Energy transfer and multicolor tunable emission in single-phase Tb3+, Eu3+ co-doped Sr3La(PO4)3 phosphors

A series of green-to-red color-tunable Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors were prepared by high temperature solid-state method. The crystal structures, photoluminescence properties, fluorescence lifetimes, and energy transfer of Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ were systematically investigated in detail. The obtained phosphors show both a green emission from Tb³⁺ and a red emission from Eu³⁺ with considerable intensity under ultraviolet (UV) excitation (~377 nm). The emission colors of the phosphors can be tuned from green (0.304, 0.589) through yellow (0.401, 0.505) and eventually to red (0.557, 0.392) due to efficient Tb³⁺-Eu³⁺ energy transfer (ET). The Tb³⁺→Eu³⁺ energy transfer process was demonstrated to be quadrupole-quadrupole mechanism by Inokuti-Hirayama model, with maximum ET efficiency of 86.3%. The results indicate that the Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors might find potential applications in the field of lighting and displays.     

Novel color tunable LaCaGaO4:Bi3+,Eu3+ phosphors for high color rendering warm white LEDs

A series of LaCaGaO₄:xBi³⁺,yEu³⁺ (x = 0.002–0.04, y = 0.02–0.45) phosphors with adjustable emission colors were synthesized by high-temperature solid-state reaction. The samples were identified as pure phases by X-ray diffraction and Rietveld refinement, and the crystal structures were analyzed in detail. The LaCaGaO₄:xBi³⁺ phosphor shows an intense blue emission under near-ultraviolet excitation, originating from the ³P₁ → ¹S₀ transition. The spectrum analysis reveals that the Bi³⁺ ions occupy two luminescence centers in the LaCaGaO₄ host and that energy transfer can occur. A model of the energy transfer between the Bi³⁺ and Eu³⁺ ions was also created and studied in detail. As the Eu³⁺-concentration increased, the emission color of the LaCaGaO₄:0.005Bi³⁺,yEu³⁺ phosphor changed from blue to pink to red. In addition, the fluorescence lifetime, quantum yield, thermal stability, and other properties of the phosphors were characterized and analyzed. Finally, two white light-emitting diode devices with R_a values of 96.6 and 95 and correlated color temperatures of 4578 and 3324 K were fabricated, indicating the potential of phosphors for warm white lighting applications.     

Synthesis,structure and luminescence of a high-purity and thermal-stable Sr9LiMg(PO4)7: Eu3+ red phosphor

Eu³⁺-activated Sr₉LiMg(PO₄)₇ phosphors, which presented bright red emissions mainly from the ⁵D₀→⁷F₂ transition of Eu³⁺ ions upon the near-ultraviolet excitation, were successfully synthesized in ambient atmosphere. The crystal structure, phase constitution, photoluminescent behaviors, decay time, internal quantum efficiency and thermal stability of the resultant phosphors were investigated in detail. Eu³⁺ ions are found to tend to occupy multiple Sr²⁺ sites, which are 7, 8 and 10-coordinated. The optimal doping concentration is 7 mol% and the electrical multipolar interaction contributed to the non-radiative energy transfer between Eu³⁺ ions in Sr₉LiMg(PO₄)₇ host lattices. Temperature-dependent PL spectra indicated Sr₉LiMg(PO₄)₇: Eu³⁺ possess excellent emission and color stability at elevated temperature. Fabricated single-chromatic LED prototype emit bright red light under 20 mA bias current, which demonstrates that Sr₉LiMg(PO₄)₇: Eu³⁺ phosphor is of great potential as converted phosphor in NUV LED application.     

White light emitting from YVO4/Y2O3:Eu3+,Bi3+ composite phosphors for UV light-emitting diodes

A series of (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 (0≤x≤0.54) composite phosphors was synthesized in one step by high temperature solid state reaction and the photoluminescence properties were investigated. By means of co-doping Eu³⁺ and Bi³⁺ ions into the composite matrices composed of YVO₄ and Y₂O₃ crystals, the YVO₄/Y₂O₃:Eu³⁺,Bi³⁺ phosphor exhibits simultaneously the blue (418 nm), green (540 nm) and orange-red (595, 620 nm) emissions. The broad blue and green emissions are attributed to the ³P₁–¹S₀ transitions of Bi³⁺ ion both in Y₂O₃ and in YVO₄ matrices. Moreover, the sharp orange-red emissions are attributed to the ⁵D₀–⁷F_1,2 transitions of Eu³⁺ ion in YVO₄ matrix. By tuning the mole ratio of YVO₄/Y₂O₃ matrices the white light-emitting could be obtained. The results indicated that when the mole ratio of Y₂O₃ (x) is at 0.11–0.54 mol, the (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 phosphors emit white light by combining the blue, green and orange-red emissions under the excitation of 360–370 nm wavelength which matches the emission of the commercial UV-LED diode. This implies that the phosphors may be the promising white light materials with broad absorption band for white light-emitting diodes.     

White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+=Eu3+, Dy3+) phosphors

A series of Eu³⁺- or Dy³⁺-doped and Eu³⁺/Dy³⁺ co-doped Y₂WO₆ in pure phase was synthesized via high-temperature solid-state reaction. X-ray diffraction, diffuse reflection spectra, photoluminescence excitation and emission spectra, the CIE chromaticity coordinates and temperature-dependent emission spectra were exploited to investigate the phosphors. Upon UV excitation at 310 nm, efficient energy transfer from the host Y₂WO₆ to dopant ions in Eu³⁺ or Dy³⁺ single-doped samples was demonstrated and those phosphors were suitable for the UV LED excitation. The intense red emission was observed in Y₂WO₆: Eu³⁺, and blue and yellow ones were observed in Y₂WO₆: Dy³⁺. Concentration quenching in Y₂WO₆: Dy³⁺ phosphors could be attributed to the electric dipole-dipole interaction. In Eu³⁺/Dy³⁺ co-doped Y₂WO₆ phosphors energy transfer process only took place from the host to Eu³⁺/Dy³⁺ ions and warm white-light emission can be obtained by adjusting the dopant concentrations. The temperature-dependent luminescence indicated Eu³⁺/Dy³⁺ co-doped Y₂WO₆ was thermally stable. Our overall results suggested that Y₂WO₆: Ln³⁺ (Ln³⁺=Eu³⁺, Dy³⁺) as warm white-light emitting host-sensitized phosphor might be potentially applied in WLEDs.     

Tunable luminescence and energy transfer properties of MgY4Si3O13: Ce3+, Tb3+, Eu3+ phosphors

The tricolor-emitting MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors for ultraviolet-LED have been prepared via a high-temperature solid-state method. X-ray diffraction, photoluminescence emission, excitation spectra and fluorescence lifetime were utilized to characterize the structure and the properties of synthesized samples. Two different lattice sites for Ce³⁺ are occupied from the host structure and the normalized PL and PLE spectra. The emissions of single-doped Ce³⁺/Tb³⁺/Eu³⁺ are located in blue, green and red region, respectively. The energy transfer from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ has been validated by spectra and decay curves and the energy transfer mode from Tb³⁺ to Eu³⁺ was calculated to be electric dipole-dipole interactions. By adjusting the content of Tb³⁺ and Eu³⁺ in MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺, the CIE coordinates can be changed from blue to green and eventually generate white light under UV excitation. All the results indicate that the MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors are potential candidates in the application of UV-WLEDs.     

Luminescence properties and energy transfer of GdAl3(BO3)4:Ce3+, Tb3+ phosphor

Ce³⁺ and Tb³⁺ singly doped and co-doped GdAl₃(BO₃)₄ phosphors were synthesized by solid state reaction. The crystal structure, the luminescent properties, the lifetimes and the temperature-dependent luminescence characteristic of the phosphors were investigated. Through an effective energy transfer, the emission spectra of GdAl₃(BO₃)₄:Ce³⁺, Tb³⁺ phosphor contains both a broad band in the range of 330–400 nm originated from Ce³⁺ ions and a series of sharp peaks at 484, 541, 583, and 623 nm due to Tb³⁺ ions. The energy transfer from Ce³⁺ to Tb³⁺ in GdAl₃(BO₃)₄ host is demonstrated to be phonon assisted nonradiative energy transfer via a dipole–dipole interaction.     

Warm-white light performance of Dy3+, Eu3+: NaLa(WO4)2 phosphors excited with a 450-nm LED

Dy³⁺, Eu³⁺: NaLa(WO₄)₂ phosphors are successfully synthesized through the solid-state reaction technique. The phase-structure and morphology are measured via X-ray diffraction and energy dispersive spectrometry. The concentrations of Dy³⁺, Eu³⁺, La³⁺, and W⁶⁺ are measured via ICP. The absorption and excited spectra are presented, which indicate that a blue band ranging from 430 to 480 nm is suitable for excitation. Using a commercial blue LED with a wavelength of 450 nm as the excitation light source, emission spectra for samples with varying dopant concentration ratios of Dy³⁺ to Eu³⁺ are obtained, which show good tunable yellow and red emission. For the purpose of investigating white LED performance, CIE spectra and a white light photo are also presented. The results reveal that varying the dopant concentration ratio of Dy³⁺ to Eu³⁺ plays a key role in the warm-white performance. With increasing concentration of Eu³⁺, the correlated color temperature decreases from 4069 to 3172 K, which indicates good warm-white performance.     

Synthesis and luminescence properties of color-tunable Dy3+/Eu3+: CeAlON phosphors

Color-tunable Dy³⁺/Eu³⁺ co-doped in Ce₂AlO₃N phosphors were synthesized via a simple conventional solid state reaction. The as-prepared samples were characterized by XRD, TEM and photoluminescence spectra. Results show that the concentrations of Eu³⁺ ions can affect the blue and yellow emission intensities of Dy³⁺, and tunable emission color can be obtained by adjusting the doping concentrations of Eu³⁺. Based on the energy levers of Eu³⁺and Dy³⁺, the mechanism of tunable color has been presented in detail. The thermal stability of Dy³⁺/Eu³⁺: Ce₂AlO₃N has also been discussed.     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

Synthesis and photoluminescence properties of CaGd2(MoO4)4:Eu3+ red phosphors

The novel red-emitting Eu³⁺ ions activated CaGd₂(MoO₄)₄ phosphors were prepared by a citrate sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure when the samples were annealed above 600 °C. The photoluminescence excitation spectra of CaGd₂(MoO₄)₄:Eu³⁺ phosphors exhibited the charge transfer band (CTB) and intense f–f transitions of Eu³⁺ ion. The optimized annealing temperature and Eu³⁺ ion concentration were analyzed for CaGd₂(MoO₄)₄:Eu³⁺ phosphors based on the dominant red (⁵D₀→⁷F₂) emission intensity under NUV (394 nm) excitation. All decay curves were well fitted by the single exponential function. These luminescent powders are expected to find potential applications such as WLEDs and optical display systems.     

Bi3+/Mn4+ co-doped dual-emission phosphors for potential plant lighting

Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi³⁺ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the ²E → ⁴A_2g transition of Mn⁴⁺ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi³⁺/Mn⁴⁺ co-doped Sr₂LaGaO₅: Bi³⁺, Mn⁴⁺ (SLGO:Bi³⁺:Mn⁴⁺) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi³⁺ and Mn⁴⁺ ions, a potential energy transfer process from Bi³⁺ to Mn⁴⁺ ions was confirmed. The relative PL intensities between Bi³⁺ and Mn⁴⁺ ions can be tuned just by adjusting the Mn⁴⁺ ion concentration. Besides, Li⁺ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn⁴⁺ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi³⁺, Mn⁴⁺, Li⁺ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.     

The effect of Li+ incorporation in Yb3+-Nd3+ co-doped CaF2 phosphors over the NIR photoluminescence emission excited under visible light

The structural and optical characteristics of Nd³⁺-Yb³⁺ doped CaF₂ phosphors with and without the addition of Li⁺ ions are described in this work. The phosphors synthetized by hydrothermal and co-precipitation methods showed near-infrared (NIR) luminescence emission associated with inter-electronic transition of the Yb³⁺ ion in the range of 900–1050 nm via energy transfer process from Nd³⁺ ions under visible light excitation. The addition of Li⁺ to these phosphors resulted in an improvement of the NIR luminescence intensity by a factor up to 5. The effect of the incorporation of Li⁺ ions into the CaF₂ crystallite structure, the reduction of luminescence quenching states, as well as the energy transfer mechanism involved are discussed.     

Near white light emission from K+ ion compensated CaSO4:Dy3+,Eu3+ phosphors

Dy³⁺:Eu³⁺ doped calcium sulfate (CaSO₄:Dy³⁺,Eu³⁺) phosphors co-doped with various K⁺ compensator concentrations were synthesized by recrystallization method. These orthorhombic phased phosphors showed intense multi-color near white light. The multi-color aspect ratios and the emission life times were strongly dependent on K⁺-concentration. These results suggest that the rare-earth (Re³⁺) ions are situated at the sites of Ca²⁺ and the site occupancy was being compensated by K⁺ ions. The near white light emission and large lifetimes suggest that present phosphor could be potentially applied as a blue excited white light-emitting phosphor for light emitting diodes.     

Preparation and photoluminescence enhancement of Au nanoparticles embedded LaPO4:Eu3+ inverse opals

In this work, we present a facile preparation approach of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opal photonic crystals. In the typical preparation process, the transparent LaPO₄:Eu³⁺ sol including HAuCI₄ was infiltrated into the opal templates. After the sintering, the 10‐20 nm Au nanoparticles were formed in the interior of nano‐sized wall of LaPO₄:Eu³⁺ inverse opal and the Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opals were obtained. The luminescence of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opal was investigated. The emission peaks located at the 593 (⁵D₀→⁷F₁), 618 (⁵D₀→⁷F₂) and 698 nm (⁵D₀→⁷F₄) from Eu³⁺ ions were observed. The 593, 618, and 698 nm emissions of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opals were enhanced in contrast to these of LaPO₄:Eu³⁺ inverse opal without the Au nanoparticles, which is from the excitation field enhancement caused by the localized surface plasmon resonance of Au nanoparticles.     

Study on luminescence properties of co-doped nanoparticles Gd2O3:Tb3+, Eu3+ synthesized by polyol route

Spherical-like Tb³⁺ and Eu³⁺ co-doped Gd₂O₃ nanoparticles with a particle size around 5.5 nm were synthesized by a polyol route. The optimized luminescence property was obtained when 5 mol% Tb³⁺ and 2 mol% Eu³⁺ were co-doped. The influence of different polyalcohol solvents (DEG/PEG) on particle size and luminescence properties was investigated. The results show that the nanoparticles Gd₂O₃:5%Tb³⁺ prepared in PEG presented greater particle size (around 79 nm) and higher luminescence intensity.     

Tunable white light and energy transfer of Dy3+ and Eu3+ doped Y2Mo4O15 phosphors

A series of Dy³⁺ or/and Eu³⁺ doped Y₂Mo₄O₁₅ phosphors were successfully synthesized at a low temperature of 600 °C via solid state reaction. The as-prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electronic microscope (SEM), photoluminescence (PL) excitation, emission spectra and PL decay curves. XRD results demonstrate that Y₂Mo₄O₁₅: Dy³⁺, Eu³⁺ has the monoclinic structure with the space group of p21/C(14). Under the excitation of ultraviolet (UV) or near-UV light, the Dy³⁺ and Eu³⁺ ions activated Y₂Mo₄O₁₅ phosphors exhibit their characteristic emissions in the blue, yellow and red regions. The emitting light color of the Y₂Mo₄O₁₅: 0.08Dy³⁺, yEu³⁺ phosphors can be adjusted by varying the concentration ratio of Dy³⁺ to Eu³⁺ ions and a white light is achieved when the doping concentration of Eu³⁺ is 5%. In addition, the energy transfer from Dy³⁺ to Eu³⁺ is also confirmed based on the luminescence spectra and decay curves.     

Tb3+/Yb3+ co-doped Y2O3 upconversion transparent ceramics: Fabrication and characterization for IR excited green emission

Tb³⁺/Yb³⁺ co-doped Y₂O₃ transparent ceramics were fabricated by vacuum sintering of the pellets (prepared from nanopowders by uniaxial pressing) at 1750 °C for 5 h. Zr⁴⁺ and La³⁺ ions were incorporated in Tb³⁺/Yb³⁺ co-doped Y₂O₃ nanoparticle to reduce the formation of pores which limits the transparency of ceramic. An optical transmittance of ∼80% was achieved in ∼450 to 2000 nm range for 1 mm thick pellet which is very close to the theoretical value by taking account of Fresnel’s correction. High intensity luminescence peak at 543 nm (green) was observed in these transparent ceramics under 976 and 929 nm excitations due to Yb–Tb energy transfer upconversion.     

SrLaNaTeO6:Eu3+ red-emitting phosphors with high luminescence efficiency and high thermal stability for high CRI white LEDs

A novel single-phase trivalent europium activated red-emitting SrLaNaTeO₆ phosphor was first synthesized in a process of traditional high-temperature solid-state. The phase purity, morphology, and spectroscopy of the prepared phosphor were analyzed. Under 395 nm excitation, the photoluminescence (PL) spectra of the SrLaNaTeO₆:Eu³⁺ products mainly contained five dominant sharp peaks. The intense red emission peak at 615 nm was the typical ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. The optimum product of high quenching concentration was the SrLaNaTeO₆:0.90Eu³⁺, which reached a high internal quantum efficiency (IQE) of 90.6%. The SrLaNaTeO₆:0.90Eu³⁺ was estimated to have R_c of 6.57 Å and possessed high color purity of 100.0%. The phosphors exhibited excellent thermal stability and high activation energy (E_a = 0.29 eV). The prepared white light-emitting diode (WLED) had a high color rendering index (CRI) R_a of 92 and a low correlated color temperature (CCT) of 5008 K. In conclusion, the phosphors have potential as red components for WLEDs.     

A new series of long wavelength red phosphors BaLaLiTe1-xO6:xMn4+ for plant cultivation LED

Mn⁴⁺ doped phosphors have been attracted more and more attention because their emitting spectra can be absorbed by chlorophyll or phytochrome (P_r and P_fr) of plants. Herein, we prepared a new series of phosphors BaLaLiTe_1-xO₆:xMn⁴⁺ (BLLT:xMn⁴⁺, x = 0.002–0.014) by solid state reaction method. Their structure and phase purity were verified by X-ray diffraction (XRD) analysis. Under 336 nm exciting, BLLT:xMn⁴⁺ can emit long wavelength red light at around 700 nm, which fits well with the P_fr spectra of plants. The Mn⁴⁺ concentration was optimized to be x = 0.01, and when it was exceeded, concentration quenching would occur. The internal (IQE) and external quantum efficiency (EQE) of BLLT:0.01Mn⁴⁺ were measured to be 32% and 23% by direct method. Besides, the BLLT:0.01Mn⁴⁺ possesses good thermostability, remaining 76% of the integrated intensity at 423 K of that at 298 K. Hence, we think BLLT:0.01Mn⁴⁺ have potentially applications for plant growth LED.