Fluorescence properties of Eu3+ ions doped borate and fluoroborate glasses containing lithium, zinc and lead

The influence of glass composition on the fluorescence properties of Eu3+ ions doped borate and fluoroborate glasses modified with Li+, Zn2+ and Pb2+ cations have been investigated. The magnitude of splittings of 7F1 levels are analyzed using crystal-field (CF) analysis. The relative intensities of 5D0 --> 7F2 to 5D0 --> 7F1 transitions, crystal-field strength parameters and decay times of the 5D0 level have been determined and are found to be lower for Pb based glasses than those of Zn/Li based glasses. The lifetimes of 5D0 level are found to increase when borate glasses are modified with pure fluorides than with oxides and oxyfluorides. The fluorescence decay of 5D0 level fits perfect single exponential in the Eu3+:glass systems studied which indicates the absence of energy transfer between Eu3+ ions in these glasses.     

LED用Sr(1-1.5x)Mo0.8Si0.2O3.8:Eu3+x红色荧光粉的制备及其荧光性能

通过高温固相法合成了LED用红色荧光粉Sr(1-1.5x)Mo0.8Si0.2O3.8∶Eu3+x（x=0.1,0.2,0.3,0.4,0.5）。 通过XRD、激发光谱和发射光谱测试了材料的物相组成以及发光性能。 x=0.1样品的XRD谱与JCPDS 08-0482(SrMoO4)的标准卡片相同。 Eu3+代替晶格中Sr2+的位置成为发光中心。 随着Eu3+含量x的增加,593 nm处的5D0-7F1跃迁和614 nm处的5D0-7F2跃迁发射强度会相互转换：当x≤0.4时,以磁偶极5D0-7F1跃迁为主,发射橙色光;而当x=0.5时,以电偶极5D0-7F2跃迁发射为主,发射红光。 可能是过量掺杂的Eu3+离子,只能存在于晶格空位形成缺陷,无法占据SrMoO4中Sr2+的格位中,Eu3+在晶格中占据非对称中心的格位,导致电偶极跃迁变成允许跃迁,从而增加了5D0-7F2跃迁,减弱了5D0-7F1跃迁。 因此,可以通过调节激活剂的含量获得不同发光色的荧光粉。 Eu3+掺杂的硅钼酸锶体系,614 nm激发下,在368 nm处出现宽的基质吸收峰和467 nm处7F0-5D2的跃迁峰,且这2处的吸收峰在x=0.5时比x=0.4时强3倍左右。 材料能非常好的吸收368 nm波长的光,产生颜色可调的橙红色。 与近紫外光LED芯片匹配良好。     

Patterning of Gd2(WO4)3:Ln3+ (Ln=Eu, Tb) luminescent films by microcontact printing route

Gd(2)(WO(4))(3) doped with Eu(3+) or Tb(3+) thin phosphor films with dot patterns have been prepared by a combinational method of sol-gel process and microcontact printing. This process utilizes a PDMS elastomeric mold as the stamp to create heterogeneous pattern on quartz substrates firstly and then combined with a Pechini-type sol-gel process to selectively deposit the luminescent phosphors on hydrophilic regions, in which a Gd(2)(WO(4))(3):Ln(3+) (Ln=Eu, Tb) precursor solutions were employed as ink. X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectra, as well as low voltage cathodoluminescence (CL) spectra were carried out to characterize the obtained samples. Under ultraviolet excitation and low-voltage electron beams excitation, the Gd(2)(WO(4))(3):Eu(3+) samples exhibit a strong red emission arising from Eu(3+)(5)D(0,1,2)-(7)F(1,2) transitions, while the Gd(2)(WO(4))(3):Tb(3+) samples show the green emission coming from the characteristic emission of Tb(3+) corresponding to (5)D(4)-(7)F(6,5,4,3) transitions. The results show that the patterning of rare earth-doped phosphors through combining microcontact printing with a Pechini-type sol-gel route has potential for field emission displays (FEDs) applications.     

橙红色荧光粉BaZnP2O7∶Eu3+的制备与发光特性

采用高温固相法合成了BaZnP2O7∶Eu3+荧光粉, 并对其发光性质进行了研究.     

Highly uniform and monodisperse beta-NaYF(4):Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu3+ (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to 5D0-3 --> 7FJ (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively. When doped with 5% Tb3+ ions, the strong DC fluorescence corresponding to 5D4 --> 7FJ (J = 6, 5, 4, 3) transitions with 5D4 --> 7F5 (green emission at 544 nm) being the most prominent group that has been observed. In addition, under 980 nm laser excitation, the Yb3+/Er3+- and Yb3+/Tm3+-codoped beta-NaYF4 samples exhibit bright green and whitish blue up-conversion (UC) luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Vibronic interaction in europium nitrates Eu(NO3)3 x 4SOR2

Luminescence and excitation of luminescence vibronic spectra of europium nitrates Eu(NO3)3 x 4SOR2 containing sulphoxide derivatives were obtained and analysed. Some factors influencing the intensity distribution in vibronic sidebands are discussed. Significant variation of the intensity distribution in antiStokes sidebands of Eu3+ electronic transitions in series of nitrates results from the difference in effective charges on coordinated oxygen atoms of ligands. Another important detail of the vibronic spectra is a redistribution of intensity in the region of 5D0, 5D1-->7F2 transitions of luminescence spectra originated in overlap of different vibronic transitions. Mixing between the 7F2 electronic state of Eu3+ and vibronic satellites of 7F0 electronic state was studied both under conditions of resonance and in case of significant detuning.     

新型双钼酸盐红色荧光粉的制备及发光性能研究

采用高温固相法合成了一种新型的白光LED用双钼酸盐红色荧光粉,利用XRD,F-4500等对其进行了研究。结果表明:该系列荧光粉可以被近紫外光(396 nm)和蓝光(466 nm)有效激发,发射峰值位于615 nm(Eu3+离子的5D0→7F2跃迁)的红光;而且在钾铕双钼酸盐荧光粉KEu(MoO4)2中引入适量的钨酸能加强其发光强度,而不改变样品的发射光谱的形状和发射峰的位置。此外,在确定WO24-/MoO42最佳比值的前提下,文章还详细探讨了碱金属离子相互置换对样品发光性能影响的机制。     

钨钼酸盐荧光粉基质组成及其退火过程对荧光性能的影响

采用高温固相法合成了一系列Eu3+掺杂的钨钼酸盐红色荧光粉CaxSr0.88-x(WO4)y(MoO4)1-y:0.08Eu3+。对其晶体结构和荧光性能进行了X射线衍射(XRD)、荧光光谱(PL)的表征,研究了不同Sr/Ca和WO4/MoO4比例对荧光粉光谱性能的影响,初步研究了不同退火过程对其发光性能的影响。所合成的Ca0.70Sr0.18(MoO4)0.5(WO4)0.5:0.08Eu3+荧光粉发光强度较好,可以被近紫外光(395 nm)和蓝光(465nm)有效激发,发射峰位于616 nm(Eu3+的5 D0→7 F2跃迁)。     

Ca3La3(BO3)5中Eu3+的光致发光

本文详细地研究了紫外光激发下,Ca_3La_3(BO_3)_5中Eu~(3+)的发光光谱和激发光谱与组成、结构的关系.发现Eu~(3+)在此基质中可能不止一个发光中心;Eu~(3+)自身浓度猝灭的机理为电四极-四极相互作用.     

空气中合成M2B4O7:Eu3+(M=Na,K)荧光体及其性质表征

以M2B4O7(M=Na,K)为基质,在空气中掺杂稀土元素Eu3+得到了Na2B4O7:Eu3+和K2B4O7:Eu3+荧光体.探讨了体系的烧结条件和荧光性质,分析了晶体的结构.结果表明,虽然两种体系的最佳合成条件不同,但是体系中都同时存在[BO4]和[BO3]结构;稀土离子Eu3+的发光以电偶极跃迁5D0-7F2为主,处于非中心对称的格位上,并且可以很好地存在于基质中,Na2B4O7:Eu3+具有较强的发光强度.     

Luminescence and microstructures of Eu(3+)-doped Ca9LiGd(2/3)(PO4)7

A red-emitting phosphor, Eu(3+)-doped Ca(9)LiGd(2/3)(PO(4))(7), was synthesized by the conventional high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirmed the pure crystalline phase of Whitlockite-type structure. The excitation spectra of Eu(3+) doped Ca(9)LiGd(2/3)(PO(4))(7) were measured in the VUV and UV region indicating an efficient energy transfer process from the host and Gd(3+) to Eu(3+) ions. Upon excitation with VUV and UV radiation, the phosphor showed strong red emission around 611 nm corresponding to the forced electric dipole (5)D(0)→(7)F(2) transition of Eu(3+) ions. The VUV- and UV-excited luminescence spectra of Ca(9)LiGd(2/3)(PO(4))(7):Eu(3+) together with the dependence of the integrated emission intensities on the doping levels were investigated. The Eu(3+) ions were investigated by a tunable laser as an excitation source. The excitation spectra of (7)F(0)→(5)D(0) transitions suggest that there are two families of inequivalent sites for Eu(3+) in this host. The concentration quenching and crystallographic site-occupancy of Eu(3+) ions in Ca(9)LiGd(2/3)(PO(4))(7) host were discussed on the basis of the site selective excitation and emission spectra, the luminescence decay and its crystal structure.     

Solvothermal synthesis and characterization of Ln (Eu3+, Tb3+) doped hydroxyapatite

Luminescent Ln (Eu3+, Tb3+) doped hydroxyapatite (Eu:HAp, Tb:HAp) phosphors were successfully fabricated via the cetyltrimethylammonium bromide (CTAB)/n-octane/n-butanol/water microemulsion-mediated solvothermal process. The structure, morphology, and optical properties were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence (PL) spectra as well as the kinetic decays, respectively. The XRD results reveal that the obtained Eu:HAp and Tb:HAp show the characteristic peaks of hydroxyapatite in a hexagonal lattice structure. It is observed that the as-prepared luminescent samples exhibit rod-like morphology with well dispersed and non-aggregated size distribution. Upon excitation by UV radiation, the phosphors demonstrate the characteristic 5D 0-7F 1-4 emission lines of Eu3+ and the characteristic 5D4-7F 3-6 emission lines of Tb3+. Moreover, the photoluminescence intensities (PL) of Eu3+ and Tb3+ can be tuned by altering the solvothermal temperature and the doping concentration of Eu3+ and Tb3+.     

电荷补偿对红色LED用荧光粉体的荧光性能改进

通过高温动态球磨固相法, 采用三种电荷补偿方式: (a) 3Ca2+/Sr2+→2Eu3+/Gd3++空穴; (b) 2Ca2+/Sr2+→2Eu3+/Gd3++M+(M+=Li+, Na+, K+中的一种或多种离子); (c) Ca2+/Sr2+→2Eu3+/Gd3++X-(X-=F-, Cl-, Br-, I-), 制备了红色发光二极管(LED)荧光粉体Ca0.54Sr0.16-δEu0.08Gd0.12(MoO4)0.2(WO4)0.8(δ=0-0.16). 研究表明, 方法(b)是一种较优的电荷补偿方式. 利用此荧光粉和390-405 nm发射LED芯制备了红色LED, 当正向驱动电流为20 mA时, 色坐标为x=0.66, y=0.33; 色纯度100%; 光强达6200 cd·m2; 发光效率约为95 lm·W-1. 器件的色坐标和显色指数等参数随正向驱动电流的变化起伏很小, 颜色稳定. 该红光荧光粉在新一代白色LED照明领域具有广阔应用前景.     

Energy transfer and tunable luminescence properties of Eu3+ in TbBO3 microspheres via a facile hydrothermal process

Tb (1- x) BO 3: xEu (3+) ( x = 0-1) microsphere phosphors have been successfully prepared by a simple hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL), low-voltage cathodoluminescence (CL), and time-resolved emission spectra as well as lifetimes were used to characterize the samples. The as-obtained phosphor samples present sphere-like agglomerates composed of nanosheets with highly crystallinity in spite of the moderate reaction temperature of 200 degrees C. Under ultraviolet excitation into the 4f (8) --> 4f (7)5d transition of Tb (3+) at 245 nm (or 284 nm) and low-voltage electron beams' excitation, TbBO 3 samples show the characteristic emission of Tb (3+) corresponding to (5)D 4 --> (7)F 6, 5, 4, 3 transitions; whereas TbBO 3:Eu (3+) samples mainly exhibit the characteristic emission of Eu (3+) corresponding to (5)D 0 --> (7)F 0, 1, 2, 3, 4 transitions due to an efficient energy transfer occurs from Tb (3+) to Eu (3+). The increase of Eu (3+) concentration leads to the increase of the energy-transfer efficiency from Tb (3+) to Eu (3+) but also enhances the probability of the interaction between neighboring Eu (3+), which results in the concentration quenching. The PL color of TbBO 3: xEu (3+) phosphors can be easily tuned from green, yellow, orange, to red-orange by changing the doping concentration ( x) of Eu (3+), making the materials have potential applications in fluorescent lamps for advertizing signs and other color display fields.     

Enhanced red light emission from LaBSiO5:Eu3+,R3+ (R=Bi or Sm) phosphors

Polycrystalline LaBSiO5:Eu3+,R3+ (R=Bi or Sm) phosphors have been synthesized by a facile sol-gel method. The phosphors have been characterized by thermogravimetric analysis/different scanning calorimeter, scanning electron microscopy, X-ray diffractometer and fluorescence measurements. It was found that the emission intensity of LaBSiO5:Eu phosphors increases clearly and reaches a maximum at 30 mol% with increasing of Eu3+ concentration. The incorporation of Bi3+ ions and/or Sm3+ ions have greatly enhanced the emission intensity of Eu3+ upon excitation with 391 nm light. The possible sensitization mechanisms of Sm3+ and/or Bi3+ on Eu3+ emission intensity have been investigated and discussed. The high brightness and short luminescence decay times make it promising red-emitting candidates for white light-emitting diodes.     

Synthesis, characterization and photoluminescence properties of CaSiO3:Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900°C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence 5D0→7FJ (J=0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to 5D0→7F2 of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to 5D0→7F1 of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration>4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO3(2-) group. The optical energy band gap is widened with increase of Eu3+ ion dopant.     

Ce3+,Tb3+,Eu3+共掺杂Sr2MgSi2O7体系的白色发光和能量传递机理

通过正交试验,采用高温固相法制备了Sr2-x-y-zMgSi2O7∶xCe3+,yTb3+,zEu3+系列样品.使用X射线衍射仪和荧光光谱仪表征了样品的物相和发光性质,并讨论了Ce3+-Tb3+-Eu3+共掺杂Sr2MgSi2O7体系中的能量传递过程.实验结果表明,在327 nm波长激发下,所合成荧光粉的发射峰主要位于387 nm(蓝紫)、542nm(绿)和611 nm(红)处;分别以387,542和611 nm为监控波长,所得激发光谱显示荧光粉在327 nm处有最好的激发.在327 nm光激发下,系列样品发光进入白光区.最优化的荧光粉为Sr1.91MgSi2O7∶0.01Ce3+,0.05Tb3+,0.03Eu3+,其色坐标为(0.337,0.313),是一种潜在的发光二极管(LED)用白色荧光粉.     

Sr2MgSi2O7∶Tb3+，Li+荧光粉的合成和发光机理

采用高温固相法合成Sr2-mMg1-nSi2O7∶mTb3+,nLi+(m=0.03~0.50,n=m)系列荧光粉。使用X射线衍射仪和荧光光谱仪对样品的物相和发光性质进行了表征。在377 nm紫外光激发下,荧光粉的发射光谱呈多谱带发射,主峰位于490 nm,542 nm,590 nm和613 nm处,分别对应于Tb3+的5D4→7FJ(J=6,5,4,3)跃迁发射。调节Tb3+离子掺杂浓度,可实现荧光粉的发光颜色从蓝到白、黄、绿的可调发射;名义组成为Sr1.95Mg0.95Si2O7∶0.05Tb3+,0.05Li+的荧光粉在紫外光(377 nm)激发下发白光,其色坐标(0.322,0.317)接近纯白光(0.33,0.33),是一种潜在的LED用单基质白光荧光粉。     

磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+,Tb3+的合成、发光和能量传递

采用高温固相法合成了系列Ce~(3+)和Ce~(3+)/Tb~(3+)激活的具有磷灰石结构荧光粉Ba_(10)(PO_4)_6F_2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO4)6F2∶x Ce~(3+)的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的激发光谱为240～330 nm的宽带,发射光谱呈现出Ce~(3+)的5d→4f跃迁紫外光(335和358 nm)发射和Tb~(3+)的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce~(3+)→Tb~(3+)能量传递,能量传递效率可以达到60%。计算Ce~(3+)和Tb~(3+)的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce~(3+)和Tb~(3+)之间的能量传递和发光的过程。通过调节Tb~(3+)的掺杂浓度,对荧光粉发光色坐标与Tb~(3+)的掺杂浓度之间的关系也进行了研究,随着Tb~(3+)的掺杂量从0增加0.52,荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。     

绿色荧光粉KNaCa2（PO4）2:Tb3+的制备及发光性能研究

采用高温固相法成功制备了KNaCa2(PO4)2:Tb3+绿色荧光粉,并研究了其发光性质。测量了其激发和发射光谱,样品发射峰位于418,440,492,545,586,622 nm,分别对应Tb3+的5 D3→7 F5,5 D3→7 F4,5 D4→7 F6,5 D4→7 F5,5 D4→7 F4,5 D4→7 F3能级跃迁,主发射峰位于545 nm。主激发峰位于350～390 nm之间,属于4f→4f电子跃迁吸收,与InGaN管芯匹配。确定了在KNaCa2(PO4)2基质中Tb3+浓度对其发光强度的影响及其自身浓度猝灭机制。研究了不同电荷补偿剂对KNaCa2(PO4)2:Tb3+材料发光的影响,其中Li+离子改善其发光强度最为明显。