The quantum cutting of Tb(3+) in Ca(6)Ln(2)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) under VUV-UV excitation: with and without Gd(3+)

The VUV-vis spectroscopic properties of Tb(3+) activated fluoro-apatite phosphors Ca(6)Ln(2-x)Tb(x)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) were studied. The results show that phosphors Ca(6)Gd(2-x)Tb(x)Na(2)(PO(4))(6)F(2) with Gd(3+) ions as sensitizers have intense absorption in the VUV range. The emission color of both phosphors can be tuned from blue to green by changing the doping concentration of Tb(3+) under 172 nm excitation. The visible quantum cutting (QC) via cross relaxation between Tb(3+) ions was observed in cases with and without Gd(3+). Though QC can be realized in phosphors Ca(6)La(2-x)Tb(x)Na(2)(PO(4))(6)F(2), we found that Gd(3+)-containg phosphors have a higher QC efficiency, confirming that the Gd(3+) ion indeed plays an important role during the quantum cutting process. In addition, the energy transfer process from Gd(3+) to Tb(3+) as well as (5)D(3)-(5)D(4) cross relaxation was investigated and discussed in terms of luminescence spectra and decay curves.     

Nanocrystalline CaYAlO4:Tb3+/Eu3+ as promising phosphors for full-color field emission displays

Eu(3+) and/or Tb(3+)-doped CaYAlO(4) phosphor samples were synthesized by Pechini-type sol-gel method. X-Ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) and cathodoluminescence (CL) spectra were used to characterize the samples. For CaYAlO(4):Tb(3+), it is shown that the Tb(3+)-doping concentration has a significant effect on the (5)D(3)/(5)D(4) emission intensity of Tb(3+), which is attributed to the cross relaxation from (5)D(3) to (5)D(4). Under the 4f(8)→ 4f(7)5d excitation of Tb(3+) or low-voltage electron beams excitation, the CaYAlO(4):Tb(3+) phosphors show tunable luminescence from blue to cyan, and then to green with the change of Tb(3+)-doping concentration. The CaYAlO(4):Eu(3+) samples exhibit a reddish-orange emission of Eu(3+) corresponding to (5)D(0,1)→(7)F(0,1,2,3) transitions. Furthermore, a white emission can be realized in the single phase CaYAlO(4) host by reasonably adjusting the doping concentrations of Tb(3+) and Eu(3+) under low-voltage electron beams excitation. Compared with the commercial blue (Y(2)SiO(5):Ce(3+)) and green (ZnO:Zn) phosphors, CaYAlO(4):0.1%Tb(3+) and CaYAlO(4):5%Tb(3+) phosphors have higher CL intensity and stability under continuous electron bombardment. Due to the excellent CL properties and good CIE chromaticity coordinates, the as-prepared Tb(3+)/Eu(3+)-doped CaYAlO(4) nanocrystalline phosphors have potential application in FEDs devices.     

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。     

Photoluminescence characterization of Ca10Na(PO4)7:Eu3+ red-emitting phosphor

Eu3+-doped Ca10Na(PO4)7 phosphors were successfully synthesized by solid-state reaction techniques. Their structures and photoluminescence characteristics were carefully studied. An efficient red emission under near-ultraviolet excitation is observed. The maximum intensity of luminescence was observed at the Eu3+ concentration around 9 mol%. The quadrupole-quadrupole interaction between Eu3+ ions is the dominant mechanism for concentration quenching of fluorescence emission from Eu3+ ions in Ca10-xNa(PO4)7:xEu3+. Due to the excitation spectrum is well coupled with near UV light, Ca10-xNa(PO4)7:xEu3+ phosphors have potential application as red phosphors in near UV chip-based white light emitting diodes.     

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.     

Tb~(3+)在YAG中的发光及Tb~(3+)与Tm~(3 +)间的能量传递

采用溶胶 -凝胶方法合成了系列化合物 (Y1 -x- yTbxTmy) 3Al5O1 2 ,研究了Tb3+在该化合物中的发光及其浓度对发光性质的影响 ,以及Tb3+与Tm3+间的能量传递现象。     

(Zn, Mg)2GeO4:Mn2+ submicrorods as promising green phosphors for field emission displays: hydrothermal synthesis and luminescence properties

(Zn(1-x-y)Mg(y))(2)GeO(4): xMn(2+) (y = 0-0.30; x = 0-0.035) phosphors with uniform submicrorod morphology were synthesized through a facile hydrothermal process. X-Ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photoluminescence (PL), and cathodoluminescence (CL) spectroscopy were utilized to characterize the samples. SEM and TEM images indicate that Zn(2)GeO(4):Mn(2+) samples consist of submicrorods with lengths around 1-2 μm and diameters around 200-250 nm, respectively. The possible formation mechanism for Zn(2)GeO(4) submicrorods has been presented. PL and CL spectroscopic characterizations show that pure Zn(2)GeO(4) sample shows a blue emission due to defects, while Zn(2)GeO(4):Mn(2+) phosphors exhibit a green emission corresponding to the characteristic transition of Mn(2+) ((4)T(1)→(6)A(1)) under the excitation of UV and low-voltage electron beam. Compared with Zn(2)GeO(4):Mn(2+) sample prepared by solid-state reaction, Zn(2)GeO(4):Mn(2+) phosphors obtained by hydrothermal process followed by high temperature annealing show better luminescence properties. In addition, codoping Mg(2+) ions into the lattice to substitute for Zn(2+) ions can enhance both the PL and CL intensity of Zn(2)GeO(4):Mn(2+) phosphors. Furthermore, Zn(2)GeO(4):Mn(2+) phosphors exhibit more saturated green emission than the commercial FEDs phosphor ZnO:Zn, and it is expected that these phosphors are promising for application in field-emission displays.     

Novel red-emitting Ba2Tb(BO3)2Cl:Eu phosphor with efficient energy transfer for potential application in white light-emitting diodes

A novel red-emitting Ba(2)Tb(BO(3))(2)Cl:Eu phosphor possessing a broad excitation band in the near-ultraviolet (n-UV) region was synthesized by the solid-state reaction. Versatile Ba(2)Tb(BO(3))(2)Cl compound has a rigid open framework, which can offer two types of sites for various valence's cations to occupy, and the coexistence of Eu(2+)/Eu(3+) and the red-emitting luminescence from Eu(3+) with the aid of efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) have been investigated. Ba(2)Tb(BO(3))(2)Cl emits green emission with the main peak around 543 nm, which originates from (5)D(4) → (7)F(5) transition of Tb(3+). Ba(2)Tb(BO(3))(2)Cl:Eu shows bright red emission from Eu(3+) with peaks around 594, 612, and 624 nm under n-UV excitation (350-420 nm). The existence of Eu(2+) can be testified by the broad-band excitation spectrum, UV-vis reflectance spectrum, X-ray photoelectron spectrum, and Eu L(3)-edge X-ray absorption spectrum. Decay time and time-resolved luminescence measurements indicated that the interesting luminescence behavior should be ascribed to efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) in Ba(2)Tb(BO(3))(2)Cl:Eu phosphors.     

Novel yellow-emitting Sr8MgLn(PO4)7:Eu2+ (Ln=Y, La) phosphors for applications in white LEDs with excellent color rendering index

Eu(2+)-activated Sr(8)MgY(PO(4))(7) and Sr(8)MgLa(PO(4))(7) yellow-emitting phosphors were successfully synthesized by solid-state reactions for applications in excellent color rendering index white light-emitting diodes (LEDs). The excitation and reflectance spectra of these phosphors show broad band excitation and absorption in the 250-450 nm near-ultraviolet region, which is ascribed to the 4f(7) → 4f(6)5d(1) transitions of Eu(2+). Therefore, these phosphors meet the application requirements for near-UV LED chips. Upon excitation at 400 nm, the Sr(8)MgY(PO(4))(7):Eu(2+) and Sr(8)MgLa(PO(4))(7):Eu(2+) phosphors exhibit strong yellow emissions centered at 518, 610, and 611 nm with better thermal stability than (Ba,Sr)(2)SiO(4) (570 nm) commodity phosphors. The composition-optimized concentrations of Eu(2+) in Sr(8)MgLa(PO(4))(7):Eu(2+) and Sr(8)MgY(PO(4))(7):Eu(2+) phosphors were determined to be 0.01 and 0.03 mol, respectively. A warm white-light near-UV LED was fabricated using a near-UV 400 nm chip pumped by a phosphor blend of blue-emitting BaMgAl(10)O(17):Eu(2+) and yellow-emitting Sr(8)MgY(PO(4))(7):0.01Eu(2+) or Sr(8)MgLa(PO(4))(7):0.03Eu(2+), driven by a 350 mA current. The Sr(8)MgY(PO(4))(7):0.01Eu(2+) and Sr(8)MgLa(PO(4))(7):0.03Eu(2+) containing LEDs produced a white light with Commission International de I'Eclairage (CIE) chromaticity coordinates of (0.348, 0.357) and (0.365, 0.328), warm correlated color temperatures of 4705 and 4100 K, and excellent color rendering indices of 95.375 and 91.75, respectively.     

A novel strategy for controllable emissions from Eu3+ or Sm3+ ions co-doped SrY2O4:Tb3+ phosphors

Trivalent rare-earth (RE) ions (Eu(3+), Tb(3+) and Sm(3+)) activated multicolor emitting SrY(2)O(4) phosphors were synthesized by a sol-gel process. The structural and morphological studies were performed by the measurements of X-ray diffraction profiles and scanning electron microscope (SEM) images. The pure phase of SrY(2)O(4) appeared after annealing at 1300 °C and the doping of RE ions did not show any effect on the structural properties. From the SEM images, the closely packed particles were observed due to the roughness of each particle tip. The photoluminescence (PL) analysis of individual RE ions activated SrY(2)O(4) phosphors exhibits excellent emission properties in their respective regions. The Eu(3+) co-activated SrY(2)O(4):Tb(3+) phosphor creates different emissions by controlling the energy transfer from Tb(3+) to Eu(3+) ions. Based on the excitation wavelengths, multiple (green, orange and white) emissions were obtained by Sm(3+) ions co-activated with SrY(2)O(4):Tb(3+) phosphors. The decay measurements were carried out for analyzing the energy transfer efficiency and the possible ways of energy transfer from donor to acceptor. The cathodoluminescence properties of these phosphors show similar behavior as PL properties except the energy transfer process. The obtained results indicated that the energy transfer process was quite opposite to the PL properties. The calculated CIE chromaticity coordinates of RE ions activated SrY(2)O(4) phosphors confirmed the red, green, orange and white emissions.     

Luminescence of Tb3+ and Eu3+ doped amorphous zinc benzoates

The Tb(3+) and Eu(3+) doped amorphous zinc benzoate were prepared. Their infrared absorption, emission and excitation spectra were measured. The luminescence mechanisms of Tb(3+) and Eu(3+) in the amorphous substrate were discussed. The bonding modes of OCO group to Zn(2+) ion have two of symmetric and asymmetric bridging bidentate. The energy of the S(1) pi,pi* excited state of benzene ring can be transferred to Tb(3+) and Eu(3+) ion, and results in characteristic emission from the 5D(4)-->(7)F(j) of Tb(3+) and 5D(0)-->(7)F(j) of Eu(3+), respectively.     

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.     

蓝色长余辉材料CaAl2O4:Eu2+,Nd3+的合成及其发光性能

采用高温固相法合成了系列单相Ca(1-x-y)Al2O4:Eu2+x,Nd3+y(0≤x≤0.045,0≤y≤0.0037)粉末样品,并表征了其发光特性.研究结果表明,样品的发射光谱为最大发射峰位于440nm的宽带谱,属于Eu2+的4f65d→4f7跃迁.通过对Eu2+,Nd3+掺杂量与样品发光性能之间关系的研究发现,Eu2+和Nd3+最佳掺杂量分别为x=0.00125和y=0.0025,并且Nd3+对改善蓝色长余辉材料CaAl4:Eu2+的余辉性能具有重要的作用.在最佳掺杂条件下,样品的余辉时间可达1000min,初始亮度大于1200mcd/m2,60min后发光粉的亮度仍然在10mcd/m2以上.利用正电子湮灭技术和热释光技术,研究了Eu2+和Nd3+对CaAl2O4:Eu2+,Nd3+材料的发光性能的影响.     

Electrospinning synthesis and luminescence properties of one-dimensional La(9.33)(SiO4)6O2: Ln3+ (Ln = Ce, Eu, Tb) microfibers

One-dimensional La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers were fabricated by a simple and cost-effective electrospinning method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and low voltage cathodoluminescence (CL) as well as kinetic decay were used to characterize the resulting samples. SEM and TEM results indicated that the diameter of the microfibers annealed at 1000 °C for 3 h was 200-245 nm. The microfibers were further composed of fine and closely linked nanoparticles. La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors showed the characteristic emission of Ce(3+) (5d → 4f), Eu(3+) ((5)D(0)→(7)F(J)) and Tb(3+) ((5)D(3,4)→(7)F(J)) under ultraviolet excitation and low-voltage electron beams (3-5 kV) excitation. An energy transfer from Ce(3+) to Tb(3+) was observed in the La(9.33)(SiO(4))(6)O(2): Ce(3+), Tb(3+) phosphor under ultraviolet excitation and low-voltage electron beam excitation. Luminescence mechanisms were proposed to explain the observed phenomena. Blue, red and green emission can be realized in La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers by changing the doping ions. So the La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors have potential applications in full-color field emission displays.     

紫外激发Sr1-x-yMgP2O7:xCe3+,yTb3+荧光粉的发光特性及能量传递

采用高温固相法合成了Sr1-x-yMgP2O7:xCe3+,yTb3+荧光粉.研究了荧光粉的晶体结构、发光特性、荧光寿命、能量传递机理和荧光粉的热稳定性.研究结果表明:在SrMgP2O7基质中,Ce3+的发射峰值为398nm,Tb3+的主发射峰值为545nm,它们分别属于5d-4f跃迁和5D4→7F5跃迁.Ce3+和Tb3+共掺时,Ce3+和Tb3+通过电偶极子-电偶极子相互作用发生能量传递,能量传递的临界距离为0.614nm.通过计算得到单掺杂Ce3+、Tb3+时热猝灭过程的激活能分别为0.122和0.111eV,Tb3+离子的发光热稳定性比Ce3+离子的好.     

A tunable single-component warm white-light Sr3Y(PO4)3:Eu2+,Mn2+ phosphor for white-light emitting diodes

The photoluminescence properties and energy transfer of the Eu(2+) and Mn(2+) co-doped Sr(3)Y(PO(4))(3) phosphors are investigated in detail. Two main emission bands attributed to the Eu(2+) and Mn(2+) ions are observed under UV light excitation via an efficient energy transfer process. When the Eu(2+) doping content is fixed, the emission chromaticity can be varied by simply adjusting the content of Mn(2+). The study of the behavior as a function of doping concentration indicates that the warm white-light can be obtained in a single host lattice. Furthermore, the analysis of the fluorescence decay curves based on the Inokuti-Hirayama theoretical model reveals that the dipole-quadrupole interaction is mainly responsible for the energy transfer mechanism from the Eu(2+) to Mn(2+) ions in the Sr(3)Y(PO(4))(3) phosphor. The developed phosphor exhibits a strong absorption in UV spectral region and white-light emission which may find utility as a single-component white-light-emitting UV-convertible phosphor in white LED devices.     

Luminescence investigation on ultraviolet-emitting rare-earth-doped phosphors using synchrotron radiation

Three series of new ultraviolet-emitting Ca(9)Y(PO(4))(7):Ln(3+) (Ln = Ce, Gd, Pr) phosphors were synthesized, and their luminescence was investigated. Under vacuum ultraviolet excitation Ca(9)Y(PO(4))(7):Ce(3+) phosphors emit UVA light with one broad emission centered at 346 nm, on account of the 5d(1) → 4f(1) transition of Ce(3+) ions; the optimal doping concentration of these phosphors is 0.2 mol. Ca(9)Y(PO(4))(7):Gd(3+) phosphors show a strong 4f(7) → 4f(7) transition and a sharp UVB emission band at 312 nm; the optimal doping concentration of these phosphors is 0.7 mol. The PL spectra of Ca(9)Y(PO(4))(7):Pr(3+) show two broad UVC emission bands centered between 230 and 340 nm, owing to the 4f(1)5d(1) → 4f(2) transition of Pr(3+) ions; the optimal doping concentration of these phosphors is 0.2 mol. Under 172 nm excitation, we found that the luminescence intensity of the UVA-emitting Ca(9)Y(PO(4))(7):0.2Ce(3+) is 0.3675 times that of BaSi(2)O(5):0.05Pb(2+), that of the UVB-emitting Ca(9)Y(PO(4))(7):0.7Gd(3+) is 1.7 times that of YAl(3)(BO(3))(4):0.25Gd(3+), and that of the UVC-emitting Ca(9)Y(PO(4))(7):0.2Pr(3+) is 1.5 times that of LaPO(4):0.1Pr(3+). The thermal stability investigation indicated that the luminescence decay was only 9.2%, 18.2%, and 10.3% for Ca(9)Y(PO(4))(7):0.2Ce(3+), Ca(9)Y(PO(4))(7):0.7Gd(3+), and Ca(9)Y(PO(4))(7):0.2Pr(3+) at 250 °C relative to that at ambient temperature, respectively. The Ca(9)Y(PO(4))(7):Ln(3+) (Ln = Ce, Gd, Pr) phosphors exhibit high emission efficiency and excellent thermal stability.     

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+.     

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.     

A Cl- anion-responsive luminescent Eu3+ complex with a chiral tripod: ligand substituent effects on ternary complex stoichiometry and anion sensing selectivity

A new series of N3,O-mixed donor tripods was prepared for luminescent Eu3+ complexes, in which the soft quinoline nitrogen, tertiary amine nitrogen, and hard amide oxygen donors were cooperatively involved. The mixed donor tripods formed more stable 1 : 1 complexes with Eu(NO3)3, La(NO3)3 and Tb(NO3)3 than the corresponding N4 donor tripods, and their Eu3+ complexes particularly exhibited anion-responsive luminescence properties. NMR, UV, and luminescence spectroscopic characterizations revealed that -CH3 substitution on the tripod skeleton remarkably altered the preferred stoichiometry of the "tripod-Eu3+-anion" ternary complex and gave anion-dependent europium luminescence. Although the disubstituted tripod preferred to form non-luminescent 2 : 1 (tripod : Eu3+) complexes with Eu(NO3)3 and other salts, it formed a luminescent 1 : 1 complex with EuCl3. Thus, this type of tripod offered Cl- anion-selective luminescence enhancement that was easily observed by the naked eye.