PL Properties of Sr<Subscript>2</Subscript>CeO<Subscript>4</Subscript> With Eu<Superscript>3+</Superscript> and Dy<Superscript>3+</Superscript> for Solid State Lighting Prepared by Precipitation Method

Photoluminescence studies of pure and Dy³⁺, Eu³⁺ doped Sr₂CeO₄ compounds are presented by oxalate precipitation method for solid state lighting. The prepared samples also characterized by XRD, SEM (EDS) and FTIR spectroscopy. The pure Sr₂CeO₄ compound displays a broad band in its emission spectrum when excited with 280 nm wavelength, which peaks centered at 488 nm, which is due to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ions. Emission spectra of Sr₂CeO₄ with different concentration of Dy³⁺ ions under near UV radiation excitation, shows that intensity of luminescence spectra is found to be affected by Dy³⁺ ions, and it increases with adding some percentages of Dy³⁺ ions. The maximum doping concentration for quenching is found to be Dy³⁺?=?0.2 mol % to Sr²⁺ions. The observed broad spectrum from 400 to 560 nm is mainly due to CT transitions in Sr₂CeO₄ matrix and some fractional contribution of transitions between ⁴F_9/2 → ⁶H_15/2 of Dy³⁺ ions. Secondly the effect of Eu³⁺ doping at the Sr²⁺ site in Sr₂CeO₄, have been studied. The results obtained by doping Eu³⁺ concentrations (0.2 mol% to 1.5 mol%), the observed excitation and emission spectra reveal excellent energy transfer between Ce⁴⁺ and Eu³⁺. The phenomena of concentration quenching are explained on the basis of electron phonon coupling and multipolar interaction. This energy transfer generates white light with a color tuning from blue to red, the tuning being dependent on the Eu³⁺ concentration. The results establish that the compound Sr₂CeO₄ with Eu³⁺?=?1 mol% is an efficient “single host lattice” for the generation of white lights under near UV-LED and blue LED irradiation. The commission internationale de I’Eclairage (CIE) coordinates were calculated by Spectrophotometric method using the spectral energy distribution of prepared phosphors.     

Synthesis and Optical Characterization of Red-Emitting BaTa<Subscript>2</Subscript>O<Subscript>6</Subscript>:Eu<Superscript>3+</Superscript> Phosphors

Undoped and Eu³⁺ doped BaTa₂O₆ phosphors were synthesized via solid state reaction method and characterized by using XRD, SEM-EDS and photoluminescence (PL) analyses. The XRD results revealed that the crystal structure of BaTa₂O₆ allowed up to 10 mol% levels of Eu³⁺ ions due to the TTB characteristic network of adjacent octahedrals. SEM-EDS analyses confirmed the formation of BaTa₂O₆ structure and EuTaO₄ secondary phase. BaTa₂O_6:Eu³⁺ phosphors exhibited orange and red emissions at 592.2 nm and 615.7 nm in the visible region respectively. The Commission Internationale d’Eclairage (CIE) chromaticity coordinates of the BaTa₂O_6:Eu³⁺ phosphors that excited at λ _ex = 400 nm ranged from orangish-red to pinkish-red depending on increasing Eu³⁺ concentration.     

Synthesis and Optical Properties of Novel Red-Emitting PbNb<Subscript>2</Subscript>O<Subscript>6</Subscript>: Eu<Superscript>3+</Superscript> Phosphors

Undoped and PbNb₂O_6:Eu³⁺ (1.0 ≤ x ≤ 6.0 mol%) phosphors were synthesized at 1100 °C for 3.5 h by the conventional solid state reaction method. Synthesized PbNb₂O₆:Eu³⁺ phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed series of excitation peaks between 350 and 430 nm due to the 4f–4f transitions of Eu³⁺. For 395.0 nm excitation, emission spectra of Eu³⁺ doped samples were observed at 591 nm (orange) and 614 nm (red) due to the ⁵D₀ → ⁷F₁ transitions and ⁵D₀ → ⁷F₂ transitions, respectively. PL analysis results also showed that the emission intensity increased by increasing Eu³⁺ ion content. No concentration quenching effect was observed. The CIE chromaticity color coordinates (x,y) of the PbNb₂O₆:Eu³⁺ phosphors were found to be in the red region of the chromaticity diagram.     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.     

Eu<Superscript>3+</Superscript> As a Luminescent Probe for Studying the Structure of R<Subscript>2</Subscript>O<Subscript>3</Subscript> Materials (R = Y,Eu, and Gd)

Spectra of Eu³⁺ in various dielectric matrices (Gd₂O₃:Eu³⁺, Y₂O₃:Eu³⁺, Eu₂O₃, and mSiO₂/Gd₂O₃:Eu³⁺ mesoporous particles) are studied by local cathodoluminescence. The results allowed identification of the local environment of Er³⁺ ions in amorphous samples and detection of the monoclinic Eu₂O₃ phase impurity in samples with yttrium oxide. The cathodoluminescence spectra of chemically pure Y₂O₃, Eu₂O₃, and Gd₂O₃ are recorded. Conclusions about the structural features of the materials are made and confirmed by other methods (XRD and EPMA).     

Optical and fluorescent properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel planar waveguides containing Tb<Superscript>3+</Superscript> doped nanocrystals

Terbium doped Y₂O₃ planar waveguides were fabricated by sol–gel process and dip-coating using yttrium acetate as precursor. Two different doping modes were compared, i.e. introduction in the sol of dispersed Tb³⁺ions from dissolved Tb(NO₃)₃, or of nanoparticles of Tb₂O₃ or [Y₂O₃:50% Tb] from an alcoholic suspension. The chemical and nanostructural properties were analyzed by infrared spectroscopy, transmission electron microscopy and X-ray diffraction. The Tb³⁺ fluorescence properties were studied as a function of temperature and atmosphere of the thermal treatments, and of the Tb³⁺ concentration. The fluorescence properties are discussed in relation to the quenching mechanisms induced by Tb⁴⁺ transformation, residual OH groups, and crystallites size and structure. Optical propagation losses of the Tb doped Y₂O₃ planar waveguides related to the doping modes and Tb³⁺ concentration are presented. Doping sol–gel films by nanoparticles is shown to be a valuable alternative to the conventional doping from dissolved terbium salt. PACS 81.21.Fw; 84.40.Az; 78.67.Bf     

Flame-synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript> nanocrystals as spectral converting materials

In flame spray pyrolysis (FSP), the generation of uniform nanoparticles can be quite challenging due to difficulties in controlling droplet sizes during liquid spraying and uneven flame temperature. Here, we report a method to produce relatively uniform nanocrystals of a Tb³⁺ doped Y₂O₃ phosphor. In ethanol, metal nitrate precursors were simply mixed with organic surfactants to form a homogeneous solution which was then subjected to FSP. Depending on relative concentrations of the surfactant (oleic acid) to the metal precursors (yttrium and terbium nitrates), different sizes and morphologies of Y₂O₃:Tb³⁺ particles were obtained. By adjusting the surfactant concentration, Y₂O₃:Tb³⁺ crystals as small as 20~25 nm were acquired. X-ray diffraction and transmittance electron microscopy were used to prove that as-synthesized nanoparticles were highly crystalline due to the high temperature of FSP. X-ray photoelectron spectroscopy revealed that terbium dopants were well distributed throughout Y₂O₃ particles and a small portion of carbonate impurities were remained on the surface of particles, presumably originated from incomplete combustion of the organic surfactants. Photoluminescence (PL) spectra of Y₂O₃:Tb³⁺ nanocrystals exhibited a green light emission ensuring that the terbium doping was successfully occurred. However, when post-annealing was performed on the nanocrystals, their PL was dramatically enhanced indicating that quenching centers such as carbonate impurities and surface defects may have been removed by the annealing process. Owing to the continuous processability of FSP, this current method can be a practical way to produce nanoparticles in a large quantity. The obtained Y₂O₃:Tb³⁺ nanocrystals were used to fabricate a transparent film with poly-ethylene-co-vinyl acetate (poly-EVA) polymer, which was suitable for a spectral converting layer for a solar cell.

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Spontaneous luminescence of Eu<Superscript>3+</Superscript> ions in porous Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

A study of the luminescence of Eu³⁺ ions in Y₂O₃ nanospheres indicates a significant influence of the porous structure of nanoparticles on the luminescence of dopant ions. It is shown that filling the nanopores of initially porous Y₂O₃ nanospheres shortens the decay time of the spontaneous luminescence of doping europium ions. The change in the decay time is associated with the change in the effective refractive index of the porous nanospheres.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Correction of the band gap of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Submicron samples of Y₂O₃:Eu³⁺ phosphor with elevated photoluminescence (PL) efficiency and activator concentration of 9 at % obtained by the sol–gel method were investigated by diffuse reflection spectroscopy and PL spectroscopy. It is found that the diffuse reflection spectrum in the vicinity of the fundamental absorption edge (<300 nm) is distorted by the superposition of the PL of Eu³⁺ ions, as a result of which the calculated value of optical band gap E _g of the Y₂O₃ matrix is overestimated. An algorithm for eliminating the PL influence on the absorption edge is proposed, and the correct E _g values are found to be 4.61 ± 0.12 and 4.50 ± 0.12 eV for annealing at 700 and 1300°C, respectively.     

A high efficient antireflective down-conversion Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Bi<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript> thin films

The high efficient antireflective down-conversion Y₂O₃:Bi, Yb films have been prepared successfully on Si(100) substrates by pulsed laser deposition (PLD) method, Upon excitation of ultraviolet photon varying from 300 to 400 nm, near-infrared emission of Yb³⁺ was observed for the film, can be efficiently absorbed by silicon (Si) solar cell. Most interestingly, there is a very low average reflectivity 1.46% for the incident light from 300 to 1100 nm. To the best of our knowledge, this is the lowest reflectance for the down-conversion thin films prepared by cost efficient method. The surface topography of the high efficient antireflective films can be controllably tuned through the substrate template regulation by optimizing process parameters. Besides, the results showed that there is a close relationship between luminescent property and morphology of the film. With the change of the surface morphology, the intensity of Bi³⁺ and Yb³⁺ emission peaks increase first and then decrease. The obtained results demonstrate that this film can enhance the Si solar cell efficiency through light trapping and spectrum shifting.     

Preparation and Photoluminescence of Sm <Superscript>3+</Superscript> Doped YAlO <Subscript>3</Subscript> Phosphor

YAlO₃: Sm³⁺ phosphor has been synthesized by the solid state reaction method with calcium flouride used as a flux. The resulting YAlO₃: Sm³⁺ phosphor was characterized by X-ray diffraction (XRD) technique, Fourier transmission infrared spectroscopy (FTIR), photoluminescence . . PL excitation spectrum was found at 254,332,380,400,407, 603 and 713 nm. Under excitation of UV(713 nm) YAlO₃: Sm³⁺ (0–3 %) broad band emission were observed from 400 to 790 nm with a maximum around 713 nm of YAlO₃ host lattice accompanied by weak emission of Sm³⁺ (⁴G_5/2 – ⁶H_5/2, ⁶H_7/2,⁶H_9/2) transitions. The results of the XRD show that obtained YAlO₃: Sm³⁺ phosphor has a orthorhombic structure. The study suggested that Sm³⁺ doped phosphors are potential luminescence material for laser diode pumping and inorganic scintillators.     

Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Structural and Near-Infrared Properties of Nd<Superscript>3+</Superscript> Activated Lu<Subscript>3</Subscript>NbO<Subscript>7</Subscript> Phosphor

Undoped and Nd³⁺ doped lutetium niobate phases have been prepared by a conventional solid state reaction method using lutetium acetate and niobium oxide at 1250 °C for 6 h. X-ray diffraction patterns of the 6 mol% Lu₃NbO₇ sample exhibited a cubic fluorite single phase. Phase structure exhibited interesting crystallization behaviour depending on increasing Nd³⁺ concentration which led to a Lu₃NbO₇ single phase formation during the heat treatment process. SEM investigations were also in agreement with the XRD results. Morphologies of Nd³⁺ doped lutetium niobate powders exhibited oval like shapes and grain sizes varied between 0.3 and 5 μm. Near-infrared luminescence properties of Nd³⁺ doped Lu₃NbO₇ were also studied. 1.06 μm laser transition characteristics of Nd³⁺ doped lutetium niobate have been observed. Concentration quenching phenomenon was not detected depending on increasing Nd³⁺ doping concentrations at room temperature.     

Microstructural and Radioluminescence Characteristics of Nd<Superscript>3+</Superscript> Doped Columbite-Type SrNb<Subscript>2</Subscript>O<Subscript>6</Subscript> Phosphor

Undoped and different concentration Nd³⁺ doped SrNb₂O₆ powders with columbite structure were synthesized by molten salt process using a mixture of strontium nitrate and niobium (V) oxide and NaCl-KCl salt mixture as a flux under relatively low calcining temperature. X-ray diffraction analysis results indicated that SrNb₂O₆ phases found to be orthorhombic columbite single phase for undoped, 0.5 and 3 mol% Nd³⁺ doping concentrations. Phase composition of the powders was examined by SEM-EDS analyses. Radioluminescence properties of Nd³⁺ doped samples from UV to near-IR spectral region were studied. The emissions increased with the doping concentration of up to 3 mol%, and then decreased due to concentration quenching effect. There is a sharp emission peak around 880 nm associated with ⁴F_5/2 → ⁴I_9/2 transition in the Nd³⁺ ion between 300 and 1100 nm. The broad emission band intensity was observed from 400 to 650 nm where the peak intensities increased by increasing Nd³⁺ doping concentration. All the measurements were taken under the room temperature.     

Luminescence characteristics of energy transfer between Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> in NaMgPO<Subscript>4</Subscript> phosphor

Powder samples of NaMgPO₄ doped with Eu²⁺ and Ce³⁺ were prepared and their photoluminescence spectra were systemically studied. Energy transfer from Ce³⁺ to Eu²⁺ in NaMgPO₄ phosphor was observed by investigating the optical properties from photoluminescence spectra in Eu²⁺ or Ce³⁺ singly doped and Eu²⁺–Ce³⁺ codoped sodium magnesium orthophosphates, NaMgPO₄. The enhancement of UV excitation is attributed to energy transfer from Ce³⁺ to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺–Eu²⁺ codoped NaMgPO₄ phosphors in which Eu²⁺ can be efficiently excited by 390 nm are potential candidates for phosphor-converted LEDs.     

Luminescence thermometry using Gd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript>

In this paper we study the possibility of using the synthesized nanopowder samples of Gd₂Zr₂O₇:Eu³⁺ for temperature measurements by analyzing the temperature effects on its photoluminescence. The nanopowder was prepared by solution combustion synthesis method. The photoluminescence spectra used for analysis of Gd₂Zr₂O₇:Eu³⁺ nano phosphor optical emission temperature dependence were acquired using continuous laser diode excitation at 405 nm. The temperature dependencies of line emission intensities of transitions from ⁵D₀ and ⁵D₁ energy levels to the ground state were analyzed. Based on this analysis we use the two lines intensity ratio method for temperature sensing. Our results show that the synthesized material can be efficiently used as thermographic phosphor up to 650 K.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.