Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors

Sr(3)AlO(4)F:RE(3+) (RE = Tm/Tb, Eu, Ce) phosphors were prepared by the conventional solid-state reaction. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra, as well as lifetimes were utilized to characterize samples. Under the excitation of UV light, Sr(3)AlO(4)F:Tm(3+), Sr(3)AlO(4)F:Tb(3+), and Sr(3)AlO(4)F:Eu(3+) exhibit the characteristic emissions of Tm(3+) ((1)D(2)→(3)F(4), blue), Tb(3+) ((5)D(4)→(7)F(5), green), and Eu(3+) ((5)D(0)→(7)F(2), red), respectively. By adjusting the doping concentration of Eu(3+) ions in Sr(3)AlO(4)F:0.10Tm(3+), 0.10Tb(3+), zEu(3+), a white emission in a single composition was obtained under the excitation of 360 nm, in which an energy transfer from Tb(3+) to Eu(3+) was observed. For Sr(3)AlO(4)F:Ce(3+),Tb(3+) samples, the energy transfer from Ce(3+) to Tb(3+) is efficient and demonstrated to be a resonant type via a dipole-quadrupole interaction by comparing the experimental data and theoretical calculation. Furthermore, the critical distance of the Ce(3+) and Tb(3+) ions has also been calculated to be 9.05 ?. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. These phosphors might be promising for use in near-UV LEDs.     

Luminescence and energy transfer characteristics of Ce3+- and Tb3+-codoped nanoporous 12CaO 7Al2O3 phosphors

The novel green-emitting phosphors of 12CaO 7Al2O3:Ce3+ , Tb3+ (C12A7:Ce3+, Tb3+) were synthesized by a solid-state reaction. Upon the excitation of Ce3+ at 350 nm, the C12A7:Ce3+, Tb3+ phosphor shows intense green emissions located at 543 nm assigning to 5D4-7F5 transitions of Tb3+ ions, and weak blue emissions centered at 434 nm due to the transitions of Ce3+ 5d-4f. The photoluminescence (PL) intensity of Ce3+ decrease with increasing Tb3+ concentration, indicating the effective energy transfer (ET) occurred from Ce3+ to Tb3+ in C12A7:Ce3+, Tb3+. The ET efficiency between Ce3+ and Tb3+ in the optimum composition reaches to 99%. Based on Dexter's ET theory, we have demonstrated that the efficient ET is a resonant type via dipole-dipole mechanism with an energy transfer critical distance of 4.02 A. Our results suggested that C12A7:Ce3+, Tb3+ phosphor would be a promising green-emitting phosphor for UV-converting white light-emitting diodes.     

Synthesis and photoluminescent properties of (La,Ca)₃Si₆N₁₁:Ce³+ fine powder phosphors for solid-state lighting

We have developed a new Ce(3+)-activated nitride phosphor, (La,Ca)(3)Si(6)N(11):Ce(3+), using the gas-reduction-nitridation method. The synthesized (La,Ca)(3)Si(6)N(11):Ce(3+) possesses tunable yellow broadband emission with the dominant wavelength of 577-581 nm and the external quantum efficiency up to ～42%, under an excitation of 450 nm. Precise steady-state and time-resolved photoluminescence analyses revealed that the only one type of Ce(3+) center is active under the blue-light excitation. By combining the synthesized (La,Ca)(3)Si(6)N(11):Ce(3+) phosphors with the 450-nm InGaN chip, a broad range of white light with the correlated color temperatures of ～2600-3800 K can be created, demonstrating their promising applicability to the warm-white light-emitting diodes.     

Spherical SiO2 @ GdPO4: Eu3+ core-shell phosphors: sol-gel synthesis and characterization

Nanocrystalline GdPO4 : Eu3+ phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by Pechini sol-gel method, resulting in the formation of core-shell structured SiO2 @ GdPO4 : Eu3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR results indicate that GdPO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the images of FESEM and TEM. Under UV light excitation, the SiO2 @ GdPO4 : Eu3+ phosphors show orange-red luminescence with Eu3+ 5D0-7F1 (593 nm) as the most prominent group. The PL excitation and emission spectra suggest that an energy transfer occurs from Gd3+ to Eu3+ in SiO2 @ GdPO4 : Eu3+ phosphors. The obtained core-shell phosphors have potential applications in FED and PDP devices.     

荧光粉Sr3-x-yAl2O6∶xCe3+,yEu2+的制备及其发光特性

采用高温固相反应法制备了Sr3-x-yAl2O6:xCe3+,yEu2+(x=0,y=0;x=0.04,y=0;x=0.04,y=0.02;x=0.04,y=0.04;x=0.04,y=0.06;x=0.04,y=0.08;x=0,y=0.04)荧光粉,研究其相组成与荧光特性,结果表明,样品具有单相Sr3Al2O6晶体结构。在360nm波长的紫外光激发下,Ce3+离子辐射出峰值在434nm附近的宽谱蓝光。通过能量传递作用,Eu2+离子辐射峰值为517nm左右的宽谱绿光。Ce3+和Eu2+的荧光组合获得了色坐标为(0.2611,0.3313)的近白光发射。样品的激发光谱分布在250～400nm的波长范围,这种荧光粉有望在紫外或近紫外激发的白光LED中获得应用。     

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.     

新型白光LED用SrMg_2(PO_4)_2单-基质荧光粉

本文通过高温固相法合成了紫外光LED用SrMg2(PO4)2为基质Eu2+,Tb3+和Mn2+为激活剂的白色荧光粉。采用XRD对荧光粉的结构和相纯度进行分析,Eu2+、Tb3+及Mn2+的加入对其结构没有明显的影响,且无杂相生成;当用Ca部分取代Sr时Eu2+和Mn2+的发射带分别发生红移和蓝移且二者之间存在着明显的能量传递;当引入共激活剂Tb3+时对其荧光光谱进行了详细研究,发现Eu2+和Tb3+,Eu2+和Mn2+之间存在部分的能量传递,通过调整它们的相对掺杂浓度可以得到发白光的荧光粉。     

新型黄绿色发光材料Sr2MgSi3O9:Ce3+,Tb3+的合成及光谱分析

采用凝胶-燃烧法在活性炭弱还原气氛下成功合成了新型荧光粉Sr2MgSi3O9 :Tb3+、Sr2MgSi3O9:Ce3+,Tb3+,用X射线粉末衍射仪(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明,所合成的发光材料与Sr2MgSi2O7具有相似的晶体结构,同属四方晶系.样品一次颗粒近似球形,粒径在100nm左右.Sr2MgSi3O9:Tb3+的激发光谱为一位于249nm的宽带,发射光谱主要由473、491、547、585nm等一系列发射峰组成,其中473nm(5D3→<7F3)为主发射峰,547nm(5D4→7F5)为次发射峰;样品Sr1.955MgSi3O9:Tb3+0.04,Ce3+0.005的激发光谱由峰值分别位于249和335nm的双激发带组成,其中后者为主激发带.在335nm激发下,其发射光谱由两部分组成,其中400nm附近的带状发射对应于Ce3+的发射,而491、547、588nm处的发射峰归属为Tb3+的5+D4→7FJ(J=6,5,4)跃迁发射,最强峰位于547nm,对应Tb3+的5D4→7F5跃迁.此外,探讨了Ce3+掺杂量对样品发光亮度的影响,发现Ce3+可以把能量传递给Tb3+,对Tb3+起到敏化作用.     

One-step synthesis of highly water-soluble LaF(3):Ln(3+) nanocrystals in methanol without using any ligands

Water-soluble infrared-to-visible fluorescent LaF(3) nanocrystals doped with different lanthanide ions (Er(3+)/Yb(3+), Eu(3+), Nd(3+), Tb(3+)) have been synthesized in methanol without using any ligands. These nanocrystals are easily dispersed in water, producing a transparent colloidal solution. The colloids of the Er(3+)/Yb(3+), Eu(3+), Nd(3+), Tb(3+) doped nanocrystals exhibit strong luminescence in the visible and near-infrared spectral regions.     

White Light Emission Characteristics of Tb~(3+)/Sm~(3+) Co-Doped Glass Ceramics Containing YPO_4 Nanocrystals

The Tb~(3+)/Sm~(3+) single-doped and co-doped glasses and glass ceramics containing YPO_4 nanocrystals have been synthesized by melt quenching method. The structural and luminescent properties of these glass specimens were investigated. Under 375 nm wavelength excitation, the emission spectra combined with blue, green and red bands were observed, which achieved the white light emission. Moreover, the energy transfer between Tb~(3+) and Sm~(3+)ions was validated by decay lifetime measurement and energy level diagram.The color coordinates(x = 0.333, y = 0.333), correlated color temperature(5595 K) and the color rendering index(Ra = 80.5) indicated that the glass ceramics were considered to be good lighting source. Hence,the YPO_(4-) based Tb~(3+)/Sm~(3+) co-doped glass ceramics can act as potential matrix materials for white lightemitting diodes under ultraviolet excitation.     

Photoluminescence green in microspheres of CaWO4:Tb processed in conventional hydrothermal

Green-phosphor spherical microparticles (2–4 μm in diameter) of CaWO₄:Tb³⁺ (CWO:Tb) exhibiting excellent emission at 545 nm have been synthesized by a conventional hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation and emission spectra and decay curve were used to characterize the CWO:Tb phosphors. Because 12 at.% CWO:Tb phosphor shows broad and strong absorption in UV region, exhibits intensive green emission under 254 nm excitation in comparison with the commercial green fluorescent lamp phosphor (LaPO₄:Ce,Tb), it is considered to be a new promising phosphor for fluorescent lamps application.     

(La,Ce,Tb)(PO_4,BO_3)绿粉的合成及发光研究

首次用磷酸硼和稀土氧化物为主要原料制备铈、铽共激活的硼磷酸盐绿色荧光粉 ,并对Ce3+-Tb3+的能量传递进行了研究 ,发现在该基质中Ce3+、Tb3+间的能量传递为电多极子相互作用的共振传递 ,能量传递效率可高达 90 %。还研究了助熔剂对荧光粉粒度和发光特性的影响 ,实验结果表明 ,加了助熔剂后所得样品的颗粒明显变大 ,在 2 54nm紫外激发下Tb3+发射大大增强 ,光的纯度也得到改善。对不同基质荧光粉的研究发现 ,用硼磷酸盐绿粉比用硼酸盐和磷酸盐绿粉更适合做三基色粉配料。     

真空紫外光激发下Tb~(3+)激活的稀土正硼酸盐的发光

报导了Tb3+、Ce3+激活的稀土正硼酸盐的真空紫外光谱。分析了Ce3+的4f75d能级随基质结构、基质阳离子的变化,讨论了温度、Tb3＋离子的浓度对发光的影响以及Ce3＋－Tb3＋间的能量传递.     

Sm3+/Ce3+/Tb3+共掺CaO-B2O3-SiO2发光玻璃的制备及发光性能研究

采用高温熔融法制备了Sm3+/Ce3+/Tb3+共掺杂的CaO-B2O3-SiO2发光玻璃材料,并用荧光分光光度计和CIE色度坐标对其发光性能进行了研究。发射光谱表明,在374nm激发下,Sm3+/Ce3+/Tb3+共掺杂CaO-B2O3-SiO2发光玻璃的发射光谱中同时观测到了红橙光、蓝光和绿光的发射带,这些发射带的混合实现了白光发射。此外,在Sm2O3和Tb4O7含量不变的情况下,随着CeO2含量的减小,Sm3+/Ce3+/Tb3+共掺杂发光玻璃的发光颜色在白光区逐渐由蓝光区附近过渡到黄光区附近。     

Effects of the mixing ratio of the CaAl12O19:mn and Zn2SiO4:mn color-conversion layer on the color tunable emissions of white organic light-emitting devices

The optical properties of white organic light-emitting devices (WOLEDs) fabricated utilizing a CaAl12O19:Mn and Zn2SiO4:Mn phosphor layer were investigated. X-ray diffraction patterns for CaAl12O19:Mn and Zn2SiO4:Mn phosphors showed that Mn ions in the CaAl12O19:Mn phosphors were completely substituted into Ca ions and that Mn ions in the Zn2SiO4:Mn phosphors were completely substituted into Zn ions. Field emission scanning electron microscopy images showed that the size of the CaAl12O19:Mn phosphor was approximately between 0.1 and 3 microm, and that the size of the Zn2SiO4:Mn phosphor was smaller than 7 microm. The color coordinates of the electroluminescence spectra for WOLEDs with phosphor thicknesses of 0.25 and 0.35 mm shifted to the white emission side because the generated blue light from the blue OLEDs combined with the red and green lights was converted by the CaAl12O19:Mn and the Zn2SiO4:Mn phosphor down-conversion layers.     

水热-均匀沉淀法制备亚微米长余辉发光材料SrAl_2O_4∶Eu,Dy

采用水热-均匀沉淀法,以尿素为沉淀剂,在聚四氟乙烯低温反应釜中160℃水热,在较低的煅烧温度下制备了亚微米级长余辉发光材料Sr0.97Al2O4∶Eu0.01,Dy0.02。XRD结果表明,在1000℃煅烧4h能得到单相的SrAl2O4∶Eu,Dy,SEM测试显示SrAl2O4∶Eu2+,Dy3+发光材料为球状形貌,粒径大小约为200～500nm,激发和发射光谱结果表明,随着煅烧温度升高,SrAl2O4∶Eu2+,Dy3+的发光强度也随之增强,其激发光谱峰值位于360nm,发射光谱峰值位于513nm,SrAl2O4∶Eu2+,Dy3+在1100℃煅烧后的余辉衰减时间比1000℃煅烧后显著提高,其热释光谱峰值在80～90℃。     

Nanostructured CaWO4, CaWO4:Eu3+ and CaWO4:Tb3+ particles: sonochemical synthesis and luminescent properties

Nanostructured CaWO4, CaWO4:Eu3+, and CaWO4:Tb3+ phosphor particles were synthesized via a facile sonochemical route. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, low voltage cathodoluminescence spectra, and photoluminescence lifetimes were used to characterize the as-obtained samples. The X-ray diffraction results indicate that the samples are well crystallized with the scheelite structure of CaWO4. The transmission electron microscopy and field emission scanning electron microscopy images illustrate that the powders consist of spherical particles with sizes from 120 to 160 nm, which are the aggregates of even smaller nanoparticles ranging from 10 to 20 nm. Under UV light or electron beam excitation, the CaWO4 powder exhibited a blue emission band with a maximum at 430 nm originating from the WO4/2- groups, while the CaWO4:Eu3+ powder showed red emission dominated by 613 nm ascribed to the 5D0 --> 7F2 of Eu3+, and the CaWO4:Tb3+ powders showed emission at 544 nm, ascribed to the 5D4 --> 7F5 transition of Tb3+. The PL excitation and emission spectra suggest that the energy is transferred from WO4/2- to Eu3+ CaWO4:Eu3+ and to Tb3+ in CaWO4:Tb3+. Moreover, the energy transfer from WO4/2- to Tb3+ in CaWO4:Tb3+ is more efficient than that from WO4/2- to EU3+ in CaWO4:Eu3+. This novel and efficient pathway could open new opportunities for further investigating the novel properties of tungstate materials.     

Self-assembled peanut-like Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2: phase control and its relevance to luminescence modification

Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2 peanuts were successfully self-assembled by a facile EDTA assisted hydrothermal treatment. EDTA played critical roles in the phase and morphology control, which regulated the phase transformation from monoclinic La2(WO4)3 flowers to tetrahedral NaLa(WO4)2 peanuts. La2(WO4)3:Tb3+ exhibited two broad excitation bands at 280 and 340 nm, which are related to the normal and perturb sites of WO4(2-). However, the excitation band for NaLa(WO4)2:Tb3+ shifted to near ultraviolet region and showed only one broad excitation band originating from perturb sites. Under ultraviolet excitation, La2(WO4)3:Tb3+ displayed green light and NaLa(WO4)2:Tb3+ showed blue-green light consisting of WO4(2-) self-activated blue emission and the characteristic Tb3+ emission. It can be clearly seen that the blue emission of WO4(2-) was not sufficiently quenched in NaLa(WO4)2 as that in La2(WO4)3, because the distortions of crystalline lattice for NaLa(WO4)2 may alter the energy migration processes. When doping with Sm3+ and Eu3+, NaLa(WO4)2 peanuts exhibited white color emission which may find practical applications in solid state lighting devices.     

Synthesis and luminescence properties of Sr2SiO4: Eu3+, Dy3+ phosphors by the sol-gel method

The Sr2SiO4:Eu3+, Dy3+ phosphors for white light emitting diodes (LEDs) were synthesized by the sol-gel method. The microstructure and luminescent properties of the obtained Sr2SiO4:Eu3+, Dy3+ particles were well characterized. The results demonstrate that the Sr2SiO4:Eu3+, Dy3+ particles, which have spherical morphology, emitted an intensive white light emission under excitation at 386 nm. The phosphors show three emission peaks: the blue emission at 486 nm corresponding to the 4F(9/2)-6H(15/2) transition of Dy3+, the yellow emission at 575 nm corresponding to the 4F(9/2)-6H(13/2) transition of Dy3+, and the red emission at 615 nm corresponding to the 5D0-7F2 transition of Eu3+. At the same time, the effect of Eu3+ concentration on the emission intensities of Sr2SiO4:Eu3+, Dy3+ was investigated in detail. The phosphors used for white LEDs were obtained by combining near ultraviolet (NUV) light (386 nm) with Sr2SiO4:0.04Dy3+, 0.01Eu3+ phosphors with the characteristic of Commission Internationale de l'Eclairage (CIE) chromaticity coordinate (x, y) of (0.33, 0.34), and color temperature Tc of 5,603 K. In addition, the effect of the charge compensators (Li+, Na+, and K+ ions) on the photoluminescence (PL) emission intensities were studied.     

Emission properties of hydrothermal Yb(3+), Er(3+) and Yb(3+), Tm(3+)-codoped Lu2O3 nanorods: upconversion, cathodoluminescence and assessment of waveguide behavior

Yb(3+) and Ln(3+) (Ln(3+) = Er(3+) or Tm(3+)) codoped Lu(2)O(3) nanorods with cubic Ia3 symmetry have been prepared by low temperature hydrothermal procedures, and their luminescence properties and waveguide behavior analyzed by means of scanning near-field optical microscopy (SNOM). Room temperature upconversion (UC) under excitation at 980 nm and cathodoluminescence (CL) spectra were studied as a function of the Yb(+) concentration in the prepared nanorods. UC spectra revealed the strong development of Er(3+) (4)F(9/2) → (4)I(15/2) (red) and Tm(3+) (1)G(4) → (3)H(6) (blue) bands, which became the pre-eminent and even unique emissions for corresponding nanorods with the higher Yb(3+) concentration. Favored by the presence of large phonons in current nanorods, UC mechanisms that privilege the population of (4)F(9/2) and (1)G(4) emitting levels through phonon-assisted energy transfer and non-radiative relaxations account for these observed UC luminescence features. CL spectra show much more moderate development of the intensity ratio between the Er(3+) (4)F(9/2) → (4)I(15/2) (red) and (2)H(11/2), (4)S(3/2) → (4)I(15/2) (green) emissions with the increase in the Yb(3+) content, while for Yb(3+), Tm(3+)-codoped Lu(2)O(3) nanorods the dominant CL emission is Tm(3+) (1)D(2) → (3)F(4) (deep-blue). Uniform light emission along Yb(3+), Er(3+)-codoped Lu(2)O(3) rods has been observed by using SNOM photoluminescence images; however, the rods seem to be too thin for propagation of light.