Effects of the surface coating of BaMgAl10O17:Eu phosphor with SiO2 nano-particles

BaMgAl₁₀O₁₇:Eu²⁺(BAM) phosphors were coated with SiO₂ nano-particles by a modified sol-gel method. In order to elucidate the effects of SiO₂ coating onto BAM phosphor, the luminescent decay time is measured before and after SiO₂ coating. It was revealed that surface coating of BAM phosphors with SiO₂ leads to an increase in luminescent decay time and quantum efficiency, due to the suppression of nonradiative decay via surface defects. The experimental results suggest that the nonradiative decay via surface defects is an important relaxation process, related to the optical properties of display devices such as plasma display panels (PDP) and lamps.     

Low-temperature synthesis of BaMgAl10O17:Eu blue phosphors

Using H₃BO₃ as the flux, pure BaMgAl₁₀O₁₇:Eu²⁺ (BAM) blue phosphors were successfully prepared via a solid-state reaction. By this approach, well-crystallized submicron BAM particles were obtained at temperatures as low as 1100 °C with a sintering duration of 2 h. The sintering temperature required by this approach was at least 400 °C lower than that required by the conventional solid-state approach for preparing BAM; moreover, the sintering time required by the former approach was also considerably shorter than that required by the latter approach. These factors are expected to lower the cost for large-scale production of BAM phosphors. Crystal structures and luminescence properties of the synthesized samples were characterized by XRD and TG–DTA, and photoluminescence spectroscopy, respectively. The reactivity of an intermediate, BaAl₂O₄, is thought to be the key factor influencing the synthesis temperature for BAM.     

SiN掺杂提高BaMgAl10O17:Eu2+荧光粉光学性能的第一性原理研究

使用基于密度泛函理论的CASTEP软件计算了BAM:Eu²⁺(BaMgAl₁₀O₁₇:Eu²⁺)荧光粉在SiN掺杂前后的能带、态密度、吸收光谱和Mulliken布居．Eu²⁺处于BR位置光吸收更强;SiN掺杂使处于BR位置的Eu²⁺的数量上升,而处于mO位置的Eu²⁺的数量下降,抵消了SiN掺杂降低Eu的态密度对光谱的影响．所以适量掺杂的SiN提高了BAM:Eu²⁺荧光粉的吸收发射光谱强度．Si-N键和Eu-N键的Mulliken布居数分别高于Al-O键和Eu-O键, 说明Si-N键和Eu-N键的共价性分别强于Al-O键和Eu-O键．发光中心Eu²⁺局域结构共价性的增强降低了BAM:Eu²⁺镜面层的活性,这是SiN掺杂提高BAM:Eu²⁺+荧光粉光学稳定性的主要原因．     

White light-emitting diodes using blue and yellow-orange-emitting phosphors

A blue-emitting phosphor, BaMgAl₁₀O₁₇:Eu²⁺ (BAM) and a yellow-orange phosphor, Ba²⁺-codoped Sr₃SiO₅:Eu²⁺ were prepared by the solid-state reaction. Excitation and emission spectra results showed that BAM and Ba²⁺-codoped Sr₃SiO₅:Eu²⁺ can be efficiently excited by near-ultraviolet (n-UV)-visible light from 250 to 440 nm. The effects of the doped-Eu²⁺ concentration in BAM and Ba²⁺-codoped Sr₃SiO₅:Eu²⁺ on the photoluminescence were investigated in detail. White light-emitting diodes (LED) was obtained by combining n-UV LED chip (GaN-based 380 nm emitting) with BaMgAl₁₀O₁₇:0.09Eu²⁺ and 0.1Ba²⁺-codoped Sr₃SiO₅: 0.2Eu²⁺ phosphors with the characteristic of color-rendering index of 86, CIE chromaticity coordinates (x,y) of (0.3216,0.3096), and color temperature T_c of 5700 K. As the current increases, the relative intensity simultaneously increases. The CIE chromaticity coordinates (x,y) of the white LED tends to decrease. The correlated color temperature T_c increases from 4100 to 7500 K and the color-rendering index R_a increases from 82 to 87 simultaneously.     

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.     

Synthesis of nano-size BaMgAl10O17:Eu blue phosphor by a rapid exothermic reaction

Ultrafine particles of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) phosphor were synthesized by a solid-state combustion reaction in a powder bed of 0.9BaCO₃+MgO+5Al₂O₃+0.05Eu₂O₃+k(KClO₃+1.5C) composition. A large exothermic reaction of the mixture (KClO₃+1.5C) leads to a self-sustaining combustion mode. Under optimized combustion conditions, the product consisted of BAM powder and KCl was obtained. BAM ultrafine particles resulting from the combustion process were easily obtained by simply washing the salt by-product with water. Combustion-processed BAM phosphor shows a homogeneous grain size of 100-500 nm, good dispersity, regular morphology, and improved luminescence properties.     

Degradation mechanisms of the blue-emitting phosphor BaMgAl10O17:Eu under baking and VUV-irradiating treatments

The luminescent properties of an Eu²⁺-activated hexagonal aluminate, BaMgAl₁₀O₁₇ (BAM), were studied under 147- and 254-nm excitations. The BAM samples were thermally treated by baking and then irradiated in vacuum ultraviolet (VUV) rays. The results show that the emission efficiency of Eu²⁺ in BAM under 147-nm excitation degraded seriously after baking or VUV-irradiating treatments, while no significant degradation was observed under 254-nm excitation. The degree of degradation depended on the excitation wavelength, and the absorption edge of the BAM host was suggested to be close to 175 nm (7.2 eV). The differences between the thermal-induced and the VUV-irradiation-induced degradations, and their mechanisms are discussed for the color plasma display applications.     

Thermally stable luminescence of blue LiSrPO4:Eu2+ phosphor for near-UV light-emitting diodes

Blue phosphor, LiSrPO₄:Eu²⁺, was prepared by solid-state reaction method under a weak reductive atmosphere and investigated by means of photoluminescence, concentration quenching process, and temperature dependence of luminescence. These results show that LiSrPO₄:Eu²⁺ can be efficiently excited by the UV-visible light of 250–440 nm and exhibits bright blue emission. Furthermore, Eu²⁺-doped LiSrPO₄ phosphor shows high thermally stable luminescence comparable to commercial phosphor BaMgAl₁₀O₁₇:Eu²⁺ (BAM). Two bright blue LEDs were fabricated by incorporating an InGaN-based near-UV chip with the obtained phosphor LiSrPO₄:Eu²⁺ and BAM, respectively. Their luminescence properties were compared based on different forward-bias currents. All the characteristics suggest that LiSrPO₄:Eu²⁺ is a good blue phosphor candidate for creating white light in phosphor-conversion white LEDs.     

Luminescent and aging characteristics of blue emitting (Ca1−x,Mgx)Al2Si2O8:Eu phosphor for PDPs application

We have evaluated thermal stability and aging property of a blue color-emitting phosphor, CaAl₂Si₂O₈:Eu²⁺ (CAS:Eu²⁺), synthesized by conventional solid-state reaction method. When both CAS:Eu²⁺ and BaMgAl₁₀O₁₉:Eu²⁺ (BAM) were baked in air at 500 °C for 20 min, the decrease of photoluminescence (PL) intensity of CAS:Eu²⁺ was lower than that of BAM. The aging property of CAS:Eu²⁺ was also better than that of BAM. Due to its rigid structure and unlimited framework of silicon-oxygen and aluminum-oxygen around Eu²⁺ ions, Eu²⁺ ions were protected from outer oxidizing atmosphere and plasma discharge. After analysis of aging property and thermal stability, the differences of these thermal stability and aging property of CAS:Eu²⁺ from those of BAM were ascribed to its crystal structure which plays a role of a shield for Eu²⁺ ions against oxidation atmosphere and Xe ion bombardment.     

Photoluminescence properties of color-tunable SrMgAl10O17:Eu2+,Mn2+ phosphors for UV LEDs

Aluminate phosphors SrMgAl₁₀O₁₇ codoped with Eu²⁺ and Mn²⁺ ions were prepared by solid-state reaction. The phase structure and photoluminescence properties of the as-prepared phosphors were characterized by powder X-ray diffraction, photoluminescence excitation and emission spectra. Upon excitation of UV light, two broad emission bands centered at 470 and 515 nm were observed, and they were assigned to Eu²⁺ and Mn²⁺ emissions, respectively. The emission color of the phosphors can be tuned from blue to cyan and finally to green by adjusting the concentration ratios of Eu²⁺ and Mn²⁺. Effective energy transfer occurs from Eu²⁺ to Mn²⁺ in the host due to the spectral overlap between the emission band of Eu²⁺ and the excitation bands of Mn²⁺. The energy transfer mechanism was demonstrated to be electric dipole–quadrupole interaction. The energy transfer efficiency and critical distance were also calculated. The phosphors exhibit strong absorption in near UV spectral region and therefore they are potentially useful as UV-convertible phosphors for white LEDs.     

蓝色荧光粉Sr2B5O9Cl:Eu2+发光特性的研究

采用高温固相法合成了近紫外光激发的蓝色荧光粉Sr₂B₅O₉Cl:Eu²⁺,研究了SrCl₂ ·6H₂O用量和Eu²⁺浓度对其结构和发光性能的影响.随着Eu²⁺浓度的增加,其结构无明显变化,发光强度先增强后减弱,当其浓度为8mol%时,荧光粉的发光强度最大;当用Ca取代Sr时,荧光粉的发射峰从425 nm红移到453 nm. 适当过量 关键词： 氯硼酸盐 蓝色荧光粉 LED     

Luminescence studies on SrMgAl10O17:Eu, Dy phosphor crystals

Using urea as fuel, SrMgAl₁₀O₁₇:Eu, Dy phosphor was prepared by a combustion method. Its luminescence properties under ultraviolet (UV) excitation were investigated. Pure SrMgAl₁₀O₁₇ phase was formed by urea-nitrate solution combustion synthesis at 550 °C. The results indicated that the emission spectra of SrMgAl₁₀O₁₇:Eu, Dy has one main peak at 460 nm and one shoulder peak near 516 nm, which are ascribed to two different types of luminescent Eu²⁺ centers existing in the SrMgAl₁₀O₁₇ matrix crystal. The blue luminescence emission of SrMgAl₁₀O₁₇:Eu phosphors was improved under UV excitation by codoping Dy³⁺ ions. The SrMgAl₁₀O₁₇:Eu phosphors showed green afterglow (λ=516 nm) when Dy³⁺ ions were doped. Dy³⁺ ions not only successfully play the role of sensitizer for energy transfer in the system, but also act as trap levels and capture the free holes in the spinel blocks.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.     

Synthesis and characterization of structural and luminescence properties of blue — green BaAlxOy:Eu2+ phosphor by solution — combustion method

Europium-doped barium aluminate (BaAl _x O _y :Eu²⁺) phosphors were obtained at low temperatures (500°C) using the solution — combustion of corresponding metal nitrate-urea solution mixtures. The particle size and morphology and the structural and luminescent properties of the synthesized phosphors were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Electron diffraction spectroscopy (EDS) and photoluminescence (PL). It was found that the change in Ba: Al molar ratios showed greatly influence not only on the particle size and morphology, but also on their PL spectra and crystalline structure. The structure of BaAl _x O _y nanophosphors changes from a hexagonal Ba₂Al₁₀O₁₇ phase for samples with 6:100 molar ratios to a hexagonal BaAl₂O₄ one with an increase in Ba content. The peak of the emission band occurs at a longer wavelength (around 615 nm) with a decrease in Ba concentration but displays a broad blue-green emission band composed from two emissions with the maximum at 495 and 530nm coming from Eu²⁺ in two sites for increasing Ba content. The blue-green emission is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects while the red emission is due to f - f transitions. These findings clearly demonstrate the possibility of fine tuning the colour emission.     

Influence of Eu doping content on photoluminescence of Gd2O3:Eu phosphors prepared by liquid-phase reaction method

Europium-doped cubic Gd₂O₃:Eu³⁺ nanoparticles containing various activator content in the range of 5-15 wt% were synthesized by a liquid-phase reaction method to investigate the influence of Eu³⁺ loading on the optical properties of phosphors by using XRD, TEM, BET, spectrometer and fluorometer. The size of Gd₂O₃:Eu³⁺ powders was in the range 21-41 nm. The phosphors showed an initial increase in luminescence and then a subsequent decrease with further doping (above 10 wt%). The decay time was reduced with increasing Eu loading; however, it decreased significantly above the 10% Eu doping. From spectroscopic studies, the Eu³⁺ doping ion distribution was uniform and homogeneous up to the 10 wt% loading because no concentration quenching effect was observed. However, further Eu³⁺ doping above 10 wt% reduced the luminescence due to the concentration quenching effect, as deduced from the shortening of the decay time.     

Effects of flux on crystal structure and luminescent properties of nitroxides phosphors

Yellow-green-emitting Sr Si2O2N2:Eu2+phosphors were synthesized with Sr2Si O4:Eu2+as precursor.The effects of flux and the concentration of Eu2+on the crystal structure and luminescent properties of the phosphors were investigated.Results suggested that the optimal content of flux Na2CO3 was 1 wt%and the optimal doping concentration of Eu2+was 0.05 mol.The emission spectra showed the most intense peaks located at 535 nm which corresponded to the 4f65d→4f7 transition of Eu2+.The excitation spectra showed that these phosphors could be effectively excited by near-ultraviolet and blue light,whichwas consistent with the widely applied output wavelengths of near-ultraviolet and blue-white light-emitting diode(LED)chips.When the influence of flux on the luminescent properties of Sr Si2O2N2:Eu2+phosphor was analyzed,the X-ray diffraction(XRD)patterns indicated that the flux could help the crystallization of the phosphors.No other phases except the triclinic structure of Sr Si2O2N2 were formed.The thermal stability and the emission intensity of synthesized Sr Si2O2N2:Eu2+phosphor were examined and compared with commercial YAG yellow phosphors.All results indicate that the yellow-green-emitting phosphor is a suitable candidate for the fabrication of white LEDs.     

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.     

Enhanced luminescent properties of long-persistent Sr2MgSi2O7:Eu, Dy phosphor prepared by the co-precipitation method

Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were prepared by the (aminopropyl)-triethoxysilane (APTES) co-precipitation method. Effects of synthesis temperature on the crystal characteristics, luminescent properties and afterglow performance of Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors have been discussed in detail and compared with the corresponding commercial product. The experimental results indicated that the sample could be synthesized at a relatively lower temperature and had better performance on the above-mentioned properties using the co-precipitation method.     

Novel green-emitting Na2CaPO4F:Eu phosphors for near-ultraviolet white light-emitting diodes

In this study, green-emitting Na₂CaPO₄F:Eu²⁺ phosphors were synthesized by solid-state reactions. The excitation spectra of the phosphors showed a broad hump between 250 and 450 nm; the spectra match well with the near-ultraviolet (NUV) emission spectra of light-emitting diodes (LEDs). The emission spectrum showed an intense broad emission band centered at 506 nm. White LEDs were fabricated by integrating a 390 nm NUV chip comprising blue-emitting BaMgAl₁₀O₁₇:Eu²⁺, green-emitting Na₂CaPO₄F:0.02 Eu²⁺, and red-emitting CaAlSiN₃:Eu²⁺ phosphors into a single package; the white LEDs exhibited white light with a correlated color temperature of 5540 K, a color-rendering index of 90.75, and color coordinates (0.332, 0.365) close to those of ideal white light.     

Luminescent properties of R2(MoO4)3:Eu (R=La, Y, Gd) phosphors prepared by sol-gel process

A series of red phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) have been synthesized by sol-gel method. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA), and the properties of these resulting phosphors have also been characterized by photoluminescence (PL) spectra and reflectance spectra. Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and the size of the samples. The results of TG-DTA and XRD indicated that all of the R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors crystallized completely at 650 °C. Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ have two structures, monoclinic and orthorhombic, while La_0.8Eu_1.2(MoO₄)₃ only adopts monoclinic structure. The luminescent properties of phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) are dependent on their structures to some extent. The orthorhombic Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ phosphors show very similar luminescent properties, which differ from those of phosphors with monoclinic structure. For all of R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors, intense red emission is obtained by exciting at ∼394 and ∼465 nm which are owing to the sharp ⁷F₀→⁵L₆ and ⁷F₀→⁵D₂ lines of Eu³⁺. Two strongest lines at 394 and 465 nm in excitation spectra of these phosphors match well with the two popular emissions from near-UV and blue GaN-based LEDs, so they could be used as red components for white light-emitting diodes.