Microwave synthesis and luminescence properties of YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript>

Europium-doped YVO₄ phosphors have been synthesized using microwave radiation of 700 W power. The uniformity and high rate of microwave heating, as well as “nonthermal” effects of microwave radiation, considerably accelerate the decomposition of precursors and YVO₄:Eu³⁺ synthesis. The europium concentration was varied from 1 to 8 at %. The luminescence intensity of YVO₄:Eu³⁺ was shown to depend on Eu³⁺ concentration, with a maximum at 8 at % Eu³⁺. According to transmission electron microscopy data, the synthesized phosphors consist of nanoparticles 6 to 8 nm in size, with an appreciable degree of agglomeration.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, RE<Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and RE³⁺ co-doped strontium aluminates SrAl₂O₄:Eu²⁺, RE³⁺ were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence of the SrAl₂O₄:Eu²⁺, RE³⁺ phosphors with different composition and doping ions were studied and compared. The results showed that the doped Eu²⁺ ion in SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy³⁺ ion can hardly yield any luminescence under UV-excitation, but can form a electron trap with appropriate depth and greatly enhance the persistent luminescence and thermo-luminescence of SrAl₂O₄:Eu²⁺. Different co-doping RE³⁺ ions showed different effects on persistent luminescence. Only the RE³⁺ ion (e.g. Dy³⁺, Nd³⁺), which has a suitable optical electro-negativity, can form the appropriate electron trap and greatly improve the persistent luminescence of SrAl₂O₄:Eu²⁺. Based on above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated.     

Facile hydrothermal synthesis for size-controlled YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> micro/nanosheets and its luminescence properties

Homogeneous and size-controlled YVO₄:Eu³⁺ micro/nanosheets were successfully synthesized on a large scale by using an ammonium oxalate (AO)-assisted hydrothermal route and post-calcination process. In this study, the shape and size of the as-prepared architectures can be changed effectively by controlling a series of experimental parameters, such as the precursor’s reaction temperature, hydrothermal reaction time and molar ratio of organic additive AO:Y³⁺. YVO₄:Eu³⁺ micro/nanosheets were synthesized with lengths ranging from 2000 to 400 nm and thicknesses ranging from 200 to 50 nm. When changing the precursor’s reaction temperature and reducing the hydrothermal reaction time to 2 h, the phase composition was transformed into Y₂O₃ instead of YVO₄. Functioning as a precipitant and shape modifier, AO exerted a dynamic effect by adjusting the growth rate of different facets under the various experimental conditions, resulting in the formation of different shapes and sizes of the final products. The correlative growth mechanism was analyzed in detail. Photoluminescence and Electroluminescence properties of the products exhibited a strong red emission focused on 618 nm under 275 nm ultraviolet excitation or direct current high-voltage field. Small sample sizes exhibited high EL intensity. The size-controlled products synthesized successfully via the hydrothermal method could provide a great opportunity for systematically evaluating their luminescence properties and accelerating the use of different types of applications in color display devices.     

NIR-excited NIR and visible luminescent properties of amphipathic YVO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> nanoparticles

This article reports the luminescence properties of amphipathic YVO₄:Er³⁺/Yb³⁺ nanoparticles (average grain size ca. 20 nm) obtained by an oleate-aided hydrothermal process. Depending on the upconversion (UPC) and downconversion (DWC) processes, they show luminescence in the visible and near-infrared (NIR) regions, respectively, by 980-nm excitation. The sample doped with Er³⁺:2.5 mol% and Yb³⁺:10 mol% showed the highest luminescence intensity in both the visible and NIR regions as a result of efficient energy transfer from Yb³⁺ to Er³⁺ ions. The hydrothermal treatment greatly enhanced both the DWC and UPC luminescence efficiencies. This is due to the reduction in the concentration of surface defects and ligands, accompanied by grain growth. NIR Fluorescence microscopy revealed for the first time that DWC luminescence is sufficiently intense for application of these nanocrystals as a NIR bioprobe.     

Luminescence studies on Eu<Superscript>2+</Superscript> and Tb<Superscript>3+</Superscript> doped Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> phosphors

Eu²⁺ and Tb³⁺ doped Ca₂MgSi₂O₇ phosphors were synthesized by conventional solid-state reaction. The phase formation was confirmed by X-ray powder diffraction technique and refined lattice parameters were calculated by rietveld refinement process using Celref v3. The photoluminescence (PL) excitation and emission spectra were investigated. The phosphors exhibited broaden green emitting luminescence peaking at 520 nm when excited at 374 nm source. Morphological studies were carried out using Scanning electron microscopy (SEM) images of the sample with optimum PL emission. The dependence of photoluminescence intensity on co-dopant concentration and the kinetic parameters were also reported. Time resolved fluorescence spectroscopy (TRFS) is used to investigate the decay in luminescence signals with respect to time. The sample proved to be a good long lasting material, which makes it useful in emergency signs, textile printing, textile exit sign boards and electronic instrument dial pads etc.     

Single phased Sr<Subscript>3</Subscript>La(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>:Eu<Superscript>2+</Superscript>/Mn<Superscript>2+</Superscript> phosphors: solid state synthesis,tunable luminescence and potential applications in white light LEDs

A series of Sr₃La(PO₄)₃:Eu²⁺/Mn²⁺ phosphors were synthesized by a solid state reaction. The phase and the optical properties of the synthesized phosphors were investigated. The XRD results indicate that the doped Eu²⁺ and Mn²⁺ ions do not change the phase of Sr₃La(PO₄)₃. The peak wavelengths of Eu²⁺ single doped and Eu²⁺/Mn²⁺ codoped Sr₃La(PO₄)₃ phosphors shift to longer wavelength due to the larger crystal field splitting for Eu²⁺ and Mn²⁺. The increases of crystal field splitting for Eu²⁺ and Mn²⁺ are induced by the substitution of Sr²⁺ by Eu²⁺ and Mn²⁺ in Sr₃La(PO₄)₃ host. Due to energy transfer from Eu²⁺ to Mn²⁺ in Sr₃La(PO₄)₃:Eu²⁺/Mn²⁺ phosphors, tunable luminescence was obtained by changing the concentration of Mn²⁺. And the white light was emitted by Sr₃La(PO₄)₃:3.0 mol%Eu²⁺/4.0 mol%Mn²⁺ and Sr₃La(PO₄)₃:3.0 mol%Eu²⁺/5.0 mol%Mn²⁺ phosphors.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

Optical properties of Eu<Superscript>3+</Superscript> activated SrLa<Subscript>2</Subscript>O<Subscript>4</Subscript> red-emitting phosphors for WLED applications

The SrLa_2?xO₄:xEu³⁺ phosphors are synthesized through high-temperature solid-state reaction method at 1473 K with various doping concentration. Their phase structures, absorption spectra, and luminescence properties are investigated by X-ray diffraction (XRD), UV–Vis spectrophotometer and photoluminescence spectrometry. The intense absorption of SrLa_2?xO₄:xEu³⁺ phosphors have occurred around 400 nm. The prominent luminescence spectra of the prepared phosphors exhibited bright red emission at 626 nm. The doping concentration 0.12 mol% of Eu³⁺ is shown to be optimal for prominent red emission and chromaticity coordinates are x?=?0.692, y?=?0.3072. Considering the high colour purity and appropriate emission intensity of Eu³⁺ doped SrLa₂O₄ can be used as red phosphors for white light emitting diodes (WLEDs).     

Photoluminescence properties of a novel red-emitting phosphor Ba<Subscript>2</Subscript>LaV<Subscript>3</Subscript>O<Subscript>11</Subscript>:Eu<Superscript>3+</Superscript>

Ba₂LaV₃O₁₁:Eu³⁺ phosphors were firstly synthesized by the traditional solid-state reaction method at 1100 °C. Their luminescence properties were investigated by photoluminescence excitation and emission spectra. The excitation spectrum shows a broad band centered at about 275 nm in the region from 200 to 370 nm, which is attributed to an overlap of the charge transfer transitions of O^2??→?V⁵⁺ and O^2??→?Eu³⁺. The phosphors exhibit the red emissions of Eu³⁺ and the emission intensity ratio of ⁵D₀?→?⁷F₂ to ⁵D₀?→?⁷F₁ is dependent on the Eu³⁺ concentration due to an environment change about Eu³⁺ ions. Concentration quenching occurs at 30 mol% in the phosphors and exchange interaction is its main mechanism. Ba₂LaV₃O₁₁:Eu³⁺ displays tunable CIE color coordinates from yellow orange to red depended on Eu³⁺ content, which may have a potential application for illuminating and display devices.     

Scintillation and dosimeter properties of <Superscript>6</Superscript>LiF/CaF<Subscript>2</Subscript>:Eu eutectic composites

We investigated scintillation and dosimeter properties of ⁶LiF/CaF₂ eutectic composites doped with different concentrations of Eu (0.005, 0.02, 0.1, 0.3, and 1.0). In the photoluminescence (PL) and scintillation spectra, an emission peak at 430 nm due to the 5d–4f transitions of Eu²⁺ was observed. The intensity of PL and scintillation for ⁶LiF/CaF₂:0.005%Eu was the highest among the samples tested. In thermally stimulated luminescence (TSL), several glow peaks of ⁶LiF/CaF₂:0.005%Eu were observed after X-ray irradiation of 1000 mGy. The TSL response exhibited a linear response against X-ray dose over a dose range of 1–10,000 mGy. In optically stimulated luminescence (OSL), an emission peak was observed at 430 nm during a stimulation by 630 nm light after X-ray irradiation of 1000 mGy. The OSL intensity was the highest for ⁶LiF/CaF₂:0.005%Eu among all the samples investigated.     

The influence of activation of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> polycrystalline matrices by Bi<Superscript>3+</Superscript> ions on the luminescence of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

The influence of activation of the Y₂O₃ matrix of the Y₂O₃:Eu³⁺ phosphor by Bi³⁺ ions on the luminescence of Eu³⁺ and Bi³⁺ ions in it and on conditions of the excitation energy transfer to luminescence centers is studied. It is shown that the presence of Bi³⁺ ions leads to the appearance of recombination luminescence with participation of bismuth ions at low concentrations (up to 6–8 at %) of the dominant activator europium and to an increase in the threshold of intrinsic concentration quenching of its luminescence.     

Hydrothermal synthesis of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> nanorods and its growth mechanism and luminescence properties

Homogeneous Y₂O₃:Eu³⁺ nanorods with the lengths of several micrometres were successfully synthesised on a large scale by using a urea-assisted hydrothermal method and a post-calcining process. In this study, the influences of urea content and NaOH concentration on the oriented growth, photoluminescence (PL) and electroluminescence (EL) intensity enhancement of Y₂O₃:Eu³⁺ were investigated. As a precipitant for isotropic growth, urea can counteract the effect of NaOH on oriented growth along the c-axis during hydrothermal treatment. The Y₂O₃:Eu³⁺ powders exhibited a strong red emission centred at 613 nm under either 245 nm UV excitation or the direct current high electric field. The PL intensity of the Y₂O₃:Eu³⁺ phosphor prepared with 0.3 g of urea reached 141 % that of the sample prepared under the same conditions but without urea. The strategy for controlling the oriented growth, PL and EL enhancement of Y₂O₃:Eu³⁺ can be extended to the synthesis of other inorganic nano/micromaterials.     

Rapid synthesis and enhancement in down conversion emission properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>,RE<Superscript>3+</Superscript> (RE<Superscript>3+</Superscript>=Y,Pr) nanophosphors

BaAl₂O₄:Eu²⁺,RE³⁺ (RE³⁺=Y, Pr) down conversion nanophosphors were prepared at 600 °C by a rapid gel combustion technique in presence of air using boron as flux and urea as a fuel. A comparative study of the prepared materials was carried out with and without the addition of boric acid. The boric acid was playing the important role of flux and reducer simultaneously. The peaks available in the XPS spectra of BaAl₂O₄:Eu²⁺ at 1126.5 and 1154.8 eV was ascribed to Eu²⁺(3d _5/2) and Eu²⁺(3d _3/2) respectively which confirmed the presence of Eu²⁺ ion in the prepared lattice. Morphology of phosphors was characterized by tunneling electron microscopy. XRD patterns revealed a dominant phase characteristics of hexagonal BaAl₂O₄ compound and the presence of dopants having unrecognizable effects on basic crystal structure of BaAl₂O₄. The addition of boric acid showed a remarkable change in luminescence properties and crystal size of nanophosphors. The emission spectra of phosphors had a broad band with maximum at 490–495 nm due to electron transition from 4f ⁶5d ¹ → 4f ⁷ of Eu²⁺ ion. The codoping of the rare earth (RE³⁺=Y, Pr) ions help in the enhancement of their luminescent properties. The prepared phosphors had brilliant optoelectronic properties that can be properly used for solid state display device applications.     

Low temperature synthesis and photoluminescence of Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> nanocrystals with Li<Superscript>+</Superscript> addition

Different crystalline Ca₃(VO₄)₂ nanocrystals have been synthesized successfully via a facile low temperature method with lithium addition. After different ration of Li⁺ doping into the Ca₃(VO₄)₂: Eu³⁺ host, the crystallinity of the sample becomes different, resulting in different of luminescence intensity of the characteristic emission of Eu³⁺ ions. This approach provides economically viable route for large-scale synthesis of this kind of nanomaterials.     

Effect of precursor morphology on the structural properties,optical absorption,and luminescence of BaI<Subscript>2</Subscript>:Eu<Superscript>2+</Superscript>,Eu<Superscript>3+</Superscript>

BaI₂:Eu²⁺,Eu³⁺ powders have been prepared by heat-treating BaCO₃:Eu³⁺ precursor powders of various morphologies in an iodinating agent atmosphere and their structural properties, morphology, optical absorption, and luminescence have been studied. The results demonstrate that the powders thus prepared consist of a mixture of crystalline hydrates of various compositions, dominated by BaI₂ ? 2Н₂О (sp. gr. C2/c), and that the Eu²⁺: Eu³⁺ ratio in the powders is determined by the morphology of the precursor.     

Hydrothermal synthesis of NaLa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> octahedrons and tunable luminescence by changing Eu<Superscript>3+</Superscript> concentration and excitation wavelength

NaLa(WO₄)₂:Eu³⁺ phosphors with different Eu³⁺ concentrations have been synthesized by a hydrothermal method. The phase is confirmed by XRD analysis, which shows a pure-phase NaLa(WO₄)₂ XRD pattern for all of NaLa(WO₄)₂:Eu³⁺ phosphors. The SEM and TEM images indicate that all of NaLa(WO₄)₂:Eu³⁺ phosphors have a octahedral morphology. These suggest that the Eu³⁺ doping has no influence on the structure and growth of NaLa(WO₄)₄ particles. By monitoring the emission of Eu³⁺ at 615 nm, NaLa(WO₄)₂:Eu³⁺ phosphors show excitation bands originating from both host and Eu³⁺ ions. Under the excitation at 271 nm corresponding to WO₄ ^2? groups, emission bands coming from the ¹A₁ → ³T₁ transition with the WO₄ ^2? groups and the ⁵D₀ → ⁷F_j (j = 0, 1, 2, 3 and 4) transitions of Eu³⁺ are observed. The emission intensity relating to WO₄ ^2? groups decreases with increasing Eu³⁺ concentration. But emission intensities of Eu³⁺ increase firstly and then decreases because of concentration quenching effect. Under the excitation at 395 nm corresponding to ⁷F₀ → ⁵L₆ transition of Eu³⁺, only characteristic Eu³⁺ emission bands can be observed. The results of this work suggest that tunable luminescence can be obtained for Eu³⁺ doped NaLa(WO₄)₂ phosphors by changing Eu³⁺ concentration and excitation wavelength.     

Temperature effect on the photoluminescence intensity and Eu<Superscript>2+</Superscript> excited state lifetime in EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript> and EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Er<Superscript>3+</Superscript>

The photoluminescence (PL) spectra and Eu²⁺ excited state lifetime of EuGa₂S₄ and EuGa₂S₄:Er³⁺ have been studied in the range 78–500 K. The spectra show a band at 545 nm, due to the 4f ⁶5d → 4f ⁷(⁸ S _7/2) transition. With increasing temperature, the full width at half maximum Γ(T) of the PL band of EuGa₂S₄ and EuGa₂S₄:Er³⁺ crystals increases from 0.15 to 0.22 and from 0.13 to 0.19 eV, respectively. Over the entire temperature range studied, Γ(T) is a linear function of T ^1/2. The 545-nm emission intensity and Eu²⁺ excited state lifetime in EuGa₂S₄ and EuGa₂S₄:Er³⁺ vary exponentially with temperature. The luminescence quenching energies evaluated from the Arrhenius plots of I(10³/T) and τ(10³/T) coincide (0.10 eV) within the error of determination.     

Synthesis and luminescence properties of a novel Eu<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript> co-doped Al<Subscript>18</Subscript>B<Subscript>4</Subscript>O<Subscript>33</Subscript> whiskers by a gel nano-coating method

Al₁₈B₄O₃₃:Eu³⁺, Tb³⁺ whiskers have been successfully prepared by a simple gel nano-coating method using aluminum isopropoxide as the starting materials. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL), and thermogravimetric analysis (TGA) were used characterize the samples. The results show coexistence of the crystal phase Al₁₈B₄O₃₃, amorphous phase, and Eu³⁺, Tb³⁺ ions of the samples with initial addition Al/B ratios from 3 to 1 are incorporated into the amorphous phase. The Al₁₈B₄O₃₃:Eu³⁺, Tb³⁺ whiskers are very straight with an average diameter of 600 nm and lengths ranging from 5 to 10 μm. Under ultraviolet excitation at 365 nm, samples show mainly exhibit the characteristic emission of Eu³⁺ corresponding to \( ^{ 5} {\text{D}}_{ 0} \to {\text{F}}_{ 1 , 2} \) transitions due to an efficient energy transfer occurs from Tb³⁺ to Eu³⁺.     

Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> luminescence in calcium and strontium aluminates

Compound CaAl₄O₇ (CA4), SrAl₄O₇ (SA4), CaAl₁₂O₁₉ (CA12) and SrAl₁₂O₁₉ (SA12) have been synthesized by using single step combustion method. The phosphors have been characterized by XRD, SEM and PL techniques. Both CA4 and SA4 possess monoclinic crystal structure whereas CA12 and SA12 possess hexagonal structure. Effects of crystal symmetry on the emission spectrum have been studied by doping the samples with Ce³⁺ and Eu²⁺ ions. The luminescence properties of Ce³⁺ and Eu²⁺ in these hosts is discussed on the basis of their covalent character and the crystal field splitting of the d-orbital of dopant ions. The spectroscopic properties, crystal field splitting, centroid shift, red shift and stokes shift have been studied. Spectroscopic properties of Eu²⁺ ions have been accurately predicted from those of Ce³⁺ ions in the same host. Most importantly experimental results were matched excellently with the calculated results. The preferential substitution of Ce³⁺ and Eu²⁺ at different Ca²⁺, Sr²⁺ crystallographic sites have been discussed. The dependence of emission wavelengths of Ce³⁺ and Eu²⁺ on the local symmetry of different crystallographic sites was also studied by using Van Uitert’s empirical relation. Differences in the emission spectrum of these samples have been observed despite their similar crystal structures and space group. Possible reasons have been discussed.     

Dy<Superscript>3+</Superscript>-activated M<Subscript>2</Subscript>SiO<Subscript>4</Subscript> (M = Ba,Mg, Sr)-type phosphors

The alkaline orthosilicates of M₂SiO₄ (M = Ba, Mg, Sr) activated with Dy³⁺ and co-doped with Ho³⁺ are prepared through conventional solid-state method, i.e., mixing and grinding of solid form precursors followed by high-temperature heat treatments of several hours in furnaces, generally under open atmosphere and investigated by X-ray diffraction (XRD) to get phase properties and photoluminescence (PL) analysis to get luminescence properties. The thermal behaviours of well-mixed samples were determined by differential thermal analysis (DTA)/thermogravimetry (TG). The PL spectra show that the 478 and 572 nm maximum emission bands are attributed, respectively, to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions.