1) phosphor synthesized at pH = 8 under the reaction time of 16 h. Finally, the thermal stability of the phosphors is analyzed at different ambient temperatures.     

Intense red emission via energy transfer from (Ce3+/Eu3+):P2O5+NaF+CaF2+AlF3 glasses for warm light sources

Europium (Eu³⁺)-doped fluorophosphate (PNCA:P₂O₅+NaF + CaF₂+AlF₃) glasses with the addition of cerium (Ce³⁺) ions were fabricated by the melt-quenching technique to know their ability for the bright red (615 nm) luminescence. The emission (PL) and excitation (PLE) spectra, decay curve measurements as well as energy transfer (ET) process of Ce³⁺→ Eu³⁺ were studied in detail. An excitation spectrum related to the ⁷F₀→ ⁵D₂ level of Eu³⁺ is used to estimate the phonon energy (1121 cm^?1) of the title glass host. Under ultraviolet (UV) irradiation of 299 nm, the PL spectra of (Ce³⁺/Eu³⁺):PNCA glasses show intense red emission at 615 nm whereas the lifetime decrease with respect to increase of Eu³⁺ that could support the observed efficient ET from Ce³⁺ to Eu³⁺. The ET:Ce³⁺ →Eu³⁺ via quadrupole-quadrupole process was confirmed by Reisfeld's approximation and Dexter's ET formula. The ET efficiency (η_ET) and critical distance (R_c) were also calculated. Interestingly, the (Ce³⁺/Eu³⁺):PNCA glasses showed intense red light emission with low correlated color temperatures and the corresponding color purity reached as great as 99%, indicating its potentiality as a red component for warm light sources.     

A New Blue‐Emitting Phosphor of Ce3+‐Activated Fluorosilicate Apatite Ba2Y3[SiO4]3F

Blue‐emitting phosphor of Ce³⁺‐activated fluorosilicate apatite Ba₂Y₃[SiO₄]₃F was prepared via conventional solid‐state reaction method. The X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) excitation and emission spectra, and the decay curves (lifetimes) were applied to characterize the phosphors. The effects of Ce³⁺ activator concentration on the luminescence properties were investigated. Ba₂Y_2.85Ce_0.15[SiO₄]₃F exhibits the brightest blue emission with CIE coordinates of (x = 0.231, y = 0.301). The crystallographic site of Ce³⁺ ions in Ba₂Y₃[SiO₄]₃F lattices was identified. Two kinds of crystallographic Ce³⁺ occupying MI and MII sites in Ba₂Y₃[SiO₄]₃F lattices result in two distinct emission centers. The internal PL quantum efficiency, the temperature‐dependent luminescence, and the activation energy of thermal quenching were investigated to evaluate the potential application. This is a new kind of blue‐emitting phosphor based on apatite structure.     

Yellow‐Emitting Y3Si6N11: Ce3+ Phosphors for White Light–Emitting Diodes (LEDs)

A novel Y_3?xSi₆N₁₁: xCe³⁺ yellow phosphor was synthesized using the carbothermal reduction and nitridition method at 1550°C for 16 h in this letter. Photoluminescence spectra indicated that the phosphor showed broad excitation spectrum and had strong absorption in range of 350–450 nm. It also gave a broad emission band (Full width at half maximum = 153 nm) centered at 575 nm under 425‐nm excitation. With increasing Ce³⁺ concentration, the strongest emission intensity was obtained at 5 mol% Ce³⁺ doping amount and a systematic redshift was observed as the Ce³⁺ concentration increased. The results indicate that this novel yellow phosphor is a promising candidate for using in blue‐chip‐excited white light–emitting diodes (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.     

Site engineering of Ce3+-doped calcium scandate phosphors and understanding of relevant red-shifted emitting from green to yellow

CaSc₂O₄:Ce³⁺ is a well-known green emitting phosphor, but needs to match with suitable red emitting phosphors in practical white lighting. Herein, a site engineering strategy is proposed to modify the local coordination environment of Ce³⁺ by introducing Y³⁺ and Mg²⁺ ions into the CaSc₂O₄ crystal lattice. The obtained results indicate in the modified Ce³⁺-doped samples (CSO-YMg), Y³⁺ ions can occupy both Sc³⁺ and Ca²⁺ sites simultaneously, and the Y³⁺ ions tend to occupy Ca²⁺ sites in low-doped stage and enter into the Sc³⁺ sites in the high-doped stage. The introduction of Y³⁺ ions gives rise to the existence of MgO in as-prepared CSO-YMg samples, and it can be effectively washed through pickling. In the spectral aspect, with the increase of Y³⁺ and Mg²⁺ ions, the main emission peak is red-shifted from 512 nm to 530 nm upon excitation at 450 nm. However, the high-doped sample presents much stronger thermally induced fluorescence quenching than CaSc₂O₄:Ce³⁺. The lattice defects caused by doped ions (Y³⁺ and Mg²⁺) and the non-radiative energy transfer process between the Ca²⁺ (Ce³⁺) and Sc³⁺ (Ce³⁺ or Ce⁴⁺) sites should be responsible for such evident quenching phenomenon in CSO-YMg, which is obviously different from the emitting feature of CaSc₂O₄:Ce³⁺ (only at Ca²⁺ sites). Besides, utilizing the as-prepared CSO-5 phosphors and a blue LED (~450 nm), a WLED was successfully fabricated, yielding a comparable performance to those with commercial Y₃Al₅O₁₂:Ce³⁺ phosphors. What discussed in this study would bring some inspirations in the exploration and understanding of Ce³⁺-based phosphors according to local structural modification.     

Novel efficient SrMgY3(SiO4)3F:Ce3+,Tb3+ phosphor with tunable color and thermal stability through energy transfer

A novel apatite-type SrMgY₃(SiO₄)₃F was synthesized by a high-temperature solid-state reaction. The crystal structure was refined using powder X-ray diffraction data. SrMgY₃(SiO₄)₃F crystallizes in P6₃/m hexagonal space group with lattice parameters of a = b = 9.45270 Å, c = 6.77617 Å, and V = 524.357 Å³. The incorporation of the Ce³⁺ and Tb³⁺ ions into the matrix can generate bright blue and green lights under ultraviolet (UV) light excitation. The codoped Ce³⁺ and Tb³⁺ in SrMgY₃(SiO₄)₃F can effectively improve green emission intensity and thermal stability through the energy transfer from the Ce³⁺ to Tb³⁺ ions. With the increase of Tb³⁺-doping content, the luminescent color of phosphor changes from blue to cyan and finally to green. SrMgY₃(SiO₄)₃F:0.06Ce³⁺,0.90Tb³⁺ phosphor exhibited intense green light emission with a quantum yield of 59.49% and good thermal stability, with an emission intensity at 150°C was 96% of that at 30°C. Finally, the prepared sample was coated on 365 nm UV chips to fabricate white light-emitting diodes with a color rendering index of 82.6 and a correlated color temperature of 2912 K, demonstrating its potential for applications in display and lighting.