A novel strong green phosphor： K3Gd（PO4）2：Ce^3＋, Tb^3＋ for a UV-excited white light-emitting-diode

A series of K3Gd1-x-y（PO4）2：xCe^3＋, yTb^3＋ phosphors are synthesized by the solid-sate reaction method. X-ray diffraction and photoluminescence spectra are utilized to characterize the structures and luminescence properties of the as-synthesized phosphors. Co-doping of Ce^3＋ enhances the emission intensity of Tb^3＋ greatly through an efficient energy transfer process from Ce^3＋ to Tb^3＋. The energy transfer is confirmed by photoluminescence spectra and decay time curves analysis. The efficiency and mechanism of energy transfer are investigated carefully. Moreover, due to the non- concentration quenching property of K3Tb（PO4）2, the photoluminescence spectra of K3Tb1-x（PO4）2：xCe^3＋ are studied and the results show that when x = 0.11 the strongest Tb^3＋ green emission can be realized.     

Preparation and Luminescence Characteristics of Ca3Y2（BO3）4：Eu^3＋ Phosphor

Ca3Y2 （BO3）4：Eu^3＋ phosphor is synthesized by high temperature solid-state reaction method, and the Iuminescence characteristics are investigated. The emission spectrum exhibits two strong red emissions at 613 and 621 nm corresponding to the electric dipole ^5 Do- ^7F2 transition of Eu^3＋ under 365 nm excitation, the reason is that Eu^3＋ substituting for Y^3＋ occupies the non-centrosymmetric position in the crystal structure of Ca3 Y2 （BO3）4. The excitation spectrum for 613 nm indicates that the phosphor can be effectively excited by ultraviolet （UV） （254 nm, 365nm and 400nm） and blue （470nm） light. The effect of Eu^3＋ concentration on the emission intensity of Ca3 Y2 （BO3）4 ：Eu^3＋ phosphor is measured, the result shows that the emission intensities increase with increasing Eu^3＋ concentration, then decrease. The CIE colour coordinates of Ca3Y2 （BO3）4：Eu^3＋ phosphor is （0.639, 0.357） at 15mol% Eu^3＋.     

Luminescent Characteristics of LiSrBO3：Eu3＋ Phosphor for White Light Emitting Diode

LiSrBO3 ：Eu3＋ phosphor is synthesized by a high solid-state reaction method, and its luminescent characteristics are investigated. The emission and excitation spectra of LiSrBO3：Eu3＋ phosphors exhibit that the phosphors can be effectively excited by near ultraviolet （401 nm） and blue （471 nm） light, and emit 615nm red light. The effect of Eua＋ concentration on the emission spectrum of LiSrBO3：Eu3＋ phosphor is studied; the results show that the emission intensity increases with increasing Eu3＋ concentration, and then decreases because of concentration quenching. It reaches the maximum at 3mol%, and the concentration self-quenching mechanism is the dipoledipole interaction according to the Dexter theory. Under the conditions of charge compensation Li＋, Na＋ or K＋ incorporated in LiSrBO3, the luminescent intensities of LiSrBO3 ：Eua＋ phosphor are enhanced.     

Sr3Bi（PO4）3：Eu^2＋ Luminescence,Concentration Quenching and Crystallographic Sites

A blue emitting phosphor Sr3Bi（PO4）3：Eu2＋ is synthesized luminescent property is investigated. Sr3Bi（PO4 ）3 ：Eu^2＋ can by a high-temperature solid state method, and its create blue emission under the 332 radiation excitation, and the prominent luminescence in blue （423nm） due to the 4fSd^1→4f^7 transition of the Eu^2＋ ion. The crystallographic sites of the Eu^2＋ ion in Sr3Bi（PO4）3 are analyzed, and the 420 and 440 nm emission peaks of the Eu^2＋ ion are assigned to the nine-coordination and eight-coordination, respectively. The emission intensity of Sr3Bi（PO4）3：Eu^2＋ is influenced by the Eu^2＋ doping content, and the concentration quenching effect is observed. The quenching mechanism is the dipole-dipole interaction, and the critical distance of energy transfer is calculated by the concentration quenching method to be approximately 1.72nm.     

Photoluminescence characteristics and energy transfer between Bi~（3＋） and Eu~（3＋） in Na_2O–CaO–GeO_2–SiO_2 glass

We report the photoluminescence（PL） of Eu^3＋-doped glass with Bi^3＋as a sensitizer. The specific glass system with the strong enhancement of the red emission of Eu3＋is obtained by adding a small number of Bi3＋ions instead of increasing the Eu^3＋ concentration. The emission band of Bi3＋overlaps with the excitation band of Eu^3＋ and the lifetime decay curves,resulting in a very efficient energy transfer from Bi^3＋ to Eu^3＋. The probability of energy transfer is strongly dependent on Bi^3＋ concentration. In addition, the intensity of 4f–4f transition is much stronger than that of a charge-transfer（CT） band in the excitation spectrum, which indicates that the Na2O–Ca O–Ge O2-Si O2 glass is a suitable red-emitting phosphor with high stability as a candidate for light-emitting diodes（LEDs）.     

Hydrothermal Synthesis and Vacuum Ultraviolet-Excited Luminescence Properties of Novel Dy^3＋-doped GdPO4 White Light Phosphors

Novel Dy^3＋-doped GdPO4 white light phosphors with a monoclinic system are successfully synthesized by the hydrothermal method at 240℃. The strong absorption at around 147nm in the excitation spectrum is assigned to the host absorption. It is suggested that the vacuum ultraviolet excited energy is transferred from the host to the Dy^3＋ ions. The f - d transition of the Dy^3＋ ion is observed to be located at 182nm, which is consistent with the calculated value using Dorenbos＇s expression. Under 147nm excitation, Gd0.92PO4：0.08Dy^3＋ phosphor exhibits two emission bands located at 572 nm （yellow） and 478 nm （blue）, which correspond to the hypersensitive transitions ^4 F9/2-^6 H13/2 and ^4 F9/2-^6 H15/2. The two emission bands lead to the white light. Because of the strong absorption at about 147nm, Gd0.92PO4：0.08Dy^3＋ under vacuum ultraviolet excitation is an effective white light phosphor, and has promising applications to mercury-free lamps.     

Luminescence Spectra of YGG：RE^3＋, Bi^3＋ （RE = Eu and Tb） and Energy Transfer from Bi^3＋ to RE^3＋

We investigate the luminescence properties of Bi^3＋ and RE^3＋ （RE = Tb or Eu） in a Y3Ga5O12 （YGG） host system. The additional doping of Bi^3＋ can enhance the luminescence of Th^3＋ or Eu^3＋ in this host. Energy transfer from Bi^3＋ to Tb^3＋ and Eu^3＋ is observed and the mechanism of energy transfer is investigated. Mechanism of energy transfer can be explained as electric multipole interaction since the Bi^3＋ emission band and Tb^3＋ or Eu^3＋ excitation band overlaps and the Bi^3＋ emission intensity decreases while the intensity of Tb^3＋ or Eu^3＋ increases with the increase of Tb^3＋ or Eu^3＋ concentration. Therefore, Bi^3＋ ion is a kind of efficient sensitizer to the Tb^3＋ and Eu^3＋ activators in the Y3Ga5O12 host.     

Preparation and characterization of nanosized GdxBi0.95-xVO4：0.05Eu3＋ solid solution as red phosphor

A complete solid solutions with monophasic zircon-type structure of vanadates of formula GdxBio.95-xVO4：0.05Eu3＋ （x = 04）.95） are synthesized by combined method of co-precipitation and hydrothermal synthesis. Their microstructures and morphologies are characterized by X-ray powder diffraction and transmission electronic microscope, and the results show that each of all the samples has a monophasic zircon-type structure. The absorption spectrum of the prepared phosphor shows a blue-shift of the fundamental absorption band edge with increasing the gadolinium content. Under UV-light and visible-light excitation, all the prepared phosphors show the typical luminescence properties of Eu3＋ in the zircon-type structure. The emission intensity of GdxBi0.95-xVO4：0.05Eu3＋ （x = 0.55） is strongest in all samples under UV-light and visible-light excitations. Finally, the mechanisms of luminescence of Eu3＋ in the GdxBi0.95-xVO4：0.05Eu3＋ （x = 0-0.95） solid solutions are analyzed and discussed.     

Abnormal Visible Luminescence Mechanism of Tb^3＋-Yb^3＋ Codoped SiOu-Al2O3-CaF2 Glass Studied by Time-Resolved Spectra

The upconversion energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass is investigated by time-resolved spectra. The effect of donor ion Yb^3＋ is involved in the dynamic decay behavior of acceptor ion Tb^3＋, which provides direct proof for the energy transfer from Yb^3＋ to Tb^3＋. The pump power dependence curves show that the upconversion luminescence is a two-photon process. The measured decay curves of the 5D4 state （Tb^3＋） contain two parts： a slow decay process corresponding to its radiation, and a fast one with a decay parameter approximately twice the lifetime of the ^2F5/2 state （Yb^3＋ ）. The fast decay process is contradictory to the generally accepted cooperative sensitization upconversion rate equation model. Since the effect of the host environmental is excluded by comparative experiments, we believe that there should be another energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass in addition to the cooperative sensitization process.     

Luminescence Properties of Ca4GdO（BO3）3：RE （RE=Eu^3＋,Tb^3＋） under VUV Excitation

We experimentally investigated the VUV excitation luminescence properties of Ca4 GdO(B03)3 :RE (RE=Eu^3 , Tb^3 )Ca4GdO(BO3)3:Eu3 and Ca4GdO(BO3)3:Tb^3 emitted bright red and green colour light, respectively, under 172 nm excitation, resulting from the favorable position of the host absorption band (186 nm) and efficient energy transfer from Gd^3 to activators (e.g. Eu^3 or Tb^3 ) by means of secondary absorption in the Ca4GdO(BO3)3 matrix. The f-d transitions of Eu^3 and Tb^3 in the host lattice are depicted.     

VUV/UV/X-Ray Excited Luminescent Properties of Eu^3＋ and Pr^3＋ Doped BiSbO4

Absorption spectra of BiSbO4 are studied. The electronic structure calculated by the DFT shows that BiSbO4 is a semiconductor, with direct band gap 2.96 eV, which is consistent with UV-visible diffuse reflectance experiment. The host lattice emission band is located at 440 nm under VUV excitation. Eu^3＋ and Pr^3＋ doped samples have high luminescence efficiency in emitting red and green light, respectively. From the partial density of states, Eu^3＋ doped emitting spectrum, and the host crystal structure parameters, the relationship between structure and optical properties is discussed. It is found that the Eu^3＋ ions occupied Bi^3＋ sites, and there could be an energy transfer from Bi^3＋ ions to RE^3＋ ions.     

Concentration and Temperature Dependences of YBO3：Bi^3＋ Luminescence under Vacuum Ultraviolet Excitation

Bi^3＋ doped YB03 phosphors are prepared by solid state reaction and their luminescent properties are investi- gated by using synchrotron radiation instrument, Concentration and temperature dependences of YBO3：Bi3＋ luminescence under VUV/UV excitation is observed, The emission and excitation spectra are assigned, and the mechanism for these phenomena is explored, which result from the energy transfer between Bi^3＋ ions occupying different sites in YB03 crystal lattice.     

Cooperative Quantum Cutting of Nano-Crystalline BaF2：Tb^3＋, Yb^3＋ in Oxyfluoride Glass Ceramics

We report on cooperative quantum cutting in Tb^3＋- Yb^3＋ codoped glass ceramics. Precipitation of BaF2 nanocrystals is confirmed by XRD and HRTEM analysis. Near-infrared emission due to transition of Yb^3＋ ions under 485 nm excitation indicates cooperative energy transfer from Tb^3＋ to Yb^3＋. The quantum efficiency of this process reaches 145%. The realization of quantum cutting in glass ceramics may have promising applications in solar cells.     

Double emitting phosphor NaSr4(BO3)3:Ce, Tb for near-UV light-emitting diodes

Blue and green double emitting phosphor, Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃, was synthesized in a weak reducing atmosphere by a conventional high temperature solid-state reaction technique. For comparison, Ce³⁺ or Tb³⁺ singly doped NaSr₄(BO₃)₃ was also prepared. The emission and excitation spectra of all samples have been investigated. NaSr₄(BO₃)₃:Tb³⁺ excitation includes a strong absorption at about 240 nm and some weak sharp lines in near-ultraviolet (n-UV) spectral region. The excitation of Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃ shows a strong broad band absorption in the n-UV region from the contribution of Ce³⁺, which makes it suitable for excitation by a n-UV LED chip. The emission of NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ consists of a blue emission band from Ce³⁺ and a green emission from Tb³⁺ under the excitation of n-UV light. Energy transfer between Ce³⁺ and Tb³⁺ is also discussed, and the relative intensity of blue emission and green emission could be tuned by adjusting the concentration of Ce³⁺ and Tb³⁺. The phosphor NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ could be considered as a double emission phosphor for n-UV excited white light-emitting diodes.     

高温高压合成CeTbO3+δ的XPS研究

 经过高温高压合成的CeTbO_3+δ进行了XPS研究，发现在1.0 GPa下，Tb⁴⁺在~600 ℃开始转变成Tb³⁺，而Ce⁴⁺在~800 ℃开始向Ce³⁺转变。在1 000~1 200 ℃形成单相萤石结构化合物CeTbO_3+δ的Ce是以Ce³⁺、Ce⁴⁺混合价形式存在，Tb全部变成Tb³⁺。实验表明，用Ce_3d谱上~888 eV峰的峰位及其与882 eV峰的相对强度变化可以定性判断化合物中是否含有Ce³⁺。研究了高温高压合成的CeTbO_3+δ的稳定性随时间的变化问题。     

Spectral Hole-Burning of Eu^3＋：Y2SiO5 Crystal at 16 K

By using an Ar^＋ ion laser, a tunable Rh 6G dye laser （linewidth 0.5cm^-1） pumped by the second harmonic of a YAG：Nd laser and a Coherent 899-21 dye laser as light sources and using a monochromator, a phase-locking amplifier and a computer as the data detecting system, we detect the optical properties of Eu^3＋-doped Y2SiO5 crystal. Persistent ,spectral hole burning （PSHB） are observed in the Eu^3＋ ions spectral lines （^5 Do-T Fo transition） in the crystal at the temperature of 16K. For 15mW dye laser burning the crystal for 0.1 s spectral holes with hole width about 80 MHz both at 579.62nm and at 579.82nm are detected and the holes can remain for a long time, more than 10h.     

Electroluminescence from Multilayered Diamond/CeF3/SiO2 Films

We report a thin film electroluminescent device with a three-layer structure （diamond/CeF3/SiO2 films）, which has a luminance of 1.5 cd/m^2 at dc voltage 215 V. The electroluminescence spectrum at room temperature shows that the main peaks locate at 527 and 593nm, which are attributed to isolated emission centers of Ce^3＋ ions.