Yb~(3+)共掺杂Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+)长余辉发光材料的制备与性能研究

通过高温固相法制备了Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+),Yb~(3+)长余辉发光材料。采用XRD、SEM、激发光谱、发射光谱和余辉衰减曲线对Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+),Yb~(3+)长余辉发光材料的微观结构以及光学性能进行了表征,研究结果表明Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+),Yb~(3+)长余辉发光材料的晶体结构和显微结构均未发生明显变化。Yb~(3+)的引入使得Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+)显示出更优良的荧光性能和余辉性能,不同Yb~(3+)掺量对长余辉发光材料的陷阱深度和电子传输速率有显著影响。实验表明,当Yb~(3+)掺杂量为0.03时,Sr_2MgSi_2O_7∶Eu~(2+),Dy~(3+),Yb~(3+)的荧光光谱相对强度最强,且表现出最佳的余辉衰减性能。     

Na_2WO_4:Eu~(3+),Tb~(3+)光致发光材料的发光性质和能量传递

利用溶胶-凝胶法,将激活离子Eu~(3+)和Tb~(3+)以单一或混合的形式掺入体系得到了光致发光材料.分别研究了材料中激活离子Eu~(3+)和Tb~(3+)的含量及其离子之间的能量传递关系.主要利用材料的三维荧光光谱,激发光谱和发射光谱对其的发光性质进行了分析;结果发现,材料中有两个发光中心,分别为Eu~(3+)和Tb~(3+),在不同的波长光的激发下得到的材料的红绿色发光强度不同,而且Eu~(3+)和Tb~(3+)的掺杂浓度比对发光色度影响很大.所以可以根据选择最适合的Eu~(3+)和Tb~(3+)的浓度比来控制材料的发光色,也可以通过不同的激发波长对材料的色度进行微调.     

稀土隔室配合物——(Ⅱ)稀土-N、N′-二(3—醛基水扬酸)二乙基三胺配合物的合成及表征

用稀土硝酸盐与N、N′-二(3—醛基水扬酸)二乙基三胺(H_4L)在甲醇介质中反应,合成了9种新的固态配合物RE(H_2L)NO_3·nH_2O,(RE~(3+)=Y~(3+)、Pr~(3+)、Sm~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+),n=0～4不等);用元素分析、红外、紫外及热分析鉴定了所有配合物,从而推测配合物中可能RE~(3+)在O_2O_2室,—COO~-单齿配位,NO_3~-双齿配位     

荧光光度法同时测定痕量铕和铽

利用稀土—六氟乙酰丙酮(HFA)—三辛基氧化膦(TOPO)荧光萃取体系,测定稀土金属离子已为文献所报道。但该法操作麻烦,且使用大量有毒溶剂。本文利用Triton X-100对上述体系的增溶和增敏作用,同时测定了铕和铽。结果表明,Eu~(3+)和Tb~(3+)在1.0×10~(-9)～5.0×10~(-7)M范围内遵守比尔定律,检出限达到10~(-10)M数量级。该法     

Study on white-light emission and light-emitting mechanism of hydrothermally synthesized YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders

White light-emitting YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders with order morphology and well crystallization were hydrothermally synthesized at 180°C. The microstructure, white-light emission, and light-emitting mechanism of the powders were carefully studied using X-ray diffractometry, scanning electron microscopy and photoluminescence spectra. The excitation and emission spectra of the phosphor powders indicated the coexistence of efficient energy transfer from Eu~(3+) to Dy~(3+) and inefficient energy transfer from Dy~(3+) to Eu~(3+) besides the energy transfer from VO_4~(3–) to Eu~(3+). Increasing the Eu~(~(3+)) concentration initially enhanced and then weakened the luminescent intensity of Dy~(3+). The white-light emissions of YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders were both related to the energy transfer between VO_4~(3–) and Dy~(3+)/Eu~(3+), as well as between Eu~(3+) and Dy~(3+). The inefficient energy transfer from Dy~(3+) to Eu~(3+) was first found.     

Luminescent properties and energy transfer mechanism from Tb~(3+) to Eu~(3+) in CaMoO_4:Tb~(3+),Eu~(3+) phosphors

A series of CaMoO_4:Tb~(3+),Eu~(3+) phosphors were prepared by the method of precipitation. The structure and morphology of the phosphors were characterized by the X-ray diffraction(XRD) and field emission scanning electron microscopy(FE-SEM). The photoluminescence properties of the prepared products were researched, and the energy transfer from Tb~(3+) to Eu~(3+) in CaMoO_4 phosphors was studied. By adjusting the doping concentration of Eu~(3+) ions in CaMoO_4:Tb~(3+),Eu~(3+) phosphors, the emitting color of the phosphors could be easily tuned from green to red. With Tb~(3+) doped in the phosphors, the red luminescence of Eu~(3+) by near UV excitation was significantly enhanced. The energy transfer efficiency, rate and average distance between Tb~(3+) and Eu~(3+) in CaMoO_4:5%Tb~(3+),x%Eu~(3+)(mole percent) phosphors(x=0.3–10) were calculated. It was found that the interaction type between Tb~(3+) and Eu~(3+) was electric dipole-dipole interaction in the phosphors.     

YV_(1-x)B_xO_(4-x):Eu~(3+)(或Dy~(3+),Bi~(3+))的合成及光谱性质的研究

本文报道了Eu~(3+)、D~(3+)在YV_(1-x)B_xO_(4-x)中的光谱性质。实验表明:B~(3+)取代V~(5+)时,可使基质和Dy~(3+)的发射强度及黄兰比下降,并使基质的吸收带短移。而B~(3+)取代Y~(3+)时,则可提高Dy~(3+)的黄兰比。同时我们还研究了Bi~(3+)和温度对YV_(0.69)B_(0.31)O_(3.69):Dy~(3+)中Dy~(3+)发射强度的影响。     

Upconversion multicolor tuning of NaY(WO4)2:Tb3+ with Eu3+ doping

A series of Tb~(3+) and Eu~(3+) co-doped NaY(WO_4)_2 phosphors were synthesized by hydrothermal reactions.The crystal structure,morphology,upconversion luminescent properties,the energy transfer from Tb~(3+) to Eu~(3+)ions and the ~5 D_4→ ~7 F_5 transition of the Tb~(3+) ion in NaY(WO_4)_2:Tb~(3+),Eu~(3+) phosphors were investigated in details.The results indicate that all the synthesized samples are of pure tetragonal phase NaY(WO_4)2.Furthermore,the micrometer-sized needle spheres and excellent dispersion of the particles are obtained by adding polyethylene glycol(PEG-2000) as the surfactant.Phosphors of NaY(WO_4)_2:Tb~(3+),Eu~(3+) exhibit the492 nm blue emission peak,546 nm green emission peak,595 nm orange emission peak and 616 nm red emission peak under 790 nm excitation.The energy transfer from Tb~(3+) to Eu~(3+) is a resonant transfer,in which electric dipole-dipole interaction plays a leading role.By adjusting the doping concentration of Eu~(3+) in NaY(WO_4)_2: 1.0 mol%Tb~(3+),xmol%Eu~(3+) phosphors,the emitting color of UC phosphors can be tuned from green to red.     

新型蓝色长余辉荧光粉SrAl_2O_(4-y)N_y∶Eu~(2+),Dy~(3+)发光性能研究

采用高温固相反应合成了SrAl_2O_(4-y)N_y∶Eu~(2+),Dy~(3+)系列长余辉荧光粉,并研究了SrAl_2O_(3.75)N_(0.25)∶Eu~(2+),Dy~(3+)体系的晶体结构、光谱特性、余辉衰减曲线及热释发光曲线。X射线衍射分析结果表明,SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)荧光材料属六方晶系,P6322空间群,晶胞参数a=b=5.14,c=8.462,γ=120°。荧光光谱测试结果表明,SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)的激发光谱和发射光谱均为宽带谱,激发光谱位于283 nm~450 nm,发射光谱的峰值位于487 nm,属于Eu~(2+)的4f65d1→4f7跃迁发射。Eu~(2+)的掺杂量并不改变SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)发射光谱的形状和峰值位置,但对相对发光强度有较大影响,Eu~(2+)的摩尔浓度为2%时相对发光强度最高。余辉衰减曲线表明,Sr_(0.97)Al_2O_(3.75)N_(0.25)∶Eu_(0.02),Dy_(0.01)的余辉衰减符合指数衰减规律,由初始的快衰减和之后的慢衰减两个过程组成。通过热释发光曲线对荧光材料中的陷阱能级进行计算,得出Sr_(0.97)Al_2O_(3.75)N_(0.25)∶Eu_(0.02),Dy_(0.01)的能级陷阱为0.42 V,掺Dy~(3+)有利于提高该荧光材料的初始发光亮度和余辉时间。     

Structural and optical properties of Dy~(3+):YAlO_3 phosphors for yellow light-emitting diode applications

The spectroscopic properties of a series of Dy~(3+) single-doped and Dy~(3+)/Nd~(3+),Dy~(3+)/Tb~(3+),and Dy~(3+)/Tm~(3+)co-doped YAlO_3(yttrium aluminum perovskite,YAP) phosphors were investigated and compared through the measurements of optical absorption,emission spectra,and fluorescence decay curves.For the Dy~(3+) ion single-doped samples,the intensity of each absorption band increases with an increment in Dy~(3+) ion doping concentration,and the identified strong absorption peak at 447 nm indicates that Dy~(3+):YAP phosphors are suitable to be pumped by a blue laser diode(LD).For all co-doped samples,absorption peaks of Dy~(3+) ion along with some of the absorption bands of Nd~(3+),Tb~(3+),and Tm~(3+) ions are observed.Under 351 and 447 nm excitation,a prominent emission peak at 572 nm was obtained in all the samples,corresponding to Dy~(3+):~4 F_(9/2)→~6 H_(13/2) transition.Here,2 at% Dy~(3+):YAP phosphor exhibits the highest yellow emission intensity under 447 nm pumping.Among the three kinds of Dy~(3+) co-doped phosphors,Dy~(3+)/Tb~(3+):YAP phosphor possesses the dominant yellow emission.The fluorescence decay curves show exponential behaviour and are fitted well.The Commission International de L'Eclairage(CIE)chromaticity coordinates were calculated following the respective emission spectra,and it is found that all the coordinates locate in the yellow region.The energy transfer(ET) processes were investigated and the concentration quenching mechanism was discussed.The obtained results suggest that Dy~(3+)-activated YAP phosphors are good candidates for yellow LED applications.     

Synthesis and optical characterization of Eu2+,Tb3+-codoped Sr3Y(PO4)3 green phosphors

A series of Eu~(2+),Tb~(3+)-codoped Sr_3 Y(PO_4)_3(SYP) green phosphors were synthesized by hightemperature solid-state reaction. Several techniques, such as X-ray diffraction, UV-vis spectrum,and photoluminescence spectrum, were used to investigate the obtained phosphors. The present study investigates in detail photoluminescence excitation and emission properties, energy transfer between the two dopants, and effects of doping ions on optical band gap. SYP:0.05 Eu2+ phosphor shows an intense and broad excitation band ranging from 220 to 400 nm and exhibits a bright green emission band with CIE chromaticity coordinates(0.189, 0.359) under 350 nm excitation. Green emission of SYP:0.03 Tb3+ is intensified by codoping with Eu~(2+), and energy transfer mechanism between them is demonstrated to be a dipole-dipole interaction. Upon 350 nm excitation, SYP:Eu~(2+),Tb~(3+) phosphors exhibits two dominating bands peaking at 466 and 545 nm, which are assigned to 4 f~65 d~1→4 f~7 transition of Eu~(2+) ions and ~5 D_4→~7 F_5 transition of Tb~(3+) ions, respectively. Optimal doping concentrations of Eu~(2+) and Tb~(3+) in the SYP host are 5 mol% and 15 mol%, respectively. Results indicate that SYP:Eu~(2+),Tb~(3+) phosphors are potentially used as green-emitting phosphors for white light-emitting diodes.     

Synthesis and luminescence of β-SrGe(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) phosphors for UV light-emitting diodes

A new series of β-Sr Ge(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) phosphors were synthesized and characterized by using X-ray powder diffraction as well as excitation, and emission spectroscopy. The results exhibited that the singly doping Eu2+, Tb~(3+) and Eu~(3+) of β-Sr Ge(PO_4)_2 emit strong blue, green and red light under UV irradiation, respectively. Based on the charge transfer transitions of O~(2–)→RE~(3+), an overlapping excitation band of the as-obtained phosphors could be found in UV region, which made β-Sr Ge(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) serve as a new series of RGB phosphors. Meanwhile, these phosphors could also be excited by 380 nm excitation simultaneously, and hence the three phosphors mixed physically could achieve the tunable hues from blue to white region by adjusting the mixed ratios.     

Structural characterization and temperature-dependent luminescence of CaF_2:Tb~(3+)/Eu~(3+) glass ceramics

Tb~(3+)/Eu~(3+) co-doped transparent glass ceramics containing CaF_2 nanocrystals were successfully synthesized by high temperature melt-quenching method and subsequent heating. The structure and morphology of the samples were investigated by X-ray diffraction(XRD), transmittance electron microscopy(TEM), high resolution TEM(HRTEM) and selected area electron diffraction(SAED). The photoluminescence properties and energy transfer process from Tb~(3+) to Eu~(3+) of CaF_2:Tb~(3+),Eu~(3+) phosphors were also investigated through excitation spectra and decay curves. In addition, the emission spectra of the glass ceramics in a wide temperature range from 21 to 320 K were recorded under the excitation of 485 nm. It was found that the fluorescence intensity ratios of Tb~(3+) at 545 nm(~5D_4→~7F_5) to Eu~(3+) at 615 nm(~5D_0→~7F_2) was highly temperature-dependent with an approximate linear relationship, and the temperature sensitivity was about 0.4%/K. It is expected that the investigated Tb~(3+)/Eu~(3+) co-doped CaF_2 glass ceramics may have prospective application in optical thermometry.     

废旧荧光粉中稀土元素浸出的电位-pH图

废旧稀土荧光粉经"酸浸-碱焙烧-水洗-酸浸"处理可浸出回收其中的Y, Eu, Tb, Ce等稀土。本文根据酸浸过程中的各组分的吉布斯自由能Δ_fG分别计算出各酸浸过程中各化学反应的吉布斯自由能Δ_rG,由能斯特公式计算出反应的电位与pH关系,进而绘制出两段酸浸过程中的电位-pH图,即不同活度的Al~(3+)与Y-Eu-H_2O系的电位-pH图和Tb-Ce-H_2O系电位-pH图,并分析了各组分的稳定区域。结果表明:废旧稀土荧光粉直接酸浸时,从25～100℃,在pH6的酸性条件下,红粉中的Y_2O_3, Eu_2O_3以Y~(3+), Eu~(3+)的形式稳定存在水溶液中, Al(OH)_3稳定区域在pH为4.8～8.3之间,为防止Al ~(3+)水解,酸浸出液终点pH值应控制在3.5～4.0之间;从25～100℃,在酸性条件下,经碱焙烧水洗除铝后得到的TbO_2, CeO_2很难被酸直接浸出,同时Tb~(4+), Ce~(4+)在水溶液中不能稳定存在,但通过加入适当的还原剂,可将Tb~(4+), Ce~(4+)还原成Tb~(3+), Ce~(3+),便可存在于水溶液中。     

支撑液膜法分离铕和钇

本文在详细研究了单一稀土Eu~(3+)、Y~(3+)在聚砜—P_(204)支撑液膜体系中迁移行为的基础上,尝试利用聚砜—P_(204)支撑液膜体系对Eu~(3+)、Y~(3+)的混合稀土进行分离。实验结果表明控制适当的实验条件,利用此支撑液膜体系可以对这两种稀土离子进行有效分离。升高原液酸度,降低膜相载体浓度,可以提高此支撑液膜体系的选择性,有利于稀土离子分离。     

Superhydrophobic and luminescent cotton fabrics prepared by dip-coating of APTMS modified SrAl-_2O_4:Eu~(2+),Dy~(3+) particles in the presence of SU8 and fluorinated alkyl silane

An organic-inorganic composite dip-coating method was adopted in order to obtain ideal water repellent cotton fabrics. To be specific, a dual-functional coating with both superhydrophobic and luminescent properties was prepared on cotton fabric by using a dip-coating solution comprising(3-aminopropyl) trimethoxysilane(APTMS) modified SrAl_2O_4:Eu~(2+),Dy~(3+) particles, SU8, and fluorinated alkyl silane(FAS). The micro/nano-scale roughness generated by SrAl_2O_4:Eu~(2+),Dy~(3+) particles, together with low-surface-energy FAS, rendered the cotton fabric superhydrophobic with a water contact angle of about 160° and a sliding angle as small as 2°. The coated fabric could withstand at least 100 cycles of standard laundry. The emission spectra of the coated fabric showed two emission peaks at 440 and 520 nm, which belonged to the blue and yellow-green color areas, respectively. The afterglow duration of the coated fabric was mainly influenced by the different depths of the trap levels in the SrAl_2O_4:Eu~(2+),Dy~(3+).     

Study of Adsorption Properties and Enriching RE on Clay Minerals by Ouantum Chemical Calculation

The order of adsorbability of three kinds of clay minerals and their selectivity of adsorption tocommon cations and RE ions have been studied by quantum chemical calculation.They are as follows:montmorilionite>halloysite>kaolinite,RE~(3+)>Al~(3+)>Ca~(2+)>Mg~(2+)>K~+>NH_4~+>Na~+,Sc~(3+)>La~(3+)>Ce~(3+)>Pr~(3+)>Nd~(3+)>Sm~(3+)>Eu~(3+)>Gd~(3+)>Tb~(3+)>Dy~(3+)>Ho~(3+)>Y~(3+)>Er~(3+)>Tm~(3+)>Yb~(3+)>Lu~(3+).Based onthese orders,the facts that RE is preferentially adsorbed in weathered residual type of clay mineral and lightRE and heavy RE are enriched at the upper layer and at the lower layer respectively in ore body have beenexplained.     

Influence of dysprosium concentration on sensitivity of luminescent thermometers of phosphors Ca_9Tb(PO_4)_5(SiO_4)F_2

Tb~(3+),Dy~(3+)-co-doped Ca_9 Tb_xDy_(1-x)(PO_4)_5(SiO_4)F_2 phosphors were prepared via high-temperature solidphase reaction method and the potential application in optical temperature measurements due to their color-tunable property was investigated in detail.The photoluminescence emission(PL) and photoluminescence excitation(PLE) spectra results show that the as-prepared phosphors exhibit both Tb~(3+) and Dy~(3+) emissions at 546 nm(~5 D_4-~7 F_5 transition of Tb~(3+)) and 587 nm(~4 F_(9/2)-~6 H_(13/2) transition of Dy~(3+)) upon376 nm excitation,respectively.In addition,the fluorescence decay analysis shows that the lifetime of the Tb3+emission rapidly decreases,which confirms the energy transfer existence between Dy~(3+) and Tb~(3+).Under 376 nm excitation,the temperature dependence of the fluorescence intensity ratios for the dualmission bands peaked at 546 and 587 nm was studied in the temperature range from 303 to 573 K.The results show that with the increase of Dy~(3+) concentration,the relative sensitivity first increases and then decreases,what's more,the maximum relative sensitivity is 3.142×10~(-3)%/K for Ca_9 Tb_xDy_(1-x)(PO_4)_5(SiO_4)-F_2(x=0.4).As a consequence,this preliminary study provides a novel method for exploring the novel thermo meters.     

Influence of reaction parameters on the luminescence properties of monodisperse NaGd(1−x−y)(WO4)2:xEu3+,yTb3+ phosphor by molten salt synthesis

Eu~(3+) activated and Eu~(3+), Tb~(3+) co-activated monodisperse sodium double tungstates NaGd(WO4)2 phosphors were prepared by molten salt method at 750 ℃ for 10 h using NaCl as a flux. The crystal structure and morphology of the as-synthesized phosphors were measured by XRD and SEM, respectively. The photoluminescence properties were characterized by PL spectra, decay lifetime and CIE. The presence of NaCl plays an important role in the morphology and luminescence properties. In this work,NaCl and one of the raw material Na_2 CO_3 in a certain proportion will form a low eutectic salt to decrease the reaction temperature and benefit the formation of monodisperse NaGd(WO_4)_2 crystals. The color of Eu~(3+) and Tb~(3+) co-doped NaGd(WO_4)_2 phosphors can be tuned from creamy white to orange, red and green by adjusting the doping concentration of rare earth ions, since the emission contain the broad blue-green emission origin from NaGd(WO_4)_2 host and characteristic red and green emission origin from Eu~(3+) and Tb~(3+) ions. The electroluminescent spectra and CIE measurement shows that the LED device with NaGd_((1-x))(WO_4)_2:xEu~(3+)(x = 0.24) phosphor can be excited by 365 nm and 380 nm LED chip, and their CIE coordinate is(x = 0.45, y = 0.45) and(x = 0.36, y = 0.37), Ra is 80.3 and 86.3, T_c is 3196 and4556 K, respectively. As a single-component phosphor, NaGd(WO_4)_2:Eu~(3+),Tb~(3+) have potential application in UV-pumped WLEDs.     

氧离子浓度对CaAlSiN_3:Eu~(2+)荧光材料温度特性的影响

采用高温固相法合成了氮化物荧光材料CaAlSiN_3:Eu~(2+),研究了不同氧含量时CaAlSiN_3:Eu~(2+)发光性能的变化。当氧含量为2.5%时,得到了最高的发光强度和最佳的温度猝灭性能。从CaAlSiN_3:Eu~(2+)结晶性能以及CaAlSiN_3基质能带结构的变化等方面分析了氧离子浓度变化引起CaAlSiN_3:Eu~(2+)发光性能改变的原因。