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.     

Combusion synthesis,structural and photo-physical characteristics of Eu<Superscript>2+</Superscript> and Dy<Superscript>3+</Superscript> co-doped SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> phosphor nanopowders

In this research, we reported the synthesis of Eu²⁺ and Dy³⁺ co-doped SrAl₂O₄ phosphor nanopowders with high brightness and long afterglow by urea-nitrate solution combustion synthesis (SCS) at 600 °C, followed by heating the resultant combustion ash at 1,200 °C in a weak reductive atmosphere (5% H₂ + 95% N₂). The broad-band UV-excited luminescence of the SrAl₂O₄: Eu²⁺, Dy³⁺ nanopowders was observed at λ _max = 517 nm due to transitions from the 4f⁶5d¹ to the 4f⁷ configuration of the emission center (Eu²⁺ ions). The excitation spectra consist of 240- and 254 nm broad peaks. Finally, it was found that the optimum ratio of urea is 2.5 times higher than theoretical quantities for the best emission condition of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphor nanopowders.     

Luminescence of Pb<Superscript>2+</Superscript> in MAl<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = Ca,Sr)

Pb²⁺ doped SrAl₂B₂O₇ was prepared by solution combustion synthesis. The synthesized material was determined by powder XRD. The photoluminescence properties of the synthesized phosphor were investigated at room temperature using a spectrofluorometer. The emission peak of Pb²⁺ doped SrAl₂B₂O₇ was observed at 420 nm upon excitation at 277 nm. The Stokes shift of SrAl₂B₂O₇:Pb²⁺ was calculated to be 12 292 cm⁻¹. The luminescence behavior of Pb²⁺ in both SrAl₂B₂O₇ and CaAl₂B₂O₇ was discussed. The text was submitted by the authors in English.     

Structural and optical characterization of RE (Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) doped SrMg<Subscript>2</Subscript>Al<Subscript>6</Subscript>Si<Subscript>9</Subscript>O<Subscript>30</Subscript> nanocrystalline phosphor

This article present the reports on optical study of Eu²⁺ and Ce³⁺ doped SrMg₂Al₆Si₉O₃₀ phosphors, which has been synthesized by combustion method at 550 °C. Here SrMg₂Al₆Si₉O₃₀:Eu²⁺ emission band observed at 425 nm by keeping the excitation wavelength constant at 342 nm, whereas SrMg₂Al₆Si₉O₃₀:Ce³⁺ ions shows the broad emission band at 383 nm, under 321 nm excitation wavelength, both the emission bands are assigned due to 5d–4f transition respectively. Further, phase purity, morphology and crystallite size are confirmed by XRD, SEM and TEM analysis. However, the TGA analysis is carried out to know the amount of weight lost during the thermal processing. The CIE coordinates of SrMg₂Al₆Si₉O₃₀:Eu²⁺ phosphor is observed at x?=?0.160, y?=?0.102 respectively, which may be used as a blue component for NUV-WLEDs. The critical distance of energy transfer between Ce³⁺ ions and host lattice is found to be 10.65 Å.     

Influence of Mg<Superscript>2+</Superscript>/Ga<Superscript>3+</Superscript> doping on luminescence of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphors

Mg²⁺/Ga³⁺ doped Y₃Al₅O₁₂:Ce³⁺ phosphors were synthesized through a solid state reaction. The phase and luminescent of the synthesized phosphors were investigated. For Ga³⁺ codoped Y_2.96Ce_0.04Al_(5?x)Ga_xO₁₂ phosphors, the emission intensity increases with the increase of Ga³⁺ concentration up to Y_2.96Ce_0.04Al_4.80Ga_0.20O₁₂ and then decreases with a further increase of Ga³⁺ concentration, but the emission peak shifts to shorter wavelength continuously in the Ga³⁺ doping concentration range of 0.05–0.25. For Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors, the emission intensity decreases and the emission peak shifts to longer wavelength continuously in the Mg²⁺ doping concentration range of 0.02–0.12. The emission spectra of Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors demonstrate that the codoped Mg²⁺/Ga³⁺ ions not only induce the enhancement of Y_2.96Ce_0.04Al₅O₁₂ emission intensity but also lead to the red shift of Y_2.96Ce_0.04Al₅O₁₂ emission peak. The decay lifetimes decrease in Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al₅O₁₂ phosphors due to defects formed by substitutions of Y³⁺ by Mg²⁺/Ga³⁺.     

Radiation-Induced Effects in Ce<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-Doped Al<Subscript>5</Subscript>O<Subscript>6</Subscript>N

Polycrystalline Al₅O₆N samples have been prepared by sol–gel synthesis followed by carbothermal reduction and nitridation. X-ray luminescence (XRL) spectra and thermoluminescence (TL) curves of Ce³⁺- and Eu²⁺-doped aluminum oxynitride have been measured in the temperature range 5–380 K and analyzed. Working TL peaks have been detected in the range 150–250 K for the Al₅O₆N:Ce³⁺ sample and in the range 140–200 K for the Al₅O₆N:Eu²⁺ samples. There are also lower temperature peaks: in the ranges 10–60 and 20–100 K. The XRL spectra of the samples have been measured at temperatures of 8 (for the first time) and 300 K.     

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.     

Single step synthesis of Ce doped CaAl2O4 and CaAl4O7 systems

Both CaAl₂O₄ (CA2) and CaAl₄O₇ (CA4) oxide-systems possess monoclinic crystal structure. Herein, we have prepared CA2 and CA4 systems via single step combustion route. A good correlation is observed between calculated and the standard lattice parameters. Ce³⁺ ions were deliberately doped as extrinsic impurities in order to understand the crystal symmetry effects on the emission characteristics in the as-prepared matrices. Large red-shift was observed in CA4-emission spectrum despite of their same crystal structures. Possible reasons are discussed.     

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⁺.     

Recombination processes in the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> scintillator

The roentgenoluminescence spectra, temperature-dependent activator luminescence, optically stimulated luminescence, and the effect of IR irradiation on the yield and spectral composition of the low-temperature roentgenoluminescence and thermoluminescence curves of the Y₃Al₅O₁₂:Ce³⁺ scintillator have been studied in the temperature range 85–295 K. The results, coupled with earlier data, suggest that the Ce³⁺ ions in the garnet crystal studied form Ce³⁺ p hole centers and increase the concentration of electronic F ^?-centers responsible for the IR stimulation band at 940 nm. The reduction in roentgenoluminescence yield on cooling Y₃Al₅O₁₂:Ce³⁺ to below 230 K is due to the significant localization of excited carriers at defects, which show up in thermoluminescence peaks and optical stimulation spectra. The low-temperature Ce³⁺ luminescence in Y₃Al₅O₁₂:Ce₃₊ seems to result from the recombination of activator-bound excitons.     

Photoluminescence properties and charge compensation investigations of novel orange-emitting Eu<Superscript>3+</Superscript> doped Na<Subscript>4</Subscript>Ca<Subscript>4</Subscript>(Si<Subscript>6</Subscript>O<Subscript>18</Subscript>) phosphors

A series of polycrystalline Na₄Ca₄(Si₆O₁₈):Eu³⁺ orange emitting phosphors were synthesized by a conventional high-temperature solid-state reaction. The phase formation was confirmed by X-ray power diffraction analysis. The excitation spectra show a strong host absorption indicating an efficient energy transfer process from O^2? to Eu³⁺ ions. Upon NUV radiation, the phosphors showed strong red emission around 610 nm (⁵D₀ → ⁷F₂) and orange emission around 591 nm (⁵D₀ → ⁷F₁), but the ⁵D_1,2,3 emission nearly can not be seen. Compared with the luminescence properties of Li⁺, Na⁺, and K⁺ co-doped samples, we deduced that Na⁺ ions probably prefer to dope into the intrinsic Na vacancies rather than Ca²⁺ ions vacancies in Na₄Ca₄(Si₆O₁₈) crystal. Thermal stability properties, quantum efficiency and chromaticity coordinates of the phosphors have been investigated for the potential application in white LEDs.     

Synthesis,tunable luminescence and thermal stability of Mg<Subscript>2</Subscript>Al<Subscript>4</Subscript>Si<Subscript>5</Subscript>O<Subscript>18</Subscript>:Ce<Superscript>3+</Superscript>/Mn<Superscript>2+</Superscript> phosphors

Ce³⁺/Mn²⁺ singly doped and codoped Mg₂Al₄Si₅O₁₈ phosphors were synthesized by a solid state reaction. The phase, luminescent properties and thermal stability of the synthesized phosphors were investigated. Ce³⁺ and Mn²⁺ singly doped Mg₂Al₄Si₅O₁₈ phosphors show emission bands locating in blue and yellow–red regions, respectively. In Ce³⁺ and Mn²⁺ codoped Mg₂Al₄Si₅O₁₈, tunable luminescence was obtained because of the energy transfer from Ce³⁺ to Mn²⁺. In Mg₂Al₄Si₅O₁₈:Ce³⁺/Mn²⁺ phosphors with a fixed Ce³⁺ concentration, energy transfer efficiency increases with the increasing Mn²⁺ concentration, which is confirmed by the continually decreasing intensity and shortening decay time of Ce³⁺ emission. Moreover, the luminescent properties and thermal stability provide a great significance on the applications in the field of light emitting diodes.     

Luminescence of Ce<Superscript>3+</Superscript> ion doped in SrZn<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> phosphor under excitation of vacuum ultraviolet

Ce³⁺ doped SrZn₂(PO₄)₂ was prepared by high temperature solid-state reaction. The phosphor was investigated by X-ray powder diffraction, scanning electron microscope, and FT-IR measurements. Spectroscopic properties of the phosphor were characterized by vacuum ultraviolet spectroscopy. According to the excitation spectrum, the five 5d levels corresponding to the 4f ¹ → 4f ⁰5d ¹ transitions of Ce³⁺ ions were clearly identified. The observed excitation bands in the VUV region are due to the PO₄³⁻ anion groups of the host, in which energy transfer to Ce³⁺ ions is rather efficient. The emission bands corresponding to the 4f ¹ → 4f ⁰5d ¹ transitions of Ce³⁺ ions were analyzed. The barycenter of Ce³⁺ ions, host absorption bands, crystal field splitting, emission wavelength and Stokes shift were calculated and discussed.     

Solid state synthesis,microstructure and photoluminescence of Eu<Superscript>3+</Superscript> and Tb<Superscript>3+</Superscript> activated strontium tungstate

The Eu³⁺ and Tb³⁺ ions activated SrWO₄ phosphors have been synthesized by solid state method. The crystal structures and morphologies of the products are characterized by Powders X-ray Diffraction (XRD) and scanning electronic microscopy (SEM). The results indicated that both SrWO₄:Eu³⁺ and SrWO₄:Tb³⁺ phosphors belong to tetragonal phase, and the particles of the phosphors become aggregate with the increase of calcinations temperature. Analyzed by luminescent spectra, the dominant emission of Eu³⁺ in SrWO_4, which is the typical hypersensitive transition ⁵D₀ → ⁷F₂ (613 nm), and the green emission (⁵D₄ → ⁷F₅) intensity of Tb³⁺ in SrWO₄:Tb³⁺ is also dominant. The reaction temperature had obvious influence on the luminescent properties. The intensity reached the strongest when it is sintered at 900 °C. Therefore, we can try to select the right temperature in order to obtain the ideal product.     

Luminescence properties and energy transfer of co-doped Ba<Subscript>3</Subscript>GdNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Ce<Superscript>3+</Superscript>,Tb<Superscript>3+</Superscript> green-emitting phosphors

Phase pure Ce³⁺ and Tb³⁺ singly doped and Ce³⁺/Tb³⁺ co-doped Ba₃GdNa(PO₄)₃F samples have been synthesized via the high temperature solid-state reaction. The crystal structures, photoluminescence properties, fluorescence lifetimes, thermal properties and energy transfer of Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ were systematically investigated. Rietveld structure refinement indicates that Ba₃GdNa(PO₄)₃F crystallizes in a hexagonal crystal system with the space group P-6. For the co-doped Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ samples, the emission color can be tuned from blue to green by varying the doping concentration of the Tb³⁺ ions. The intense green emission was realized in the Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ phosphors on the basis of the highly efficient energy transfer from Ce³⁺ to Tb³⁺. Also the energy transfer mechanism has been confirmed to be quadrupole–quadrupole interaction, which can be validated via the agreement of critical distances obtained from the concentration quenching (13.84 Å). These results show that the developed phosphors may possess potential applications in near-ultraviolet pumped white light-emitting diodes.     

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.     

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.     

Synthesis,crystal structure and luminescence in Ca<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript>

Bluish green emitting phosphor, Ca₃Al₂O₆:Ce³⁺, is prepared by low-temperature combustion method. X-ray diffraction, photoluminescence, scanning electron microscopy techniques are used to characterize the synthesized phosphor. The most efficient bluish green (483 nm) emission is observed under the excitation by near UV light. The emission characteristics are credited to 5d → 4f type transitions in Ce³⁺. The luminescence properties of Eu²⁺ are predicted for the first time from those of Ce³⁺. Also, photoluminescence of Eu³⁺ is studied in the same host. The emission spectrum of Ca₃Al₂O₆:Eu³⁺ shows the peak at 592 (orange) and 614 nm (red) wavelengths. Ca₃Al₂O₆:Ce³⁺phosphor can be a potential blue phosphor for field emission display, solid-state lighting and LED.     

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.     

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.