Near-UV light excited Eu3+, Tb3+, Bi3+ co-doped LaPO4 phosphors: Synthesis and enhancement of red emission for WLEDs

A series of single-phase Eu³⁺, Tb³⁺, Bi³⁺ co-doped LaPO₄ phosphors were synthesized by solid-state reaction at 800 °C. Crystal structures of the phosphors were investigated by X-ray diffraction (XRD). A monoclinic phase was confirmed. The excitation (PLE) and emission (PL) spectra showed that the phosphors could emit red light centered at 591 nm under the 392 nm excitation, which is in good agreement with the emission wavelength from near-ultraviolet (n-UV) LED chip (370–410 nm). The results of PLE and PL indicated that the co-doped Tb³⁺ and Bi³⁺could enhance emission of Eu³⁺ and the fluorescent intensities of the phosphors excited at 392 nm could reach to a maximum value when the doping molar concentration of Tb³⁺ and Bi³⁺ is about 2.0% and 2.0%, respectively. The co-doping Tb³⁺ and Bi³⁺ ions can strengthen the absorption of near UV region. They can also be efficient to sensitize the emission of Eu³⁺, indicating that the energy transfer occurs from Tb³⁺ and Bi³⁺ to Eu³⁺ ions. From further investigation it can be found that co-doping Tb³⁺ and Bi³⁺ ions can also induce excitation energy reassignment between ⁵D₀–⁷F₁ and ⁵D₀–⁷F₂ in these phosphors, and result in more energy assignment to ⁵D₀–⁷F₂ emission in LaPO₄:Eu³⁺, Tb³⁺, Bi³⁺. Our research results displayed that La_0.94PO₄:Eu³⁺_0.02, Tb³⁺_0.02, Bi³⁺_0.02 could be a new one and could provide a potential red-emitting phosphor for UV-based white LED.     

Spectroscopic and photoluminescence characteristics of Sm3+ doped calcium aluminozincate phosphor for applications in w-LED

Monophase Calcium Aluminozincate (Ca₃Al₄ZnO₁₀) phosphor doped with Sm³⁺ ions by varying concentrations have been prepared at 1300 °C using conventional solid state reaction technique. The crystal structure and phase analysis of the as-prepared phosphor has been carried out by X-ray Diffraction (XRD) studies. Morphology and functional groups present in the phosphor have been investigated thoroughly by using Scanning Electron Microscope (SEM) and Fourier Transform Infrared (FT-IR) spectral measurements, respectively. Under 401 nm excitation, the as-prepared phosphor exhibit intense visible orange emission at 601 nm. It has been observed that 1.0 mol% of Sm³⁺ ions concentration is optimum to give intense visible orange emission. The PL analysis reveals that the dipole-dipole interaction is primarily responsible for the concentration quenching observed beyond 1.0 mol% of Sm³⁺ ions. The TR-PL study reveals a bi-exponential behavior of decay curves with an average lifetime of the order of microseconds. The CIE coordinates (x=0.574 and y=0.424) measured for the optimized phosphor are very close to the intense orange emission coordinates specified by Nichia Corporation developed Amber LED NSPAR 70BS (0.570, 0.420). The spectroscopic, PL and TR-PL studies suggest the potential use of Sm³⁺ doped calcium aluminozincate phosphors for display and white light emitting devices.     

Luminescent properties of Gd3+ sensitized low-phonon energy CaGd4O7:Tb3+ green emitting novel phosphors

The trivalent terbium (Tb³⁺) ions activated CaGd₄O₇ (CG) phosphors were synthesized by a sol–gel method. The characterizations were performed after the samples annealed at 1500 °C. The structural and morphological properties were analyzed from the X-ray diffraction patterns and scanning electron microscope images. The photoluminescence excitation spectra showed a broad-band between the wavelengths 250 and 300 nm, which were overlapped with the Gd³⁺ excitation bands. The photoluminescence spectra exhibited efficient green emission due to the sensitization effect of Gd³⁺ ions on the Tb³⁺ ions when exciting with the Gd³⁺ wavelength at 278 nm. In order to analyze the influence of Tb³⁺ concentration on the luminescence behavior of Tb³⁺ ions in the CG host lattice, the decay curves were measured. The temperature-dependent luminescence measurements were done to identify the thermal stability of CG:Tb³⁺ phosphors at elevated temperatures. The cathodoluminescent spectra also showed a similar behavior to that observed in PL spectra. The CIE chromaticity coordinates as a function of Tb³⁺ concentration were calculated and all the obtained chromaticity coordinates have been placed in the green spectral region.     

Preparation and properties of CdSiO3: Mn2+, Tb3+ phosphor

CdSiO₃: Mn²⁺, Tb³⁺ long-lasting phosphor was prepared by the conventional high temperature solid-state method. Effects of the content of Mn²⁺ and Tb³⁺ on the luminescent properties of phosphor CdSiO₃: Mn²⁺, Tb³⁺ were investigated by means of photoluminescence (PL) spectra, the afterglow intensity decay curves and the thermoluminescence (TL) spectra. It was found that when the Mn²⁺ and Tb³⁺ dopant-concentrations were 0.4 mol% and 0.8 mol% of Cd²⁺ ions in CdSiO₃, respectively, the luminescence of phosphor prepared had better luminescent property and longer afterglow time. Role of Tb³⁺ co-doped into CdSiO₃: Mn²⁺ matrix was discussed in this paper.     

Luminescence properties and energy transfer investigations of Sr2B2O5:Ce3+,Tb3+ phosphors

Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were synthesized by the solid-state method. X-ray diffraction (XRD) was used to characterize the phase structure. The luminescent properties of Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were investigated by using the photoluminescence emission, excitation spectra and reflectance spectra, respectively. The excitation spectra indicate that this phosphor can be effectively excited by near ultraviolet (n-UV) light of 317 nm. Under the excitation of 317 nm, Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors exhibited blue emission corresponding to the f–d transition of Ce³⁺ ions and green emission bands corresponding to the f–f transition of Tb³⁺ ions, respectively. The Reflectance spectra of the Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors are noted that combine with Ce³⁺ and Tb³⁺ ion absorptions. Effective energy transfer occurred from Ce³⁺ to Tb³⁺ in Sr₂B₂O₅ host due to the observed spectra overlap between the emission spectrum of Ce³⁺ ion and the excitation spectrum of Tb³⁺ ion. The energy transfer efficiency from Ce³⁺ ion to Tb³⁺ ion was also calculated to be 90%. The phosphor Sr₂B₂O₅:Ce³⁺,Tb³⁺ could be considered as one of double emission phosphor for n-UV excited white light emitting diodes.     

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.     

Citrate-based sol–gel synthesis and luminescent properties of Y6WO12:Eu3+, Dy3+ phosphors for solid-state lighting applications

The rare-earth ions (Eu³⁺, Dy³⁺) doped Y₆WO₁₂ phosphors were prepared by a citrate-based sol–gel method. The morphologies and structural properties of the as-prepared and doped samples were analyzed by scanning electron microscope images and X-ray diffraction patterns. The luminescent properties were studied by examining the excitation and emission spectra of the samples. The Eu³⁺ and Dy³⁺ ions doped samples exhibited their characteristic emission bands in the visible region under ultraviolet light excitation. The temperature-dependent photoluminescence (PL) properties of the samples were also investigated. The PL spectra of the synthesized samples by the sol–gel method were compared with those of the bulk sample prepared by a solid-state reaction. Similarly, the Commission International de I’Eclairage chromaticity coordinates and the decay times of Y₆WO₁₂:Eu³⁺ (3 mol%) and Y₆WO₁₂:Dy³⁺ (2 mol%) phosphors were studied.     

Characteristics of nano-sized ZnGa2O4 phosphor prepared by solution combustion method and solid state reaction method

ZnGa₂O₄ phosphors were prepared by both SCM (solution combustion method) and SSRM (solid state reaction method). The properties of the both ZnGa₂O₄ phosphors were investigated by TGA (Thermogravimetric analysis), SEM (scanning electron microscope), BET (Brunauer Emmett Teller), PL (photoluminescence) and XRD (X-ray diffraction). The particle size of SCM phosphor was about one-hundredth of SSRM phosphor. The PL intensity of SCM phosphor was about 1.5-fold higher than that of SSRM phosphor. The SCM phosphor was also tried to be doped with Mn²⁺ ions. The highest PL peak was observed with Mn²⁺ ions of 0.003 mol fraction. The peak was shifted from blue (470 nm) to green (513 nm) color. These results might be very useful for high efficiency phosphors for displays such as field emission displays and plasma display panels.     

A novel tunable green-to-red emitting phosphor Ca4LaO(BO3)3:Tb,Eu via energy transfer with high quantum yield

A novel green phosphor composed of Ca₄LaO(BO₃)₃:Tb³⁺ (CLBO:Tb) has been synthesized by a combustion method with urea. Its crystal structure, temperature-dependent luminescence, and quantum yield (QY) have been characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra with heating device and integrate sphere. No concentration quenching has been observed when all of La³⁺ ions are substituted with Tb³⁺ ions. Green phosphor Ca₄TbO(BO₃)₃ (CTBO) has 200% luminescence intensity of commercially available phosphor LaPO₄:Ce, Tb (LPO:Ce, Tb) under 378 nm excitation. The QY of CTBO is as high as 98%. Through a Dexter energy transfer mechanism, Eu³⁺ ions are efficiently sensitized by Tb³⁺, resulting in an emission with color tunable from green to red under ultraviolet excitation. A possible mechanism of energy transfer from Tb³⁺ to Eu³⁺ has been investigated by PL spectra and decay measurements. The energy transfer efficiency from Tb³⁺ to Eu³⁺ increases linearly with concentration of Eu³⁺ increasing.     

Preparation and characterization of a green emitting Li2Ca0.4Sr0.6SiO4:Tb3+ phosphor with afterglow behavior

A novel green emitting long afterglow phosphor Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ was obtained via a high temperature solid-state reaction in air atmosphere. X-ray diffraction (XRD), photoluminescence spectroscope (PLS), long afterglow spectroscope (LAS) and thermal luminescence spectroscope (TLS) were performed to characterize the physical properties of the phosphors. Typical ⁵D₄-⁷F_j transitions of Tb³⁺ ions were detected by PL spectra, corresponding to CIE chromaticity coordinates of x =0.3456, y =0.5745. An optimal concentration of Tb³⁺ in the substrate was determined as 0.8 at%. The Li₂Ca_0.4Sr_0.6SiO₄ phosphors showed a typical afterglow behavior when the UV source was switched off. A typical triple exponential decay behavior was confirmed after fitting the experimental data. Thermal simulated luminescence study further indicated that the afterglow behavior of Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ phosphors was generated by the recombination of electrons with the holes resulted from the doping of rare-earth ions (Tb³⁺) in Li₂Ca_0.4Sr_0.6SiO₄ host. The long afterglow luminescence mechanism of Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ is illustrated and discussed in detail on the basis of experimental results.     

Structure evolution and delayed quenching of the double perovskite NaLaMgWO6:Eu3+ phosphor for white LEDs

Eu³⁺ ions activated NaLaMgWO₆ phosphors were successfully synthesized by an improved sol-gel method using citric acid and polyethylene glycol as complexing agents. Crystal structure and doping site were investigated by XRD, Rietveld refinement and Raman spectra. The phosphors had monoclinic double perovskite structure with space group C2/m, as well as layered ordering of A-site and rock-salt ordering of B-site. The blueshift of Raman T_2g(1) mode manifested Eu³⁺ ions had entered into A-site. Thereafter, luminescence properties, such as excitation and emission spectra, CIE coordinates, concentration quenching and thermal quenching were discussed. The quenching concentration for hypersensitive electric dipole transition of Eu³⁺ reached up to 50.0 mol%. The delayed concentration quenching was observed in NaLaMgWO₆: Eu³⁺ phosphor. The theoretical quenching concentration was obtained based on L. Ozawa's theory, and the quenching mechanism on Dexter's theory. Excellent thermal stability of this phosphor shows that it is a potential red phosphor for solid state lighting.     

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.     

Luminescent and structural properties of manganese-doped zinc aluminate spinel nanocrystals

Manganese-doped zinc aluminate spinel (ZnAl₂O₄:Mn; Mn=0–6.0 mol%) phosphor nanoparticles were prepared by the sol–gel process. The effects of thermal annealing and dopant concentration on the structure, microstructure and luminescence of the powder phosphors were investigated. The X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) results confirmed that a single-phase spinel started to crystallize at around 600 °C for the investigated powders. On heating at 600–1200 °C, the powders had the average crystallite sizes of around 12–33 nm. The crystallite size and lattice constant increased as the doping level of Mn increased. FT-IR spectra exhibited only absorption bands of the AlO₆ octahedral groups, which suggested that the powder phosphors mainly crystallized in a normal spinel structure. Scanning electron microscopy (SEM) investigations showed the primary particle sizes were around 20–25 nm for the powders annealed at 1000 °C, and less than ca. 50 nm for those annealed at 1200 °C. Photoluminescence (PL) spectra under UV or visible light excitation exhibited a strong green emission band centered at 510 nm, corresponding to the typical ⁴T₁(⁴G)—⁶A₁(⁶S) transition of tetrahedral Mn²⁺ ions. The most intense PL emission was obtained by exciting at 458 nm. The PL intensity was significantly enhanced by the improved crystallinity and diminished OH^? groups. Optimum brightness occurred at a doping of 3.0 mol% Mn.     

Synthesis,photoluminescence properties and energy transfer behavior of color-tunable fluorapatite phosphor Sr9Gd(PO4)5(SiO4)F2:Tb3+/Sm3+

Tb³⁺-Sm³⁺ co-doped Sr₉Gd(PO₄)₅(SiO₄)F₂ (SGPSF) phosphors were prepared through a solid-state reaction, and their luminescence properties as well as energy transfer mechanism have been investigated in detail. The SGPSF:Tb³⁺, Sm³⁺ phosphors system could be efficiently excited at wavelengths ranging from 200 to 500 nm, which is well matched with the spectra of near ultraviolet chips. The emission of SGPSF:Tb³⁺, Sm³⁺ phosphor covers the entire visible region with sharp peaks in the blue, green, and red regions. The emission color of SGPSF:Tb³⁺, Sm³⁺ could be adjusted from green (0.275, 0.378) to red (0.519, 0.295) by controlling the doping content of Sm³⁺/Tb³⁺.     

Synthesis of Ca2SiO4:Dy3+ phosphors from agricultural waste for solid state lighting applications

Trivalent dysprosium (Dy³⁺) ions -doped calcium silicate (Ca₂SiO₄) phosphors have been synthesized by utilizing agricultural waste of egg shell and rice husk through solid-state reaction method. The synthesized Ca₂SiO₄ powders thus obtained are crystallized in monoclinic structure with unit cell parameters of a = 5.53 Å; b = 6.67 Å; c = 9.13 Å; β = 87.43° and irregular shape morphology. Luminescent properties of Dy³⁺:Ca₂SiO₄ phosphors were studied by varying active ion concentration. The phosphors emit characteristic blue and yellow emissions of Dy³⁺ ions corresponding to the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions, respectively. Color coordinates evaluated from emission spectra are found to fall in the white light region. Decay curves for the ⁴F_9/2 level of Dy³⁺ ions exhibit single exponential nature and turn into non-exponential with shortening of lifetime from 739 µs to 510 µs when Dy³⁺ ion concentration is increased from 0.001 to 0.5 mol%. All these results confirm that Ca₂SiO₄:Dy³⁺ phosphors are suitable for the use as low cost white light emitting phosphors.     

Tunable single-phased white-emitting Sr3Y(PO4)3:Dy3+ phosphors for near-ultraviolet white light-emitting diodes

Single-component white-emitting Sr₃Y(PO₄)₃:Dy³⁺ phosphors were synthesized by a high-energy deformation process. X-ray diffraction patterns showed the resulting crystallized phase to be of cubic structure, space group I-43d (no. 220). The broad-band excitation spectra between 250 and 500 nm were observed by monitoring the emission wavelength at 576 nm, which matches well with commercial near-UV or blue LED chips. Under a 352 nm excitation, the emission peaks were observed at 483 nm (blue), 576 nm (yellow), and 666 nm (red), corresponding to the ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺ ions. The optimized doping concentration of Dy³⁺ ion was 8 mol%. By controlling the Dy³⁺ ion concentration, tunable colors from white to yellow were obtained in Sr₃Y(PO₄)₃:Dy³⁺ phosphors. These results reveal that studied materials may be a promising candidate for white LED applications.     

Upconversion emission,cathodoluminescence and temperature sensing behaviors of Yb3+ ions sensitized NaY(WO4)2:Er3+ phosphors

A series of Yb³⁺ ions sensitized NaY(WO₄)₂:Er³⁺ phosphors were synthesized through a solid-sate reaction method. The X-ray diffraction (XRD), upconversion (UC) emission and cathodoluminescence (CL) measurments were applied to characterize the as-prepared samples. Under the excitation of 980 nm light, bright green UC emissions corresponding to (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions were observed and the UC emission intensities showed an upward trend with increasing the Yb³⁺ ion concentration, achieving its optimum value at 25 mol%. Furthermore, the temperature sensing behavior based on the thermally coupled levels (²H_11/2,⁴S_3/2) of Er³⁺ ions was analyzed by a fluorescence intensity ratio technique. It was found that the obtained samples can be operated in a wide temperature range of 133–773 K with a maximum sensitivity of approximately 0.0112 K⁻¹ at 515 K. Ultimately, strong CL properties were observed in NaY(WO₄)₂:0.01Er³⁺/0.25Yb³⁺ phosphors and the CL emission intensity increased gradually with the increment of accelerating voltage and filament current.     

Development of red-emitting Ba2LaSbO6:Mn4+ phosphors for latent fingerprint detection

Latent fingerprints provide crucial affirmations of identity in forensic science. However, they are microscopic. In this study, novel fluorescence materials, Ba₂LaSbO₆:Mn⁴⁺ (BLSO:Mn⁴⁺) phosphors, were developed by a sol–gel method for the fluorescence imaging of latent fingerprints. The structural properties of the phosphors were investigated by powder X-ray diffraction (XRD) and its Rietveld refinement analyses, and transmission electron microscopy and scanning electron microscopy techniques. The photoluminescence properties of the BLSO:Mn⁴⁺ phosphors were evaluated comprehensively by recording the emission, excitation, and decay curves. The BLSO:Mn⁴⁺ phosphors provide a high-intensity red emission at 677 nm under 350 nm excitation caused by the ²E_g→⁴A_2g transition of Mn⁴⁺. The optimum concentration of Mn⁴⁺ in the BLSO host was determined to be ~0.2 mol%. The calculated Commission International de L'Eclairage (CIE) chromaticity coordinates (0.716, 0.283) of the emission from the BLSO:Mn⁴⁺ phosphor are located in the pure red region of the CIE 1931 diagram. The red-emitting BLSO:0.2Mn⁴⁺ phosphor was used as a fluorescence imaging powder for visualizing latent fingerprints on various substrates with high resolution, high contrast, and high efficiency, as well as good selectivity.     

Synthesis,crystal structure and temperature dependent luminescence of Eu3+ doped SrGd2O4 host: An approach towards tunable red emissions for display applications

In the present paper, an investigation on the structural and photoluminescence (PL) properties of SrGd₂O₄:Eu³⁺ ceramic phosphors synthesized by homogeneous precipitation method followed by combustion process has been reported. The samples, annealed at 1200 °C, were crystallized into orthorhombic phase without any impurities. Microscopic studies revealed the irregular morphology of the obtained ceramic phosphor particles having sizes in the range of 0.3–3 µm. The characteristic photoluminescence properties and decay curves were studied in detail as a function of Eu³⁺ concentration and temperature. The Eu³⁺ doped ceramic samples illuminated with UV light revealed the characteristic red luminescence corresponding to ⁵D₀→⁷F_J transitions of Eu³⁺. The concentration quenching phenomenon of Eu³⁺ ions in the present host, analyzed in the light of ion-ion interaction, indicated multipolar interaction between Eu³⁺ ions. Finally, the intensity parameters (Ω₂, Ω₄) and various radiative properties such as stimulated emission cross-section (σ_e), gain band-width (σ_e×Δλ_eff) and optical gain (σ_e×τ_exp) of Eu³⁺ in the SrGd₂O₄ ceramic phosphors have been calculated by using Judd-Ofelt theory. The present phosphor system exhibited efficient red emission with high red color purity (95%) and adequate thermal stability even at 200 °C. Present research broadly indicated the suitability of SrGd₂O₄:Eu³⁺ ceramic phosphor for display applications.     

Photoluminescence properties of Tb3+ doped Al2O3 microfibers via a hydrothermal route followed by heat treatment

Uniform Al₂O₃:Tb³⁺ microfibers were synthesized via a hydrothermal route and thermal decomposition of a precursor of Tb³⁺ doped ammonium aluminum hydroxide carbonate, and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curves. XRD results indicate that various crystallographic phase Al₂O₃:Tb³⁺ microfibers are obtained by postannealing at different temperatures. SEM results show that the length and diameter of these Tb³⁺ doped α-Al₂O₃ microfibers are about 6–8 μm and 300 nm, respectively. The PL spectra indicate that the ⁵D₄ → ⁷F₅ (545 nm) electric dipole transition is the most intensive when excited at 240 nm. It is shown that the 2.0 mol% of doping concentration of Tb³⁺ ions in α-Al₂O₃:Tb³⁺ is optimum. According to Dexter's theory, the critical distance between Tb³⁺ ions for energy transfer was determined to be 12.7 Å. It is found that the decay curves follow the single-exponential decay.