Red-emitting enhancement of Bi4Si3O12:Sm3+ phosphor by Pr3+ co-doping for White LEDs application

In this account, Bi₄Si₃O₁₂:Sm³⁺ and (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) red phosphors were prepared by solution combustion method fueled by citric acid at 900 °C for 1 h. The effects of co-doping Pr³⁺ ions on red emission properties of Bi₄Si₃O₁₂:Sm³⁺ phosphors, as well as the mechanism of interaction between Sm³⁺ and Pr³⁺ ions were investigated by various methods. X-ray diffraction (XRD) and Scanning electron microscopy (SEM) revealed that smaller amounts of doped rare earth ions did not change the crystal structure and particle morphology of the phosphors. The photoluminescence spectroscopy (PL) indicated that shape and position of the emission peaks of (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors excited at λ_ex=403 nm were similar to those of Bi₄Si₃O₁₂:Sm³⁺ phosphors. The strongest emission peak was recorded at 607 nm, which was attributed to the ⁴G_5/2→⁶H_7/2 transition of the Sm³⁺ ion. The photoluminescence intensities of Bi₄Si₃O₁₂:Sm³⁺ phosphors were significantly improved by co-doping with Pr³⁺ ions and were maximized at Sm³⁺ and Pr³⁺ ions doping concentrations of 4 mol% and 0.1 mol%, respectively. The characteristic peaks of Sm³⁺ ions were displayed in the emission spectra of (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors excited at respectively λ_ex=443 nm and λ_ex=481 nm (Pr:³H₄→³P₂, ³H₄→³P₀). This indicated the existence of Pr³⁺→Sm³⁺ energy transfer in (Bi₄Si₃O₁₂:Sm³⁺, Pr³⁺) phosphors.     

Photoluminescence properties of a double perovskite tungstate based red-emitting phosphor NaLaMgWO6:Sm3+

In this work, the conventional solid-state method was applied to synthesize a series of red-emitting NaLaMgWO₆:Sm³⁺ phosphors. The crystal structure, phase purity, morphology, particle size distribution as well as elemental composition of the as-prepared phosphors were investigated carefully with the aid of XRD, SEM, EDS, FT-IR analyses, indicating the high-purity and micron-sized NaLaMgWO₆:Sm³⁺ phosphors with monoclinic structure were prepared successfully. The spectroscopic properties of Sm³⁺ in NaLaMgWO₆ host including UV–vis diffuse reflection spectrum, photoluminescence excitation and emission spectra, decay curves, chromaticity coordinates and internal quantum efficiency were investigated in detail. Upon excitation with UV (290 nm) and n-UV (406 nm), NaLaMgWO₆:Sm³⁺ phosphor presented red emission corresponding to the ⁴G_5/2→⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) transitions of Sm³⁺, in which the hypersensitive electronic dipole transition ⁴G_5/2→⁶H_9/2 (645 nm) was with the strongest emission intensity because Sm³⁺ ions were located at a lattice site with anti-inversion symmetry. The optimal concentration of Sm³⁺ was different for the given excitation wavelength such as 290 nm and 406 nm, which was interpreted by the extra effect of the energy transfer from W⁶⁺-O^2- group to Sm³⁺. The decay lifetime for ⁴G_5/2→⁶H_9/2 transition of Sm³⁺ was very short (< 1 ms) and decreased with the increasing Sm³⁺ concentration. The present investigation indicates that NaLaMgWO₆:Sm³⁺ phosphor could be a potential red component for application in w-LEDs.     

White luminescence of bismuth and samarium codoped Y2O3 phosphors

In this work Sm³⁺ (0–2.0 at%) and Bi³⁺ (0–2.0 at%) doped Y₂O₃ luminescent powders were prepared by a sol–gel method from yttrium acetylacetonate, samarium and bismuth nitrates as metal sources. The as prepared powders (chemical composition is close to stoichiometric Y₂O₃) present the cubic structure from 700 °C, and at 900 °C are characterized by the presence of rounded particles with heterogeneous size of 42.9 nm. Luminescent effect of ions of Sm³⁺ and Bi³⁺ into Y₂O₃ host as was studied on heat treated powders from 800 to 1100 °C. The combination of the red luminescence from the Sm³⁺ ions and the bluish from Bi³⁺, makes the synthesized phosphors candidates to be used in fabrication of phosphor-converted light-emitting diodes (LEDs).     

Luminescence properties of Sm3+ ions doped heavy metal oxide tellurite-tungstate-antimonate glasses

The trivalent Sm³⁺ ion doped tellurium-antimony-tungsten oxides based glasses were prepared by conventional melt quenching and pressing method. Spectroscopic characterizations such as optical absorption, photoluminescence and decay profile measurements were performed on the glasses. Judd-Ofelt theory is used to evaluate the oscillator strengths and the three phenomenological intensity parameters (Ω_λ, λ = 2, 4, 6) of the glasses. The photoluminescence spectra recorded under 479 nm excitation exhibited the emission bands at 562, 598, 645 and 708 nm corresponding to the transitions ⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, 11/2) respectively. Using J-O parameters (Ω_λ) various important radiative parameters viz., transition probabilities, emission cross-sections, branching ratios of various emission bands were evaluated. Decay profiles were recorded to find the lifetime of the ⁴G_5/2 excited level and the obtained life time values are observed to decrease with an increase of Sm³⁺ ion concentration; such decrease is attributed due to clustering of Sm³⁺ ions which may cause luminescence quenching.     

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

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

Photoluminescence properties and thermal stability of samarium-doped barium phosphate phosphors

In this paper, Sm³⁺-doped Ca₆BaP₄O₁₇ phosphors were synthesized via a conventional solid-state reaction method. Orange-red emission was observed from these phosphors under near-ultraviolet (UV) excitation at 405 nm. The luminescence properties of the obtained phosphors were characterized. The Ca₆BaP₄O₁₇:Sm³⁺ phosphor can be efficiently excited by near-UV and blue light, and their emission spectrum consists of three emission peaks, at 567, 602, and 650 nm, respectively. The thermal stability of Ca₆BaP₄O₁₇:Sm³⁺ phosphors was investigated systematically and corresponding mechanisms were proposed. Based on the results, the as-prepared Ca₆BaP₄O₁₇:Sm³⁺ phosphors are promising orange-red-emitting phosphors for near-UV-based white light-emitting diodes.     

Tunable emission of single-phased NaY(WO4)2:Sm3+ phosphor based on energy transfer

A series of NaY(WO₄)₂:Sm³⁺ phosphors were prepared by high temperature solid state reaction. When excited by ultraviolet and blue light, their emission spectra cover entirely visible light region, due to intrinsic luminescence of WO₄^2- group as well as Sm³⁺ 4f-4f transitions. White light emission was obtained from NaY_0.99Sm_0.01(WO₄)₂ phosphor under radiation of 265 nm UV light, and intense yellow and red emission from ⁶H_{J(J=5/2, 7/2, 9/2)} transitions were observed when pumped Sm^{3+ 4}G_5/2 by 405 nm blue light. With incorporation of Sm³⁺ into NaY(WO₄)₂ host, higher-level emission from Sm³⁺ at 650 nm was generated by energy transfer from WO₄^2- to Sm³⁺ under excitation of 265 nm. The corresponding energy transfer mechanism was demonstrated to be a dipole-dipole interaction. In addition, tunable emission from blue to white and, finally, to red was realized by increasing Sm³⁺ doping concentration. The band gap of NaY(WO₄)₂ calculated from diffuse reflection spectra indicates a semiconducting character. All these results show that NaY_1−xSm_x(WO₄)₂ phosphor provides promising application for conversion of frequencies emitted by UV or blue LEDs.     

Gel-combustion assisted synthesis of eulytite-type Sr3Y(PO4)3 as a single host for narrow-band Eu3+ and broad-band Eu2+ emissions

A series of eulytite-type Sr₃Y_1-x(PO₄)₃:xEu³⁺ (x = 0–0.13) and Sr_3-yY(PO₄)₃:yEu²⁺ (y = 0–0.10) phosphors were successfully synthesized via gel-combustion and subsequent calcination in O₂ and Ar/H₂ atmospheres at 1250 °C, respectively. Detailed crystal structure analysis via Rietveld refinement showed that the phosphors were crystallized in the cubic system (space group I-43d, No. 220), in which the Eu³⁺ and Eu²⁺ activators reside at the Y³⁺ and Sr²⁺ sites, respectively. The trivalent Eu³⁺ ions (CN = 6) exhibited typical narrow-band luminescence via intra-4f⁶ transitions, with the red emission at ~ 615 nm being dominant (⁵D₀ → ⁷F₂ transition, FWHM = 15.9 ± 0.2 nm). The divalent Eu²⁺ ions (CN = 6 and 9) showed broad-band luminescence ranging from light-blue to blue via 4f⁶5d¹ → 4f⁷ transitions (FWHM = 115 ± 2 nm). The optimal Eu³⁺ and Eu²⁺ concentrations were determined to be 10 at% (x = 0.10) and 7 at% (y = 0.07), respectively, and the mechanisms of concentration quenching were discussed. The excitation/emission properties, fluorescence decay kinetics, CIE chromaticity, and particularly the rarely addressed thermal stability of the phosphors were investigated in detail.     

Luminescence properties of a novel greenish-blue emission long persistent phosphor Sr3TaAl3Si2O14:Pr3+

Pr³⁺exhibits prominent red emission in most oxide phosphors, which derives from the ¹D₂→³H₄ transition, and green or blue emission from ³P₀→³H_{4, 5} transitions are normally less intense in most cases. However, a greenish-blue emission was observed from Sr₃TaAl₃Si₂O₁₄:Pr³⁺prepared via solid state reaction. All as-prepared phosphors were studied systematically by X-ray diffraction (XRD), photoluminescence spectra, decay curves, long afterglow (LAG) spectra and thermoluminescence (TL) glow curves. Based on the excitation and emission spectra, the Sr₃TaAl₃Si₂O₁₄ (STAS) host is proved to be a self-activated luminescent host lattice. In the emission spectra for Pr³⁺doped STAS, the predominant greenish-blue emission locating at ~489 nm and ~507 nm coming from ³P_0,1→³H₄ transitions were observed. And the different mechanisms for concentration quenching in both cases were discussed. At last, a model was proposed on the basis of experimental results to discuss the LAG mechanism of STAS:Pr³⁺in detail.     

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.     

Crystal structure and luminescence properties of novel Sr10−x(SiO4)3(SO4)3O:xEu2+ phosphor with apatite structure

In this paper, a series of novel luminescent Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors with apatite structure were synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, as well as the PL thermal stability were investigated. Sr_9.92(SiO₄)₃(SO₄)₃O:0.08Eu²⁺ phosphor exhibits better thermal quenching resistance, retaining the luminance of 66.55% at 150 °C compared with that at 25 °C. The quenching concentration of Eu²⁺ in Sr₁₀(SiO₄)₃(SO₄)₃O was about 0.08 (mol) with the dipole–quadrupole interaction. The Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors exhibited a broad-band green emission at 538 nm upon excitation at 396 nm. The results indicate that Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors have potential applications as near UV-convertible phosphors for white-light UV LEDs.     

LiSr3SiO4Cl3—A novel host lattice for Eu2+-activated luminescent materials

Eu²⁺-activated LiSr₃SiO₄Cl₃ phosphors were successfully designed, and prepared at low calcination temperature (650 °C). The crystal structure, morphology, and photoluminescence properties have been investigated in detail. The LiSr₃SiO₄Cl₃ crystallizes in orthorhombic LiEu₃SiO₄Cl₃-type structure. Under 316 nm excitation, the phosphor exhibits an asymmetric emission band peaking at 495 nm, which is probably attributed to the 4f–5d transitions of Eu²⁺ in various crystallographic sites. Their luminescence properties are investigated as a function of activator concentration (Eu²⁺). The quenching concentration of Eu²⁺ in LiEu₃SiO₄Cl₃ is about 0.01 due to dipole–dipole interaction. The investigation indicates that Eu²⁺-activated LiEu₃SiO₄Cl₃ phosphor can be used as a green emitting phosphor for white LEDs.     

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.     

Efficient sensitization of Tb3+ emission by Dy3+ in CaMoO4 phosphors: Energy transfer,tunable emission and optical thermometry

Dy³⁺/Tb³⁺ codoped CaMoO₄ phosphors were synthesized by a simple sol–gel method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. The energy transfer process of Dy³⁺→Tb³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results verified that the efficient emission of Tb³⁺ was sensitized by Dy³⁺ under the excitation of 354 nm, realizing tunable emission in CaMoO₄ phosphors. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺: ⁵D₄→⁷F₅ (~546 nm) and Dy³⁺: ⁴F_9/2→⁶H_13/2 (~575 nm). It is expected that the investigated CaMoO₄ nanograins doped with Dy³⁺/Tb³⁺ have prospective applications in display technology and optical thermometry.     

Ultraviolet to near-infrared down-conversion in Bi3+–Yb3+ co-doped YAM phosphor

Direct measurements of external quantum yield (QY) were applied to down-converting phosphors of Y₄Al₂O₉ (YAM) co-doped with Bi³⁺ and Yb³⁺. The QY measurements were combined with studies of photoluminescence (PL), photoluminescence excitation (PLE) and photoluminescence decay kinetics. It was found that the energy transfer occurs mainly from one of the four possible types of Bi³⁺ centers in YAM, namely Bi³⁺(I), with excitation and emission maxima at 278 nm and 360 nm, respectively. The absolute QY measurements show large discrepancy between the measured quantum efficiencies of the UV to near-IR down-conversion process and the efficiencies estimated from the shortening of the Bi³⁺ luminescence decay time. Results presented in the paper testify the conversion ratio (which should be 2.0 for an ideal quantum cutting mechanism) to be no more than 1.0 in the studied material.     

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.     

Improved photoluminescence,thermal stability and temperature sensing performances of K+ incorporated perovskite BaTiO3:Eu3+ red emitting phosphors

K⁺ ions incorporated perovskite Ba_(1−x)TiO₃:x Eu³⁺ red emitting phosphors synthesized via facile solid -state reaction method has been investigated in the current study. The photoluminescence and decay time behavior of Ba_(1−x−y)TiO₃:x Eu³⁺,yK⁺ phosphors are investigated as a function of Eu³⁺, K⁺ concentration and temperature. An intense and sharp emission peak at 615 nm was exhibited by the phosphors upon excitation at 397 nm (⁷F₀→⁵L₆). It can be credited to the hypersensitive electric dipole transition ⁵D₀→⁷F₂, which confirms that Eu³⁺ ions are located at non-centrosymmetric site of the host. The incorporation of K⁺ ions in optimized Ba_0.95TiO₃:0.05 Eu³⁺ phosphor resulted in a remarkable enhancement of photoluminescence intensity by 2.33 times as compared to bare one. The Ba_0.89TiO₃:0.05 Eu³⁺, 0.06 K⁺ phosphors were found to observe good temperature sensing along with adequate thermal stability even at 427 K. Furthermore, the photometric parameters have been also studied which are strongly facilitate the prepared ceramic samples as suitable for potential application in lighting.     

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.     

Synthesis and photoluminescence properties of Sr3(PO4)2:Re3+, Li+ (Re = Eu,Sm) red phosphors for white light-emitting diodes

Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) red phosphors were prepared via a high temperature solid state reaction, and their structure and luminescence properties were investigated. X-ray diffraction patterns indicate that the phase of as-prepared samples is in good agreement with standard Sr₃(PO₄)₂ structure. Under 395 nm excitation, the emission of Sr₃(PO₄)₂:Eu³⁺ consists of a strong peak centered at 622 nm and two weak peaks centered at 598 nm and 660 nm, which correspond to ⁵D₀→⁷F₂, ⁵D₀→⁷F₁ and ⁵D₀→⁷F₃ transitions, respectively. Also, the emission spectrum of Sr₃(PO₄)₂:Sm³⁺ shows three main peaks at 568 nm, 603 nm and 651 nm, which are attributed to ⁴G_5/2→⁶H_I/2 (I = 5, 7, 9) transitions of Sm³⁺. Furthermore, luminescence properties of Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) samples are enhanced significantly by Li⁺ ions doping as charge compensator. Results indicate that as-prepared Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) could be the potential red phosphors used in white light-emitting diodes.     

Photoluminescence and LED application of β-SiAlON:Eu2+ green phosphor

We successfully prepared β-SiAlON:Eu²⁺ phosphors with composition of Eu_xSi_6?zAl_zO_yN_8?y (y = z ? 2x, x = 0.018, z = 0.23) by gas-pressured synthesis for application to LED. The crystal phase, microstructure, PL emission and thermal quenching properties were investigated in detail. The β-SiAlON:Eu²⁺ phosphors absorbed broad UV–vis spectral region, and showed a single intense broadband emission near 538 nm. The Stokes shift and zero-phonon line were calculated mathematically, and also estimated from the spectral data. The β-SiAlON:Eu²⁺ green phosphor showed superior thermal quenching properties compared to commercial silicate (SrBaSiO₄:Eu²⁺) green phosphor. The white light-emitting diode (LED) using the prepared β-SiAlON:Eu²⁺ green phosphor exhibited high color gamut, and good optical stability in high working temperature.