Effect of Sr2+-doping on structure and luminescence properties of BaAl2Si2O8:Eu2+ phosphors

Sr²⁺ doped BaAl₂Si₂O₈:Eu²⁺ phosphor was synthesized by chemical co-precipitation method. With the increase of Sr²⁺ concentration, the phase structure of (Ba_0.965 ? xSr_xEu_0.035)Al₂Si₂O₈ changes from hexagonal phase to monoclinic phase owing to large activation energy in SrAl₂Si₂O₈ system. (Ba_0.965 ? xSr_xEu_0.035)Al₂Si₂O₈ phosphor exhibits a broad blue band peaking at 425 nm due to the 4f⁶5d–4f⁷(⁸S_7/2) transition of Eu²⁺ ions. The emission intensity increases, accompanied by the blue shift of emission maximum from 459 to 417 nm with the Sr²⁺ doping concentration increasing. The optimal concentration of Sr²⁺ ion is 40%, and the phosphor shows high color stability in CIE chromaticity diagram. The result indicates that Sr²⁺ doped phosphor not only can enhance the relative intensity but also can adjust the chromaticity coordinate.     

Photoluminescence and phosphorescence properties of MAl2O4:Eu, Dy (M=Ca, Ba, Sr) phosphors prepared at an initiating combustion temperature of 500 °C

Eu²⁺ and Dy³⁺ co-doped calcium aluminate, barium aluminate and strontium aluminate phosphors were synthesized at an initiating combustion temperature of 500 °C using urea as an organic fuel. The crystallinity of the phosphors was investigated by using X-ray diffraction (XRD) and the morphology was determined by a scanning electron microscope (SEM). The low temperature monoclinic structure for both CaAl₂O₄ and SrAl₂O₄ and the hexagonal structure of BaAl₂O₄ were observed. The effect of the host materials on the photoluminescence (PL) and phosphorescence properties were investigated by using a He-Cd Laser and a Cary Eclipse fluorescence spectrophotometer, respectively. The broad band emission spectra observed at 449 nm for CaAl₂O₄:Eu²⁺, Dy³⁺, 450 nm (with a shoulder-peak at 500 nm) for BaAl₂O₄:Eu²⁺, Dy³⁺ and 528 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ are attributed to the 4f⁶5d¹ to 4f⁷ transition in the Eu²⁺ ion in the different hosts.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

Blue emission in Eu2+ activated MgXAl10O17 (X = Sr,Ca) phosphors

Here we reported photoluminescence properties of Eu²⁺ activated in novel and existing MgXAl₁₀O₁₇ (X = Sr, Ca) phosphor which has been prepared by combustion synthesis at 550 °C under UV and near UV excitation wavelength. The PL emission properties of MgSrAl₁₀O₁₇:Eu²⁺ were monitored at 254 nm and 354 nm respectively keeping emission wavelength at 469 nm. Whereas novel MgCaAl₁₀O₁₇:Eu²⁺ exhibit emission band at 452 nm keeping excitation at 378 nm. These blue emission corresponds to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions. Further phosphor was analyzed by XRD for the confirmation of desired phase and purity.     

Eu3+ emission in SrAl2B2O7 based phosphors

Eu³⁺ doped SrAl₂B₂O₇ phosphors were fabricated by the wet method. The structures of the phosphors were characterized by XRD. The doping content of Eu³⁺ ions in SrAl₂B₂O₇:Eu³⁺ phosphors are 1%, 4%, 6%, 8%, 10% (molar fraction), respectively. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. The luminescent properties of SrAl₂B₂O₇:Eu³⁺ phosphors are discussed. It is shown that from 4% to 6% of doping content of Eu³⁺ ions under 392 nm excitation in SrAl₂B₂O₇:Eu³⁺ phosphors is optimum.     

Optical study of rare earth activated NaBa0.45Sr0.55PO4 phosphor

Dy³⁺ and Eu²⁺ activated triple phosphate NaBa_0.45Sr_0.55PO₄ phosphors were prepared by facile combustion synthesis. Excellent emission observed when NaBa_0.45Sr_0.55PO₄:Dy³⁺ and NaBa_0.45Sr_0.55PO₄:Eu²⁺ excited at 348 nm and 354 nm wavelength respectively. From a powder X-ray diffraction (XRD) analysis, the formation of compound with a trigonal–hexagonal scalenohedral structure was confirmed. In the photoluminescence spectra, the NaBa_0.45Sr_0.55PO₄:Dy³⁺ phosphor emits two distinctive colours: a blue band centred at 482 nm and a yellow band at 576 nm originating from Dy³⁺ whereas NaBa_0.45Sr_0.55PO₄:Eu²⁺ emits blue colour at 470 nm. Also, surface morphology has been studied by scanning electron microscope (SEM). Phosphors exhibit a strong absorption in the range of 340–400 nm and chromatic properties indicated that present phosphor is a hopeful candidate for near ultra violet light emitting diodes (nUV LEDs).     

Probing lattice defects in Sr2MgSi2O7:Eu2+,Dy3+

The Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ materials were prepared with a solid state reaction and their microscopic structure (at 295 K only) and luminescence were studied at selected temperatures between 150 and 295 K. Undisturbed Sr crystal planes were common in the TEM images of the undoped Sr₂MgSi₂O₇ material, whereas with Eu²⁺ doping more disturbed planes were observed even in the nanometer scale. With Dy³⁺ co-doping, a large number of small lattice domains created by the discontinuities in the crystal structure was observed. The domains with different orientations seem to be centered around point defects. The decay curves of Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ showed fast (ms scale) persistent luminescence. The intensity of persistent luminescence increased considerably between 200 and 250 K while remaining constant in the ranges of 150–200 and 250–295 K. The changes were used to study the depth of the traps. In general, Dy³⁺ co-doping was found to deepen the traps.     

Preparation and luminescence properties of Eu2+-doped BaSi2O5 glass-ceramics

We report on the preparation of Eu²⁺-doped BaSi₂O₅ glass-ceramics by crystallizing an Eu³⁺-doped barium-silicate glass at temperatures in the range from 750 to 1100 °C. Single phase BaSi₂O₅ glass ceramics can be obtained by thermal annealing at temperatures of about 950 °C. The luminescence intensity of Eu²⁺ increases dramatically if monoclinic BaSi₂O₅ is formed. Monoclinic Eu²⁺:BaSi₂O₅ shows efficient, broad band luminescence between 450 and 550 nm by excitation in the near UV. Annealing at temperatures >1000 °C leads to orthorhombic BaSi₂O₅ with much smaller Eu²⁺ luminescence. Static and time-resolved luminescence measurements indicate that Eu²⁺ ions are incorporated into the BaSi₂O₅ crystallites while Eu³⁺ ions remain in the amorphous phase.     

Spectroscopy study of SrAl2O4:Eu3+

Computational and experimental method is employed to study optical properties SrAl₂O₄ induced by europium dopant. Atomistic modeling is used to predict the doping sites and charge-compensation schemes for SrAl₂O₄:Eu systems and also to calculate the symmetry and the detailed geometry of the dopant site. This information is then used to calculate the crystal field parameters. SrAl₂O₄ doped with europium were prepared via a sol–gel proteic methodology. The photoluminescence experiments were performed at room temperature and at 13 K. The transition energy for the Eu³⁺-doped material is compared to the theoretical results. Based on Judd-Ofelt approach, the intensity parameters Ω_2,4 of Eu³⁺ in the SrAl₂O₄ matrix were calculated.     

Photoluminescence properties of Eu2+–Mn2+ codoped Ca-α-SiAlON phosphors

Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors, Ca_0.736?ySi_9.6Al_2.4O_0.8N_15.2:0.064 Eu²⁺, yMn²⁺, were firstly synthesized by the high temperature solid state reaction method. The effects of doped Eu²⁺ and Eu²⁺–Mn²⁺ concentrations on the photoluminescence properties of the as-prepared phosphors were investigated systematically. Powder X-ray diffraction shows that pure Ca-α-SiAlON phase is synthesized after sintering at 1700 °C for 2 h under 0.5 MPa N₂ atmosphere. The excitation spectra of Eu²⁺-doped Ca-α-SiAlON phosphors are characterized by two dominant bands centered at 286 nm and 395 nm, respectively. The photoluminescent spectrum of Eu²⁺-doped Ca-α-SiAlON phosphor exhibits an intense emission band centered at 580 nm due to the allowed 4f ⁶5d→4f ⁷ transition of Eu²⁺, showing that the phosphor is a good candidate for creating white light when coupled to a blue LED chip. The intensities of both excitation and emission spectra monotonously decrease with the increment of codoped Mn²⁺ content (i.e. y value), indicating that energy transfer between Eu²⁺ and Mn²⁺ is inefficient in the case of Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors.     

The influence of Eu3+ doping on photoluminescent properties of red emitting phosphor YInGe2O7:Eu3+ by microwave assisted and conventional sintering method

This paper describes an investigation of the crystalline morphology and photoluminescent properties of YInGe₂O₇ powders doped with different Eu³⁺ concentrations using microwave assisted sintering and conventional sintering. X-ray powder diffraction analysis confirmed the formation of monoclinic YInGe₂O₇ structure as YInGe₂O₇:Eu³⁺ powders were sintered at 1200 °C in microwave furnace for 1 h, and the raw material phase of Y₂O₃ was observed when Eu³⁺ concentration was below 30 mol%. Scanning electron microscopy showed microwave assisted sintering results in smaller particle size and more uniform grain size distribution. In the photoluminescent (PL) studies, the concentration quenching effect was observed under the excitation at 393 nm, but not under the excitation at CTS band. The ⁵D₀→⁷F₂ transition (620 nm), exhibits a non-exponential decay behavior as YInGe₂O₇:Eu³⁺ powders were sintered by microwave with the Eu³⁺ concentration higher than 50 mol%.     

Temperature sensing performance of dysprosium doped aluminum oxide powders

Dy³⁺-doped Al₂O₃ powders were prepared by combustion synthesis. Down-converted luminescence lines peaked at 451 and 471, 572, 660, 708 and 752 nm were obtained under 355 nm pulsed laser irradiation for as-prepared Dy³⁺ doping concentrations of 0.5, 1.0 and 2.0 wt.%. The fact that the relative intensities of the 451 and 471 nm luminescence bands changed with the samples temperature allowed the use of these emission lines for temperature sensing. We found that the maximum sensitivity of the temperature sensor based on the luminescence intensity ratio of those transitions changed with Dy³⁺ doping concentration indicating different coupling strengths between the crystal field and the rare-earth.     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.     

PHASE DEPENDENCE OF LUMINESCENT EMISSION OF Eu2+ DOPED SrAl2O4

In this work, we made five samples of SrAl₂O₄: Eu²⁺, Dy³⁺, the α phase and β phase SrAl₂O₄:Eu²⁺,Dy³⁺ powder and pellet samples, and α phase single crystal. We have measured the emission spectra of all the samples. All the emission peaks are around 520 nm, which correspond to the transition from 4f⁶5d¹(²E_g) to 4f⁷(⁸S_7/2) of Eu²⁺ in SrAl₂O₄ host. The intensity of emission of the β phase is stronger than that of the α phase. We believe that it is because the Eu²⁺ ions have occupied the two types of sites in the α phase SrAl₂O₄ host and the lifetime of the transition of Eu²⁺ in the A site is longer than that in the B site. This result also proves that the β phase of the material is brighter than the α phase. In addition, the β phase can be achieved by quenching technique.     

Crystal structure and photoluminescence correlations in white emitting nanocrystalline ZrO2:Eu3+ phosphor: Effect of doping and annealing

White emitting nanocrystalline ZrO₂:Eu³⁺ phosphors were synthesized by a simple precipitation route without using a capping agent. X-ray diffraction (XRD) study of ZrO₂ and ZrO₂:Eu³⁺samples revealed the presence of monoclinic and tetragonal phases. The monoclinic phase increases with increase in the annealing temperature while the tetragonal phase increases with increase in the concentration of Eu³⁺. This can be attributed to the presence of oxygen vacancy evolved when Zr⁴⁺ is replaced by Eu³⁺. Photoluminescence (PL) emission peaks of Eu³⁺ are observed at 591, 596, 606 and 613 nm on monitoring excitation wavelengths at 250, 286, 394 and 470 nm. The peaks at 591 and 606 nm were found to correlate with the tetragonal phase and those at 596 and 613 nm with the monoclinic phase. Intensities of these peaks are found to change as the crystal structure changes. The lifetime value corresponding to 591 nm peak increases with Eu³⁺ concentration at a particular heating temperature indicating increase of tetragonal phase with respect to monoclinic phase. The CIE co-ordinates of the doped samples were found to be close to that of white color (0.33, 0.33). The changes in the crystal structure of the doped samples due to doping and annealing did not affect the white color emission.     

Synthesis and luminescence properties of green phosphors Ca6Sr4(Si2O7)3Cl2:Eu2+ for white light emitting diodes

Divalent europium-activated chlorosilicate Ca₆Sr₄(Si₂O₇)₃Cl₂:Eu²⁺ phosphors were synthesized by a conventional solid-state reaction under reductive atmosphere. These phosphors can be efficiently excited by UV–visible light from 320 to 420 nm, which matches that of a near UV-emitting InGaN chip. Under the 360 nm excitation, Ca₆Sr_3.97(Si₂O₇)₃Cl₂:0.03Eu²⁺ phosphor shows a strong and broad emission centering at 515 nm, which is attributed to the 5d→4f transition of Eu²⁺ ion. The mechanism of concentration quenching was determined to be the dipole–dipole interaction and the critical energy-transfer distance of Eu²⁺ was calculated as 3.31 nm. The CIE chromaticity coordinates of Ca₆Sr_3.96(Si₂O₇)₃Cl₂:0.03Eu²⁺ phosphor are (0.127, 0.770) according to the emission spectrum. It can be expected that Ca₆Sr₄(Si₂O₇)₃Cl₂:Eu²⁺ phosphor is a promising candidate as the green component for near-ultraviolet InGaN-based white LED.     

Phase dependent photoluminescence and energy transfer in Ca2P2O7: Eu2+, Mn2+ phosphors for white LEDs

α- and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ phosphors were prepared by solid-state reaction. Phase transition from tetragonal (β-phase) to monoclinic (α-phase) is performed. A strong orange emission of Mn²⁺ is observed in both α-and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ upon near ultraviolet (UV) excitation through energy transfer from Eu²⁺ to Mn²⁺. The transfer efficiencies for various Mn²⁺ concentrations are estimated based on lifetime measurements of the fluorescence of Eu²⁺ in the two phases. The photoluminescence excitation spectra of α-Ca₂P₂O₇: Eu²⁺, Mn²⁺ can cover 400 nm of the near-UV range, denoting its potential use as a phosphor with intense orange component for white light emitting diodes (LEDs).     

Radioluminescence properties of rare earths doped SrAl2O4 nanopowders

Nanopowders of SrAl₂O₄ pure and doped with rare earths were prepared via a proteic sol-gel methodology. The prepared materials presented a single crystalline phase, confirmed by XRD measurements. AFM results indicate that the average particle size is about 53 nm for SrAl₂O₄ powders. The radioluminescence spectrum of SrAl₂O₄: Eu²⁺, Dy³⁺ is composed by two intense peaks around 520 and 570 nm followed by a weaker emission peaking at 615 nm. It was observed that the intensity of RL emission during irradiation with X-rays decreased as a function of the irradiation time, indicating the build up of radiation damage in the nanopowders. The irradiated samples exhibited a persistent radiation damage that changes the colour of the sample, and also influenced the reduction in the scintillation efficiency. The saturation level of SrAl₂O₄: Eu²⁺ is 96%, exhibiting good resistance to radiation damage.     

Persistent luminescence dosimetric properties of UV-irradiated SrAl2O4:Eu, Dy phosphor

Current radiation dosimetry methods involve the release of trapped charge carriers in the form of electrons-holes pairs generated by irradiation exposure of the dosimetric materials. Thermal and optical stimulations of the irradiated material freed the trapped charges that eventually recombine with interband centers producing the emission of light. The integrated intensity of the emitted light is proportional to the radiation dose exposure. In this work, we present an UV radiation dosimetry technique based on the characteristic persistence luminescence (PLUM) 4f⁶5d¹→4f⁷ electronic transition of Eu²⁺ ions in SrAl₂O₄:Eu²⁺, Dy³⁺. The dose assessment is carried out by measuring the PLUM signal integrated during a certain time. The PLUM performance of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphor exhibited a linear behavior for the first 50 s of UV irradiation. For higher UV time exposure the behavior is sublinear with no apparent saturation during a 10 min period. The PLUM dosimetry response was performed at 400 nm that corresponds to the main band component of the PLUM excitation spectrum in the 250-500 nm range. The main advantage of a dosimeter device based on the PLUM of SrAl₂O₄:Eu²⁺, Dy³⁺ is that neither thermal nor optical stimulation is required, avoiding the need of cumbersome electronic photo/thermal stimulation equipment. Due to the highly efficient 250-500 nm PLUM response of SrAl₂O₄:Eu²⁺, Dy³⁺, it could have potential application as UV radiation dosimeter in the UV range of grate human health concerns caused by UV solar radiation.     

Synthesis and luminescence of La2BaZnO5 phosphors

A modified synthesis of La₂BaZnO₅ phosphors activated with rare earths Eu³⁺, Tb³⁺, Pr³⁺ and Sm³⁺, and ns² ion Bi³⁺ is reported. RE₂BaZnO₅ compounds are conventionally prepared by two step solid state reaction. In the first step, carbonates or similar precursors are intimately mixed and heated at 900 °C to decompose the precursors to oxides. To eliminate the unwanted phases like BaRE₂O₄, the resulting powders are reheated at 1100 °C for long time. We prepared La₂BaZnO₅ phosphors activated with various activators by replacing the first step by combustion synthesis. Results on photoluminescence are presented. PL results on Eu³⁺ and Tb³⁺ are in good agreement with the literature reports. PL emission from Sm³⁺, Pr³⁺ and Bi³⁺ had not been reported earlier. Excitation spectrum of Eu³⁺ is dominated by a charge transfer band around 318 nm, while for the other rare earths a band at 240 nm is always present. This is attributed to the host absorption.