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.     

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     

A novel white light-emitting diode (w-LED) fabricated with Sr<Subscript>6</Subscript>BP<Subscript>5</Subscript>O<Subscript>20</Subscript>:Eu<Superscript>2+</Superscript> phosphor

Sr₆BP₅O₂₀:Eu²⁺ phosphor was prepared by the solid-state reaction method under a weak reductive atmosphere and the photoluminescence properties were studied systematically. The bluish-green emission band of Sr₆BP₅O₂₀:Eu²⁺ phosphor is peaking at 475 nm, and the excitation bands are broad with peaks at about 290 and 365 nm with a shoulder around 390 nm, respectively. By combining with Ga(In)N-based near-ultraviolet LEDs, a bluish-green LED was fabricated based on the Sr₆BP₅O₂₀:Eu²⁺ phosphor, and a novel intense white LED was fabricated based on the bluish-green phosphor Sr₆BP₅O₂₀:Eu²⁺ and the red phosphor (Sr,Ca)₅(PO₄)₃Cl:Eu²⁺,Mn²⁺. When this two-phosphor white LED is operated under 20-mA forward-bias current at room temperature, the Commission Internationale de l’Eclairage(CIE) chromaticity coordinates (x,y), the correlated color temperature Tc, and the color rendering index Ra are calculated to be (0.3281,0.3071), 5687 K, and 87.3, respectively. The dependence of the bluish-green and two-phosphor white LEDs on different forward-bias currents from 5 mA to 50 mA shows a similar behavior. As the current increases, the relative intensity simultaneously increases. The CIE chromaticity coordinates (x,y) of the two-phosphor white LED tend to decrease. Consequently, the correlated color temperature Tc increases from 3800 K to 9400 K and the color rendering index Ra of the two-phosphor white LED increases from 83.4 to 91.8 simultaneously. PACS 07.60.-j; 42.70.-a; 71.55.Eq     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

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.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

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.     

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.     

Luminescence and energy transfer mechanism in Eu<Superscript>3+</Superscript>/Tb<Superscript>3+</Superscript>-co-doped ZrO<Subscript>2</Subscript> nanocrystal rods

Nanocrystal rods of Eu³⁺/Tb³⁺-co-doped ZrO₂ were synthesized using a simple chemical precipitation technique. Both ions were successfully doped into the Zr⁴⁺ ion site in a mixed structure containing both monoclinic and tetragonal phases. The Eu³⁺ or Tb³⁺ singly doped zirconia produced red and green luminescence which are characteristics of Eu³⁺ and Tb³⁺ ions, respectively. The co-doped zirconia samples produced blue emission from defect states transitions in the host ZrO₂, red and green luminescence from dopant ions giving cool to warm white light emissions. The phosphors were efficiently excited by ultraviolet and near-ultraviolet/blue radiations giving white and red light, respectively. The decay lifetime was found to increase with increasing donor ion concentration contrary to conventional observations reported by previous researchers. Weak quadrupole–quatdrupole multipolar process was responsible for energy transfer from Tb³⁺ (donor) ion to Eu³⁺ ion. No energy back-transfer from Eu³⁺ to Tb³⁺ ion was observed from the excitation spectra. Temperature-dependent photoluminescence shows the presence of defects at low temperature, but these defects vanished at room temperature and beyond. The Eu³⁺/Tb³⁺-co-doped ZrO₂ nanocrystal rod is a potential phosphor for white light application using UV as an excitation source. Thermoluminescence measurements show that the inclusion of Tb³⁺ ion increases trap depths in the host zirconia.     

Luminescent properties of SrMg<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript> as a potential phosphor for ultraviolet light-emitting diodes

Eu²⁺ and Mn²⁺ co-doped SrMg₂(PO₄)₂ phosphors with blue and red two emission bands were prepared by the high temperature solid state method and their luminescent properties have been investigated as a function of activator and co-activator concentrations. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the Eu²⁺ emission spectrum and the excitation spectrum of Mn²⁺. Efficiencies of energy transfer were also calculated according to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission. According to the principle of energy transfer, we demonstrated that the phosphor SrMg₂(PO₄)₂:Eu²⁺,Mn²⁺ with double emission bands exhibited a great potential as a phosphor for ultraviolet light-emitting diodes and the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺. PACS 78.55.-m     

Photoluminescence,thermoluminescence and electron spin resonance studies on Eu<Superscript>3+</Superscript> doped Ca<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript> red phosphors

Tricalcium aluminate doped with Eu³⁺ was prepared at furnace temperatures as low as 500°C by using the convenient combustion route and examined using powder X-ray diffraction, scanning electron microscope and photoluminescence techniques. A room-temperature photoluminescence study showed that the phosphors can be efficiently excited by UV/Visible region, emitting a red light with a peak wavelength of 616 nm corresponding to the ⁵D₀–⁷F₂ transition of Eu³⁺ ions. The phosphor exhibits three thermoluminescence (TL) peaks at 195°C, 325°C and 390°C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the defect centres responsible for the TL process. Room-temperature ESR spectrum of irradiated phosphor appears to be a superposition of three distinct centres. One of the centres (centre I) with principal g-value 2.0130 is identified as O⁻ ion while centre II with an axially symmetric principal values g _∥=2.0030 and g _⊥=2.0072 is assigned to an F⁺ centre (singly ionized oxygen vacancy). O⁻ ion (hole centre) correlates with the TL peak at 195°C and the F⁺ centre (electron centre), which acts as a recombination centre, is also correlated to the 195°C TL peak. F⁺ centre further appears to be related to the high temperature peak at 390°C. Centre III is also assigned to an F⁺ centre and seems to be the recombination centre for the TL peak at 325°C.     

Quantum cutting in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript>: Eu<Superscript>3+</Superscript> by VUV excitation

The emission and excitation spectra of Gd₂SiO₅∶Eu³⁺ were investigated using the VUV beam line of the Beijing Synchrotron Radiation Facility (BSRF). The experimental results were discussed in the frame of visible quantum cutting process involved in Gd³⁺−Eu³⁺ system. Upon direct excitation into the⁶G _J states of Gd³⁺, two visible photon emissions from Eu³⁺ were observed. Cursory evaluation proved that Gd₂SiO₅∶Eu³⁺ is an efficient visible quantum cutter.     

Red,Yellow, Blue and Green Emission from Eu<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript> and Bi<Superscript>3+</Superscript> Doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>nano-Phosphors

Rare earth elements (RE = Eu³⁺& Dy³⁺)and Bi³⁺ doped Y₂O₃ nanoparticles were synthesized by urea hydrolysis method in ethylene glycol, which acts as reaction medium as well as a capping agent, at a low temperature of 140 °C,followed by calcination of the obtained product. Transmission electron microscope (TEM) images reveals that ovoid shaped Y₂O₃ nanoparticles of around 22–24 nm size range were obtained in this method. The respective RE and Bi³⁺ doped Y₂O₃ precursor nanoparticles when heated at 600 and 750 °C, retains the same shape as that of the as-synthesized Y₂O₃ precursor samples. From EDAX spectra, the incorporation of RE ions into the host has been studied. XRD pattern reveals the crystalline nature of the heated nanoparticles and indicate the absence of any impurity phase other than cubic Y₂O₃.However, the as-synthesized nanoparticles were highly amorphous without the presence of any sharp XRD peaks. Photoluminescence study suggests that the synthesized samples could be used as red (Eu³⁺), yellow (Dy³⁺), blue and green (Bi³⁺)emitting phosphors.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

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.     

溶胶-凝胶法制备BaGd1-xEuxB9O16红色磷光粉的发光

采用溶胶-凝胶法制备出BaGd_1-xEu_xB₉O₁₆红色磷光粉,对过程的物料配比、前驱体处理和晶化温度等制备条件进行了讨论。结果表明,样品在850 ℃下开始晶化,900 ℃时就能够获得较好的晶化产物,结合不同晶化温度下的发光强度比较确定,晶化温度为950 ℃时,BaGd_1-xEu_xB₉O₁₆磷光粉具有较高的结晶状态和发光强度。当Eu浓度x=0.9时具有最大的发光强度;初始原料配比硼酸须按计量过量15%。所得荧光粉的激发光谱峰值为264,394,465,534 nm等,分别归属于Eu-O电荷迁移带及Eu³⁺的⁷F₀-⁵L₆、⁷F₀-⁵D₂和⁷F₀-⁵D₁跃迁,发射光谱呈Eu³⁺的特征红光,最强的发射峰位于614 nm,归属于⁵D₀-⁷F₂跃迁。进一步研究表明该磷光粉中存在着Gd³⁺对Eu³⁺的能量传递。     

Synthesis and luminescence properties of the red phosphor CaZrO<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> for white light-emitting diode application

Eu³⁺-doped CaZrO₃ phosphor with perovskite-type structure was synthesized by the high temperature solid-state method. The samples were characterized by X-ray diffraction, scanning electron microscopy, fluorescence spectrophotometer and UV-vis spectrophotometer, respectively. XRD analysis showed that the formation of CaZrO₃ was at the calcinations temperature of 1400°C. The average diameter of CaZrO₃ with 4 mol% doped-Eu³⁺ was 2μm. The PL spectra demonstrated that CaZrO₃:Eu³⁺ phosphor could be excited effectively in the near ultraviolet light region (397 nm) and emitted strong red-emission lines at 616 nm corresponding to the forced electric dipole ⁵ D ₀ → ⁷ F ₂ transitions of Eu³⁺. Meanwhile, the light-emitting diode was fabricated with the Ca_0.96ZrO³:Eu_0.04³⁺ phosphor, which can efficiently absorb ∼ 400 nm irradiation and emit red light. Therefore Ca_0.96ZrO₃:Eu_0.04³⁺ may have applications for a near ultraviolet InGaN chip-based white light-emitting diode.     

Sol-gel method and luminescence properties of the ZrO<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> phosphors with different charge compensation

Eu³⁺-doped ZrO₂ phosphors with different charge compensators (Li⁺, Na⁺, K⁺) were prepared by the sol-gel method. The properties of the as-obtained samples are characterized by X-ray diffraction, scanning electron microscope, photoluminescence spectra, and decay curve. The results show that ZrO₂:Eu³⁺ phosphors with different charge compensation are mixed phase of tetragonal and monoclinic phase, and the volume fraction of tetragonal phase of ZrO₂:Eu³⁺/Na⁺ phosphor is bigger than the other phosphors. The phosphors can emit strong red light at 606~616 nm (⁵D₀ → ⁷F₂) excited by ultraviolet light (395 nm). Compared with two charge compensation patterns in the ZrO₂:Eu³⁺, it has been found that ZrO₂:Eu³⁺ phosphors used Na⁺ as charge compensator show greatly enhanced red emission under 395 nm excitation and longer luminescence lifetime.     

Tunable bluish green to yellowish green Ca<Subscript>2(1-x)</Subscript>Sr<Subscript>2x</Subscript>Al<Subscript>2</Subscript>SiO<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphors for potential LED application

A series of solid solutions with a general formula of Ca_2(1-x)Sr_2xAl₂SiO₇:Eu²⁺ were synthesized by a high temperature solid state reaction. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and lifetimes of phosphors were investigated. XRD results show that Ca₂Al₂SiO₇ is totally miscible with Sr₂Al₂SiO₇. These solid solution phosphors show a broad excitation band of 350–450 nm that matches well with the output lights of near-UV LEDs and tunable emission from bluish green to yellowish green. These optical properties originate from the 4f⁷–4f⁶5d transition of Eu²⁺ ions. The crystal field strength was considered to be tailed by controlling the host composition, which leads to the shift of absorption band and emission band, and the varying of color coordinates. PACS  78.55.-m; 42.70.-a; 61.05.C-     

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.