Luminescence properties of Eu2+ and Mn2+ doped Sr1.7Mg0.3SiO4 phosphors

Eu²⁺, Mn²⁺ doped Sr_1.7Mg_0.3SiO₄ phosphors were prepared by high temperature solid-state reaction method. Their luminescence properties were studied. The emission spectra of Eu²⁺ singly doped Sr_1.7Mg_0.3SiO₄ consist of a blue band (455 nm) and a green band (550 nm). The relative intensities of two emissions varied with Eu²⁺ concentration. Eu²⁺ and Mn²⁺ co-doped Sr_1.7Mg_0.3SiO₄ phosphors emit three color lights and present whitish color. The blue (455 nm) and green (550 nm) emissions are attributed to the transitions of Eu²⁺, while the red (670 nm) emission is originated from the transition of Mn²⁺ ion. The results indicate the energy transfer from Eu²⁺ to Mn²⁺. The mechanism of the energy transfer is resonance-type energy transfer due to the spectral overlap between the emission of Eu²⁺and the absorption of Mn²⁺.     

Self-crystallized Ba2LaF7:Nd3+/Eu3+ glass ceramics for optical thermometry

Eu³⁺/Nd³⁺-codoped Ba₂LaF₇ transparent bulk glass ceramics were successfully fabricated by glass self-crystallization. The structure and morphology of the sample were investigated by X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction. The fluorescence intensity ratios of Nd³⁺ emission at 800 nm to the Eu³⁺ emission at 699 nm (⁵D₀ → ⁷F₄) were measured under 578.3 nm laser excitation in a wide temperature range from 290 to 740 K. A relatively good temperature sensing performance was obtained with a maximum relative sensitivity of 1.02% K⁻¹ at 420 K. Both the emission peaks for temperature sensing were located in the optical window of biological tissue, which is favorable for biomedical applications. The results indicate that Ba₂LaF₇:Nd³⁺/Eu³⁺ glass ceramics have a potential application as temperature probes.     

Luminescent Eu3+-doped transparent alumina ceramics with high hardness

The Eu³⁺-doped transparent aluminas were prepared by wet shaping technique followed by pressure-less sintering and hot isostatic pressing. The effect of dopant amount on microstructure, real in-line transmission (RIT), photoluminescence (PL) properties, hardness and fracture behaviour was studied. The RIT decreased with increasing amount of the dopant. The PL emission spectra of Al₂O₃:Eu³⁺ ceramics exhibited predominant red light emission with the highest intensity (under 394 nm excitation) for material containing 0.125 at.% of Eu³⁺ and colour coordinates (0.645, 0.355) comparable with commercial red phosphors. The doping resulted in hardness increase from 26.1 GPa for undoped alumina to 27.6 GPa for Eu-doped sample. The study of fracture surfaces showed predominantly intergranular crack propagation micro-mechanism.     

Energy transfer,tunable emission and optical thermometry in Tb3+/Eu3+ co-doped transparent NaCaPO4 glass ceramics

Tb³⁺/Eu³⁺ co-doped glass ceramics containing NaCaPO₄ nanocrystals were successfully synthesized via traditional melt-quenching route with further heat-treatment and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy. The energy transfer process of Tb³⁺→Eu³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results indicated that the efficient emission of Eu³⁺ was sensitized by Tb³⁺ under the excitation of 378 nm, realizing tunable emission in the transparent bulk glass ceramics containing NaCaPO₄ nanocrystals. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺:⁵D₄→⁷F₅ (~542 nm) and Eu³⁺:⁵D₀→⁷F₂ (~612 nm). The maximum absolute sensitivity of 4.55% K⁻¹ at 293 K and the maximal relative sensitivity of 0.66% K⁻¹ at T=573 K for Tb³⁺/Eu³⁺ co-doped transparent NaCaPO₄ glass ceramic are obtained. It is expected that the investigated transparent NaCaPO₄ glass ceramics doped with Tb³⁺/Eu³⁺ have prospective applications in display technology and optical thermometry.     

Crystal structure,luminescent properties and white light emitting diode application of Ba3GdNa(PO4)3F:Eu2+ single-phase white light-emitting phosphor

A series of single-phase white-light-emitting phosphors, Eu²⁺-activated Ba₃GdNa(PO₄)₃F phosphors were synthesized by solid-state reactions. The crystal structure of Ba₃GdNa(PO₄)₃F was been identified by Rietveld refinement of X-ray diffraction pattern. The Eu²⁺-activated Ba₃GdNa(PO₄)₃F phosphors exhibit broad excitation spectra from 250 to 420 nm, which matched well with the n-UV LED chips. Under the excitation of 365 nm, the emission spectrum almost covered the entire visible region including two emission bands peaked at 472 nm and 640 nm. Three different Eu²⁺ emission centers in Ba₃GdNa(PO₄)₃F:Eu²⁺ phosphor were confirmed by their fluorescence decay lifetimes. The optimal concentration of Eu²⁺ in Ba₃GdNa(PO₄)₃F:xEu²⁺ was 3 mol% and the corresponding concentration quenching mechanism was verified to be exchange coupling interaction. Furthermore, the white light-emitting diode fabricated with Ba₃GdNa(PO₄)₃F:0.05Eu²⁺ phosphor and a 370 nm UV chip has a CIE of (0.3267, 0.2976) with a color-rendering index of 78.4 at the CCT of 5287 K.     

Warm with high color rendering index white light from hybridization of Ca2BO3Cl:Eu2+ yellow phosphor and CdSe/ZnS nanocrystals

Yellow emitting Ca₂BO₃Cl:Eu²⁺ phosphor was prepared by solid state reaction at 900 °C. The particle was monoclinic crystal structure, and showed broad band emission at around 540–590 nm due to the 5d–4f transition. Single Ca₂BO₃Cl:Eu²⁺ phosphor converted white LED exhibited the CIE coordinates of (0.3441, 0.2675) with low CRI of 67.4. Hybridization of Ca₂BO₃Cl:Eu²⁺ with 535 and 610 nm emitting CdSe/ZnS nanocrystals contributed to increasing white spectrum and generated the warm color temperature (4055 K) with high CRI (83.9) of white light. The acceptable color stability was also observed from (0.3687, 0.3051) at 20 mA to (0.3645, 0.3101) at 80 mA.     

Luminescence and structural properties of Gd2SiO5:Eu3+ phosphors synthesized from the modified solid state method

This paper reports the preparation of Eu³⁺ doped Gadolinium oxyorthosilicate (Gd₂SiO₅:Eu³⁺) phosphor with different concentration of Eu³⁺(0.1–2.5 mol%) using the modified solid state reaction method. The synthesis procedure of the Gd₂SiO₅:Eu³⁺phosphor using inorganic materials such as Gd₂O₃, silicon dioxide (SiO₂), europium oxide (Eu₂O₃) and boric acid (H₃BO₃) as flux is discussed in detail. The prepared phosphor samples were characterized by using X-Ray Diffraction (XRD), Field Emission Gun Scanning Electron Microscopy (FEGSEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Photoluminescence (PL) and Thermoluminescence (TL). The Commission Internationale de l′Eclairage(CIE) coordinates were also calculated. The PL emission was observed in the 350–630 nm range for the Gd₂SiO₅:Eu³⁺ phosphor. PL excitation peaks were observed at 266, 275, 312 and 395 nm while the emission peaks were observed at 380, 416, 437, 545, 579, 589, 607, 615 and 628 nm. The emission peak at 615 nm was the most intense peak for all the different Eu³⁺ concentration samples. From the XRD data, using the Scherrer's formula, the average crystallite size of the Gd₂SiO₅:Eu³⁺ phosphor was calculated to be 33 nm. TL was carried out for the phosphor after both UV and gamma irradiation. The TL response of the Gd₂SiO₅:Eu³⁺ phosphor for the two different radiations was compared and studied in detail. It was found that the present phosphor can acts as a single host for red emission (1.5 mol%) for display devices and light emitting diode (LED) and white light emission for Eu³⁺(0.1 mol%) and it might be used as a TL dosimetric material for gamma dose detection.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Synthesis and characterization of the crystalline powders on the basis of Lu2O3:Eu3+spherical submicron-sized particles

This study is devoted to the preparation of the crystalline powders on the basis of non-agglomerated monodisperse Lu₂O₃:Eu³⁺ spherical particles with the diameters in the range of 50–250 nm by the soft chemistry co-precipitation route. The influence of the synthesis parameters on control morphology, particles size and agglomeration in the final Lu₂O₃:Eu³⁺ powder was considered. Lu₂O₃:Eu³⁺ crystalline powders were characterized by means of electron microscopy methods (TEM, SEM), FT-IR spectroscopy, thermal analysis (TG-DTA) and X-ray diffractometry. The mechanisms of the precursor decomposition and crystallization at the temperatures ranging from 60 to 900 °C were discussed. It was shown that the powders obtained were characterized by the effective luminescence under X-ray excitation in λ = 575–725 nm spectral region corresponding to ⁵D₀ → ⁷F_J transitions (J = 0–4) of Eu³⁺ ions with a maximum at 612 nm and the luminescence intensity strongly depends on annealing temperature. The relative densities of the green-bodies on the basis of Lu₂O₃:Eu³⁺ powders were estimated and the sintering of compacts at the temperatures up to 1500 °C was studied.     

Preparation and photoluminescence properties of Eu3+-doped ZrO2 nanotube arrays

Zr–Eu alloy containing 3 at% Eu was prepared by a powder metallurgical method and Eu³⁺-doped ZrO₂ nanotube arrays were prepared by anodising the Zr–Eu alloy. The properties of Eu³⁺-doped ZrO₂ nanotube arrays were studied in contrast to undoped ZrO₂ nanotube arrays under different annealing temperatures. Results showed that the Eu³⁺ ions could not only stabilise the tetragonal phase of zirconium oxide, but also make the crystallite sizes smaller. Annealing temperature exerted a significant influence on the absorbance value, as well as the intensity and position of the photoluminescence peaks. When the excitation wavelength was either 248 nm or 270 nm, the sample annealed at 600 °C displayed the strongest emission peak; while under excitation at 232 nm, the sample annealed at 400 °C exhibited the strongest emission peak.     

Monodisperse nanospheres of yttrium oxysulfide: Synthesis,characterization, and luminescent properties

A red long-lasting phosphorescent material, monodisperse Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ nanospheres have been prepared successfully. Y(OH)(CO₃): Eu³⁺ nanospheres were firstly synthesized via an urea-based homogeneous precipitation technique to serve as the precursor. Nanospheres long-lasting phosphors Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ were obtained by calcinating the precursor in CS₂ atmosphere. XRD investigation shows a pure phase of Y₂O₂S, indicating no other impurity phase appeared. SEM observation reveals that the structures are nanosphere. The Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ nanospheres with particle size about 100–150 nm show uniform size and well-dispersed distribution. After irradiation by ultraviolet radiation with 325 nm for 5 min, the phosphor emitted red color long-lasting phosphorescence corresponding to typical emission of Eu³⁺ ion. The main emission peaks are ascribed to Eu³⁺ ions transition from ⁵D_J (J = 0, 1, 2) to ⁷F_J (J = 0, 1, 2, 3, 4). Both the PL spectra and luminance decay revealed that this phosphor had efficient luminescent and long-lasting properties. It was considered that the red-emitting long-lasting phosphorescence was due to the persistent energy transfer from the traps to the Ti⁴⁺ and Mg²⁺ ions.     

Structural and spectral properties of red light emitting Eu3+ activated TiO2 nanophosphor for white LED application

The structural and luminescent properties of Eu³⁺ doped TiO₂ nanophosphors synthesized by low cost combustion method were investigated. The X-ray diffraction analysis revealed that crystallite size decreases with doping concentration. Lattice volume expansion occurred due to the substitution of Ti⁴⁺ ions by larger ionic radii ions Eu³⁺. FESEM images showed prepared phosphors to be nano size spherical shaped particles. Energy band gap of 3 mol% Eu³⁺ doped samples decreased to 3.15 eV due to doping effect. The Eu³⁺ doped TiO₂ nanophosphors exhibited main red emission peak centered at 616 nm under 395 nm UV light excitation. Concentration quenching was observed at 3 mol% doping, that has been ascribed to dipole-dipole interaction. The covalent nature of Eu-O bond and environment around Eu³⁺ ions were discussed using Judd-Ofelt (J-O) intensity parameters. Internal quantum efficiency was calculated using excited state lifetime ⁵D₀ state of Eu³⁺ ion and J-O theory. The CIE colour coordinates and colour purity were calculated using the spectral energy distribution function. Low excited state life time indicated that Eu³⁺ doped TiO₂ can be used as red emitting phosphor for white light emitting diode applications.     

Molten salt synthesis and optical properties of Eu3+, Dy3+or Nd3+ doped NiNb2O6 columbite-type phosphors

Pure, Eu³⁺, Dy³⁺ or Nd³⁺-doped NiNb₂O₆ powders have been prepared by a molten salt synthesis method by using Li₂SO₄–Na₂SO₄ salt mixture as a flux at relatively low temperatures as compared to the solid state reaction method. X-ray diffraction patterns of pure NiNb₂O₆ samples indicated an orthorhombic single phase. For Eu³⁺-doped NiNb₂O₆ samples, the luminescence of Eu³⁺ was observed at 615 nm as red emission while Dy³⁺-doped NiNb₂O₆ showed yellow emission at 577 nm and Nd³⁺ doped sample exhibited a typical emission at 1064 nm varying with the Eu³⁺ or Nd³⁺ doping concentrations. These luminescence characteristics of the doped samples may be attributed to the energy transfer between rare earth ions and NiO₆ octahedral groups in the columbite structure.     

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.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Persistent photoluminescence emission from SrTa2O6:Pr3+ phosphor prepared at different temperatures

Phosphors with persistent emission are of interest for security and emergency signage, and medical diagnosis. Three SrTa₂O₆:Pr³⁺phosphor samples with persistent emission were prepared by solid state reaction at 1200, 1400 and 1500 °C. Structural crystallization was shown to improve with an increase in temperature as identified by X-ray diffraction. The scanning electron microscopy images showed that the particles of the phosphor were agglomerated and co-melting was induced by increasing the synthesis temperature. The ion distribution in the phosphors was determined using the time of flight secondary ion mass spectroscopy. The red emission was obtained from the D₂→³H₄ and the ³P₀→³H₆ transitions at 608 and 619 nm, respectively. The main absorption occurred at 225 nm (5.5 eV), and the band gap (E_g) calculations confirmed that it corresponds to band-to-band excitation. Another excitation due to charge transfer at 300 nm was also obtained which makes the phosphor suitable to be used in red light emitting diodes. The persistent emission time parameters (260–296 s) were calculated from the phosphorescence decay curves using the second order exponential decay equation. The corresponding electron trapping centers were determined using the thermoluminescence spectroscopy, and the activation energy was determined using the initial rise method.     

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.     

Structural and optical investigations of Eu3+-doped TiO2 nanopowders

This paper presents an evaluation of photoluminescent and structural properties of Eu³⁺-doped TiO₂ materials in powder form prepared by sol–gel process. The increase of heat-treatment temperature of synthesis results in the TiO₂ phase transition, obtaining anatase, rutile and sometimes brookite, examined by Raman and XRD techniques. Crystallite size as well as microstrains in the crystal structure were evaluated as a function of Eu³⁺ and heat-treatment temperature. It was found that when Eu³⁺ is introduced in anatase phase an intense color emission is observed under excitation at 394 and 463 nm. The rutile phase presents inversion center symmetry, and apparently the Eu³⁺ tends to occupy this site, which decreases the intensity of the emission assigned to the ⁵D₀→⁷F₂ transition. The materials obtained at 700 °C showed most intensity of emission in the red region, verified by the ratio between ⁵D₀→⁷F₂/⁵D₀→⁷F₁ transitions of Eu³⁺. The results showed that the materials are interesting absorber in the ultraviolet and red region and can be used for improvement of energy conversion in solar cells devices.     

Sintering of Yb3+:Y2O3 transparent ceramics in hydrogen atmosphere

Highly transparent Yb³⁺:Y₂O₃ ceramics with doping concentration up to 40.0 at.% had been fabricated successfully via hydrogen atmosphere sintering, where the raw powders were synthesized by co-precipitation method. The sintering temperature is about 600 °C lower than its melting temperature. SEM investigation revealed the average grain size of Yb³⁺:Y₂O₃ ceramics sintered at 1850 °C for 9 h was about 7 μm. The highest transmittance of as-prepared 1 mm thickness samples around wavelength of 1050 nm reached 80%, which is close to the theoretical value of Y₂O₃. The optical spectroscopic properties of Yb³⁺:Y₂O₃ transparent ceramics have also been investigated, which shows that it is a very good laser material for diode laser pumping and short pulse mode-locked laser.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.