Luminescence properties of Eu3+ or Dy3+/Au co-doped SiO2 nanoparticles

Silica nanoparticles, prepared by the Stober method, have been doped with Eu³⁺, Dy³⁺, or processed to result in Au nanoparticles on the silica surface. The luminescence of the rare earth (RE)-doped SiO₂ particles has been studied as a function of the nature of the RE, their concentration and also of the presence of Au nanoparticles at the surface of the SiO₂ nanoparticles. We have shown that the Eu³⁺ emission is observable over the experimental conditions examined, whereas it was not possible to observe any emission for Dy³⁺ doped materials. No enhancement of the Eu³⁺ emission was observed following the adsorption of gold nanoparticles at the surface of the SiO₂ nanoparticle, however an excitation at 250 nm leads to both the emission of the matrix and Eu³⁺ showing an energy transfer from the SiO₂ matrix to Eu³⁺ ions.     

Photoluminescence spectra tuning of Eu2+ activated orthosilicate phosphors used for white light emitting diodes

Divalent europium activated alkaline earth orthosilicate M₂SiO₄ (M = Ba, Sr, Ca) phosphors were synthesized through solid-state reaction technique and their luminescent properties were investigated. Photoluminescence emission spectra of Sr₂SiO₄:Eu²⁺ phosphor was tuned by substitution of Sr²⁺ with 10 mol% Ca²⁺ or Mg²⁺. Two emission bands originated from the 4f–5d transition of Eu²⁺ ion doped into different cation sites in the M₂SiO₄ host lattice were observed under ultraviolet excitation. The Sr₂SiO₄:Eu²⁺ phosphor showed a blue and a green broad emission bands peaked around 475 and 555 nm with some variation for different Eu²⁺ doping concentration. When 10 mol% of Sr²⁺ was substituted by Ca²⁺ or Mg²⁺, the blue emission band blue-shifted to 460 nm and the green emission band shifted to even longer wavelength. An energy loss due to energy transfer from one Eu²⁺ to another Eu²⁺ ion, changing of the crystal field strength and covalence in the host lattice together were assigned for the tuning effect. With an overview of the excitation spectra and the emission spectra in blue and green-yellow color, these co-doped phosphors can become a promising phosphor candidate for white light-emitting-diodes (LEDs) pumped by ultraviolet chip.     

Luminescent properties of Ca2BO3Cl:Eu yellow-emitting phosphor for white light-emitting diodes

The Ca₂BO₃Cl:Eu²⁺ phosphor was synthesized by the general high temperature solid-state reaction and an efficient yellow emission under near-ultraviolet and blue excitation was observed. The emission spectrum shows a single intense broad emission band centered at 573 nm, which corresponds to the allowed f-d transition of Eu²⁺. The excitation spectrum is very broad extending from 350 to 500 nm, which is coupled well with the emission of UV LED (350-410 nm) and blue LED (450-470 nm). The measured emission of In-GaN-based Ca₂BO₃Cl:Eu²⁺ LED shows white light to the naked eye with a chromatic coordinate of (0.33, 0.36). The Ca₂BO₃Cl:Eu²⁺ is a very appropriate yellow-emitting phosphor for white LEDs.     

Synthesis and characterization Y2O3:Eu3+ nanocrystals prepared via solvothermal refluxing route

Y₂O₃:Eu³⁺ nanocrystals were prepared via co-precipitation–solvothermal refluxing–calcination method using three kinds of organic solvents, propylene glycol, 1,3-butanediol and polyethylene glycol and yttrium chloride hexahydrate and europium chloride as starting materials. The Y₂O₃:Eu³⁺ nanocrystals with diameter of 20–50 nm prepared by refluxing in polyethylene glycol followed by calcinations at 800–1000 °C exhibited the strongest luminescence at 611 nm under the excitation wavelength of 254 nm than the reference sample prepared via conventional co-precipitation method. The photoluminescence spectra of the samples were recorded at room temperature. The effect of concentration of Eu³⁺ (Eu³⁺/Y³⁺ atomic ratio: 0.01–0.1) on the photoluminescence intensity was also investigated. The samples with the Eu³⁺/Y³⁺ atomic ratio of 0.07 exhibited the strongest emission at 611 nm and quenching effect was observed above 0.10.     

Enhancement of red emission intensity of Ca9Y(VO4)7:Eu phosphor via Bi co-doping for the application to white LEDs

The present investigation aims at the luminescence properties of Ca₉Y(VO₄)₇:Eu³⁺, Bi³⁺ red phosphor materials. The red emission at 613 nm originating from ⁵D₀–⁷F₂ transition of Eu³⁺ in Ca₉Y(VO₄)₇ is enhanced strongly with Bi³⁺–V⁵⁺ couple as the sensitizer, under excitation either into the ⁵L₆ state or the ⁵D₂ state. The energy transfer from Bi³⁺–V⁵⁺ to Eu³⁺ is discussed. For a fixed Eu³⁺ concentration, there is an optimal Bi³⁺ concentration with 15 mol%, at which the maximum luminescence intensity of Eu³⁺ is achieved. The red emission of Ca₉Y(VO₄)₇:0.8Eu³⁺, 0.15Bi³⁺ (under 395 nm and 465 nm excitations) is stronger than that of commercial Y₂O₃:Eu³⁺ phosphor (under 395 nm and 467 nm excitations). Based on the ratios of the red emission at 613 nm to orange one at 592 nm, it is considered that the symmetry of Eu³⁺ site decreases with doping of Bi³⁺, leading to more opposite parity components. Lifetime and diffuse reflection spectra measurements indicate that the red emission enhancement is due to the enhanced transition probabilities from the ground state to ⁵L₆ and ⁵D₂ states of Eu³⁺ in the distorted crystal field. Therefore the present material is a promising red-emitting phosphor for white-light diodes with near-ultraviolet/blue GaN-based chips.     

The blue-light emission enhancement mechanism of Eu in Eu, Dy: SiO2 matrix

A Eu, Dy co-doped SiO₂ matrix xerogel with blue emission was prepared by the sol–gel method. Strong blue emission located between 425 nm and 525 nm with a peak at 486 nm is observed under UV laser excitation at room temperature, which is related to a 4f → 5d energy transition of Eu²⁺. Such techniques as FT-IR and TGA–DSC were used to measure the microstructure of the luminescent materials. The influence of Dy³⁺ ions on the luminescent property of Eu²⁺ was investigated. The emission intensity of Eu, Dy-codoped samples is stronger than that of Eu doped samples. The emission enhancement mechanism relating to Eu²⁺ is attributed to an energy transfer involving Dy³⁺ → Eu²⁺. Using energy transition theory, we speculate that the mechanism may be one of the resonance transfers via multi-polar interactions, and present a possible energy transfer model. The Eu²⁺ blue emission intensity reaches the maximum when the Dy³⁺ concentration is 0.1 mol%. When the concentration of Dy³⁺ is 0.3 mol%, a fluorescence quenching appears which might be related to the overlap part of Eu²⁺ excitation and emission levels, and also suggests the existence of Eu²⁺ → Eu²⁺ energy transfer.     

Synthesis and photoluminescence properties of Eu-doped γ-Ca3(PO4)2

Eu³⁺-doped (1% and 3%) γ-Ca₃(PO₄)₂ was synthesized by high-pressure and high-temperature experimental method and the samples were characterized by X-ray diffraction. The luminescence properties of samples were investigated by emission and excitation spectra. The excitation spectra of Eu³⁺-doped γ-Ca₃(PO₄)₂ showed that samples were mainly attributed to Eu³⁺–O²⁻ charge-transfer band at 270 nm, and some sharp lines were also attributed to Eu³⁺ f–f transitions in near-UV regions with the strongest peaks at 395 nm. Under the 395 nm excitation, the intense red emission peak at 611 nm was observed. The strongest line (395 nm) in excitation spectra of those phosphors matched well with the output wavelength of UV InGaN-based light-emitting diodes (LEDs) chip. The luminescent properties suggested that Eu³⁺-doped γ-Ca₃(PO₄)₂ might be regarded as a potential red phosphor candidate for near-UV LEDs.     

Optical studies on X and γ irradiated vacuum grown CsBrI:Eu2+ crystals

CsBr_0.9I_0.1:Eu²⁺ crystals were grown by Bridgman technique. Optical absorption spectrum of the unirradiated CsBr_0.9I_0.1:Eu²⁺ crystals show absorption bands at 270 nm and 340 nm. Irradiated CsBr_0.9I_0.1:Eu²⁺ shows single F band for F(Br⁻) and F(I⁻) centers at 730 nm. Conversion of Eu²⁺ to Eu³⁺ after irradiation is confirmed by optical absorption technique. Sharp and single Photoluminescence (PL) emission band is observed at 440 nm for CsBr_0.9I_0.1:Eu²⁺ crystals. Photostimulated Luminescence (PSL) emission band observed for CsBr_0.9I_0.1:Eu²⁺ crystals at 442 nm due to excitation at 730 nm shows that the F centers are photostimulable. PSL emission intensity increases linearly with irradiation dose up to 2.5 Krad.     

Luminescence properties of Eu2+-activated Sr5(PO4)2(SiO4) for green-emitting phosphor

A green-emitting phosphor of Eu²⁺-activated Sr₅(PO₄)₂(SiO₄) was synthesized by the conventional solid-state reaction. It was characterized by photoluminescence excitation and emission spectra, and lifetimes. In Sr₅(PO₄)₂(SiO₄):Eu²⁺, there are at least two distinguishable Eu²⁺ sites, which result in one broad emission situating at about 495 nm and 560 nm. The phosphor can be efficiently excited in the wavelength range of 250–440 nm where the near UV (～ 395 nm) Ga(In)N LED is well matched. The dependence of luminescence intensities on temperature was investigated. With the increasing of temperature, the luminescence of the phosphor shows good thermal stability and stable color chromaticity. The luminescence characteristics indicate that this phosphor has a potential application as a white light emitting diode phosphor.     

Luminescent properties of Eu3+ activated MLa2(MoO4)4 based (M = Ba,Sr and Ca) novel red-emitting phosphors

Eu³⁺-activated novel red phosphors, MLa₂(MoO₄)₄ (M = Ba, Sr and Ca) were synthesized by the conventional solid state method. The excitation and emission spectra indicate that these phosphors can be effectively excited by UV (395 nm) and blue (466 nm) light, and exhibit a satisfactory red performance at 614 nm. Upon excitation with a 466 nm light, our synthesized phosphors have stronger emission intensity than the sulfide red phosphors used in white LEDs. Due to high emission intensity and a good excitation profile, the Eu³⁺-doped CaLa₂(MoO₄)₄ phosphor may be a promising candidate in solid-state lighting applications.     

Luminescence properties and energy transfer of Ba2Mg(PO4)2:Eu2+, Mn2+ phosphor synthesized by co-precipitation method

The Ba₂Mg(PO₄)₂:Eu²⁺, Mn²⁺ phosphor is synthesized by a co-precipitation method. Crystal phase, morphology, excitation and emission spectra of sample phosphors are analyzed by XRD, SEM and FL, respectively. The results indicate particles synthesized by a co-precipitation method have a smaller size in diameter than that synthesized by conventional solid-state reaction method. Emission spectra of BMP:Eu²⁺, Mn²⁺ phosphor show a broad blue and a broad yellow emission bands with two peaks at about 456 nm and 575 nm under 380 nm excitation. An overlap between Eu²⁺ emission band and Mn²⁺ excitation band proves the existence of energy transfer from Eu²⁺ to Mn²⁺. Emitting color of the BMP:Eu²⁺, Mn²⁺ phosphor could be tuned by adjusting relative contents of Eu²⁺ and Mn²⁺ owing to energy transfer formula. Therefore, BMP:Eu²⁺, Mn²⁺ may be considered as a potential candidate for phosphor for near-UV white LED.     

Photoluminescence and thermal stability of yellow-emitting Sr-α-SiAlON:Eu<Superscript>2+</Superscript> phosphor

Novel α-SiAlON:Eu²⁺-based yellow oxynitride phosphors with the formula Sr_0.375−x Eu _x ²⁺Si_12−m−n Al _m+n O _n N_16−n (m = 0.75, n = x = 0.004–0.04) have been prepared by firing the powder mixture of SrSi₂, α-Si₃N₄, AlN, and Eu₂O₃ at 2,000 °C for 2 h under 1 MPa nitrogen atmosphere. The luminescence properties, the dependence of the activator concentration of Eu²⁺ and the thermal stability of Sr-α-SiAlON:Eu²⁺ phosphor have been investigated in comparison with Ca-α-SiAlON:Eu²⁺ phosphor. Similar to Ca-α-SiAlON:Eu²⁺ phosphor, Sr-α-SiAlON:Eu²⁺ phosphor has the excitation wavelength ranging from the ultraviolet region to 500 nm, and exhibit intense yellow light. The strongest luminescence was achieved at about x = 0.02 with the emission peak at 578 nm, slightly shorter than that of Ca-α-SiAlON:Eu²⁺ phosphor at 581 nm. Temperature-dependent emission intensity of Sr-α-SiAlON:Eu²⁺ phosphor is comparable to that of Ca-α-SiAlON:Eu²⁺ phosphor. The results suggest that the different position of the emission peak for Sr- and Ca-α-SiAlON:Eu²⁺ depends on the composition and the Stokes shift, and the thermal stability is nearly independent of Sr and Ca or fixed by the network of (Si, Al)–(O, N) in α-SiAlON at the same Eu²⁺ concentration.     

Synthesis and photoluminescence of Eu-Mg co-doped γ-AlON phosphors

Eu²⁺-Mg²⁺ co-doped AlON phosphors were prepared by a solid-state reaction route. Their structure and photoluminescence properties were studied. The substitution of Al by Mg favored the formation of pure spinel-type AlON phase and the incorporation of Eu into AlON crystal lattice. Second phase appeared in Eu containing powders. Under ultraviolet excitation at 310 nm, 3% Eu²⁺-10% Mg²⁺ co-doped phosphors exhibited a strong broad emission band in the wavelength range of 430-620 nm with a maximum at about 490 nm assigned to the typical 4f⁶5d¹-4f⁷ transition of the Eu²⁺ ion. Red shift of the emission peak is observed as the increase of Eu²⁺ concentration due to interaction between Eu²⁺ ions.     

Site-specific luminescence of Eu<Superscript>3+</Superscript> in gel-combustion-derived strontium zirconate perovskite nanophosphors

SrZrO₃:Eu³⁺ nanoparticles with a size of about 100 nm were synthesized by a simple gel combustion route and characterized by X-ray diffraction, scanning electron microscopy, dynamic light scattering, and photoluminescence techniques. Based on the time-resolved emission data, it was inferred that three different types of Eu³⁺ ions were present in the matrix. The first type was a long-lived species (~τ = 6.0 ms) present at symmetric “Sr²⁺” sites, observed for excitations at 229 and 393 nm. The second was a short-lived species (τ = 1.0 ms) observed for excitations at 229, 296, and 393 nm, while for 296-nm excitation, a long-lived species (τ = 4.0 ms) was also observed. This suggested that Eu³⁺ ions can be present at relatively lower symmetric “Zr⁴⁺” sites with two different environments, which differ in the presence of charge-compensating defects. The color coordinates of the system were evaluated and plotted on a CIE index diagram.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Observation of an ultraviolet emission band in TiO<Subscript>2</Subscript> nanocrystals doped with Eu<Superscript>3+</Superscript>

The photoluminescence spectra of titanium dioxide (TiO₂) nanocrystals doped with Eu³⁺ (molar ratio Eu³⁺/TiO₂ = 0, 1, 2, 4%) are investigated under different excitation wavelengths. An ultraviolet band of emission energy higher than the energy gap is found for excitation wavelengths larger than 315 nm when the Eu³⁺ content is higher than 2%. The new emission band redshifts and its emission intensity is intensified with the increase of excitation wavelength. The emission mechanism for the new ultraviolet emission band is analyzed.     

Effect of Mg and Ti doping on the luminescence of Y2O2S:Eu

The Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV (x_Eu = 0.028, x_Mg = 0.086, x_Ti = 0.03) materials were prepared with the flux fusion method. According to X-ray powder diffraction, the materials had the hexagonal crystal structure. The emission of Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV was centered at 627 nm (λ_exc : 250 nm) due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em : 627 nm) showed broad bands at 240 and 320 nm due to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, respectively. The latter band can also overlap with the Ti → Eu³⁺ energy transfer. In the excitation spectra with synchrotron radiation, in addition to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, excitation over the band gap was observed at 4.8 eV (258 nm). The red persistent luminescence due to the ⁵D₀ → ⁷F₂ emission from Eu³⁺ residing in the regular Y³⁺ site of the host was ca. 10 min with 1 min fluorescent lamp irradiation. In addition, a very broad band was observed at 600 nm probably due to the Ti³⁺ emission.     

Synthesis,photoluminescence and mechanoluminescence properties of Eu<Superscript>3+</Superscript> ions activated Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> phosphors

A new series of Eu³⁺ ions-activated calcium gadolinium tungstate [Ca₂Gd₂W₃O₁₄] phosphors were synthesized by conventional solid-state reaction method. The X-ray diffraction patterns of the powder samples indicate that the Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors are of tetragonal structure. The prepared phosphors were well characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), and mechanoluminescence (ML) spectra. PL spectra of Eu³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ _exci = 392 nm (⁷F₀ → ⁵L₆). The energy transfer from tungstate groups to europium ions has also reported. Mechanoluminescence studies of Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors have also been explained systematically.     

Effect of annealing on the morphology and properties of ZnS:Mn nanoparticles/PVP nanofibers

As one kind of new optoelectronic materials, ZnS:Mn nanoparticles/PVP composite nanofibers are prepared by the electrospinning technique successfully. SEM, XRD, FT-IR spectroscopy, photoluminescence and TEM measurements are employed in the study. By the method of annealing, the effect on the morphology and properties of the composite nanofibers is studied. After annealing treatment, the separating state of the nanofibers is improved obviously, ZnS:Mn nanoparticles are well dispersed in the nanofiber, the PL peak originated from ⁴T₁→⁶A₁ transition of Mn ions shifts from 605 nm to 599 nm. The existence of orange emission peaks confirms that ZnS:Mn nanoparticles are formed in the fibers.     

The effect of GdF3 on red emission of Eu3+: LiYF4 single crystals grown by the Bridgman method

The bulk LiYF₄ single crystals with high-quality doped 0.5 mol% Eu³⁺ and various Gd³⁺ from 1.5 to 4.5 mol% in size of about Φ 10?×?65 mm were successfully grown by an improved Bridgman method. The X-ray diffraction (XRD) measurement and Rietveld refinement analysis were conducted to verify the structure of the obtained crystal crystals. The spectroscopic properties of the single crystals as change of GdF₃ concentration were investigated with the help of absorption, excitation, emission spectra, and decay curves of their fluorescence. The characteristic absorption bands of Gd³⁺ at 277 nm and Eu³⁺ at 395 nm were observed in the co-doped samples. Significant enhanced emission intensity of 613 nm was observed as increasing of GdF₃ content into Eu³⁺:LiYF₄ single crystal upon excitations of both 277 nm and 395 nm lights. The former was owing to the energy transfer (ET) between Gd³⁺ and Eu³⁺, while the latter was due to the change of crystal field environment around Eu³⁺ by the increasing of GdF₃ content. The ET from Gd³⁺ to Eu³⁺ ions was further confirmed from the result of the luminescence decay analysis. Besides, the full width half-maximum (FWHM) of 613 nm emission band was estimated to be?~?4.5 nm. The Eu³⁺/Gd³⁺ co-doped LiYF₄ single crystal with excellent optical and physicochemical properties might has significant applications in red laser and display devices.