Controlling the energy transfer via multi luminescent centers to achieve white light/tunable emissions in a single-phased X2-type Y2SiO5:Eu(3+),Bi(3+) phosphor for ultraviolet converted LEDs.

So far, more than 1000 UV converted phosphors have been reported for potential application in white light-emitting diodes (WLEDs), but most of them (e.g., Y2O2S:Eu, YAG:Ce or CaAlSiN3:Eu) suffer from intrinsic problems such as thermal instability, color aging or re-absorption by commixed phosphors in the coating of the devices. In this case, it becomes significant to search a single-phased phosphor, which can efficiently convert UV light to white lights. Herein, we report a promising candidate of a white light emitting X2-type Y2SiO5:Eu(3+),Bi(3+) phosphor, which can be excitable by UV light and address the problems mentioned above. Single Bi(3+)-doped X2-type Y2SiO5 exhibits three discernible emission peaks at ∼355, ∼408, and ∼504 nm, respectively, upon UV excitation due to three types of bismuth emission centers, and their relative intensity depends tightly on the incident excitation wavelength. In this regard, proper selection of excitation wavelength can lead to tunable emissions of Y2SiO5:Bi(3+) between blue and green, which is partially due to the energy transfer among the Bi centers. As a red emission center Eu(3+) is codoped into Y2SiO5:Bi(3+), energy transfer has been confirmed happening from Bi(3+) to Eu(3+) via an electric dipole-dipole (d-d) interaction. Our experiments reveal that it is easily realizable to create the white or tunable emissions by adjusting the Eu(3+) content and the excitation schemes. Moreover, a single-phased white light emission phosphor, X2-type Y1.998SiO5:0.01Eu(3+),0.01 Bi(3+), has been achieved with excellent resistance against thermal quenching and a QE of 78%. At 200 °C, it preserves >90% emission intensity of that at 25 °C. Consequent three time yoyo experiments of heating-cooling prove no occurrence of thermal degradation. A WLED lamp has been successfully fabricated with a CIE chromaticity coordinate (0.3702, 0.2933), color temperature 4756 K, and color rendering index of 65 by applying the phosphor onto a UV LED chip.

[1]  M. Peng,et al.  Processing-dependence and the nature of the blue-shift of Bi3+-related photoemission in ScVO4at elevated temperatures , 2014 .

[2]  M. Peng,et al.  Abnormal anti-quenching and controllable multi-transitions of Bi3+ luminescence by temperature in a yellow-emitting LuVO4 :Bi3+ phosphor for UV-converted white LEDs. , 2014, Chemistry.

[3]  Angela S. Wochnik,et al.  Narrow-band red-emitting Sr[LiAl₃N₄]:Eu²⁺ as a next-generation LED-phosphor material. , 2014, Nature materials.

[4]  Zhipeng Ci,et al.  Structure, photoluminescence and thermal properties of Ce3+, Mn2+ co-doped phosphosilicate Sr7La3[(PO4)2.5(SiO4)3(BO4)0.5](BO2) emission-tunable phosphor , 2014 .

[5]  M. Yin,et al.  Spectroscopic distinctions between two types of Ce(3+) ions in X2-Y2SiO5: a theoretical investigation. , 2014, The journal of physical chemistry. A.

[6]  Quansheng Wu,et al.  Preparation of Sr1−xCaxYSi4N7:Eu2+ solid solutions and their luminescence properties , 2014 .

[7]  Q. Pang,et al.  Tunable Luminescence and Ce3+ → Tb3+ → Eu3+ Energy Transfer of Broadband-Excited and Narrow Line Red Emitting Y2SiO5:Ce3+, Tb3+, Eu3+ Phosphor , 2014 .

[8]  Xiaobao Yang,et al.  Red Photoluminescence from Bi3+ and the Influence of the Oxygen-Vacancy Perturbation in ScVO4: A Combined Experimental and Theoretical Study , 2014 .

[9]  Zhijun Ma,et al.  Broadly Tunable Emission from CaMoO4:Bi Phosphor Based on Locally Modifying the Microenvironment Around Bi3+ Ions , 2014 .

[10]  Jun Lin,et al.  How to produce white light in a single-phase host? , 2014, Chemical Society reviews.

[11]  Yongchao Jia,et al.  Crystal Structure and Luminescence Properties of Ca8Mg3Al2Si7O28:Eu2+ for WLEDs , 2014 .

[12]  M. Peng,et al.  A new study on the energy transfer in the color-tunable phosphor CaWO4:Bi. , 2014, Dalton transactions.

[13]  Haifeng Zhao,et al.  New yellow-emitting nitride phosphor SrAlSi4N7:Ce3+ and important role of excessive AlN in material synthesis. , 2013, ACS applied materials & interfaces.

[14]  Xuewen Yin,et al.  Temperature dependent red luminescence from a distorted Mn4+ site in CaAl4O7:Mn4+. , 2013, Optics express.

[15]  B. Jia,et al.  Exceeding the limit of plasmonic light trapping in textured screen-printed solar cells using Al nanoparticles and wrinkle-like graphene sheets , 2013, Light: Science & Applications.

[16]  Jun Lin,et al.  Tunable and White‐Light Emission from Single‐Phase Ca2YF4PO4:Eu2+,Mn2+ Phosphors for Application in W‐LEDs , 2013 .

[17]  Yongchao Jia,et al.  Tunable color of Ce3+/Tb3+/Mn(2+)-coactivated CaScAlSiO6 via energy transfer: a single-component red/white-emitting phosphor. , 2013, Inorganic chemistry.

[18]  J. Ueda,et al.  Photochromism and white long-lasting persistent luminescence in Bi 3+ -doped ZnGa 2 O 4 ceramics , 2012 .

[19]  Yichun Liu,et al.  Single-phased white-emitting 12CaO·7Al2O3:Ce3+, Dy3+ phosphors with suitable electrical conductivity for field emission displays , 2012 .

[20]  Ru‐Shi Liu,et al.  Tunable Blue-Green Color Emission and Energy Transfer of Ca2Al3O6F:Ce3+,Tb3+ Phosphors for Near-UV White LEDs , 2012 .

[21]  Jane P. Chang,et al.  High-Quality White Light Using Core–Shell RE3+:LaPO4 (RE = Eu, Tb, Dy, Ce) Phosphors , 2012 .

[22]  Jun Lin,et al.  Blue Emitting Ca8La2(PO4)6O2:Ce3+/Eu2+ Phosphors with High Color Purity and Brightness for White LED: Soft-Chemical Synthesis, Luminescence, and Energy Transfer Properties , 2012 .

[23]  Jun Lin,et al.  Patterning of red, green, and blue luminescent films based on CaWO4:Eu3+, CaWO4:Tb3+, and CaWO4 phosphors via microcontact printing route. , 2011, ACS applied materials & interfaces.

[24]  Xiaojun Wang,et al.  Tunable full-color-emitting Ca3Sc2Si3O12:Ce3+, Mn2+ phosphor via charge compensation and energy transfer. , 2011, Chemical communications.

[25]  Xiaojun Wang,et al.  Tunable full-color emitting BaMg2Al6Si9O30:Eu2+, Tb3+, Mn2+ phosphors based on energy transfer. , 2011, Inorganic chemistry.

[26]  Jyhfu Lee,et al.  (Ca,Mg,Sr)9Y(PO4)7:Eu2+,Mn2+: Phosphors for white-light near-UV LEDs through crystal field tuning and energy transfer , 2011 .

[27]  Bright White Up-Conversion Emission from Ho3+/Yb3+/Tm3+ Tri-Doped Y2SiO5 Phosphors , 2011 .

[28]  Jun Lin,et al.  Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors. , 2011, ACS applied materials & interfaces.

[29]  Liang Shi,et al.  Tunable white-light emission in single-phased K2Y(1-x)Eu(x)Zr(PO4)3 phosphor. , 2011, Optics express.

[30]  K. Okuyama,et al.  Novel rare-earth-free tunable-color-emitting BCNO phosphors , 2011 .

[31]  M. Peng,et al.  Photoluminescence of Sr(2)P(2)O(7):Bi(2+) as a red phosphor for additive light generation. , 2010, Optics letters.

[32]  R. Xie,et al.  Rare-Earth Activated Nitride Phosphors: Synthesis, Luminescence and Applications , 2010, Materials.

[33]  M. Peng,et al.  Orange‐to‐Red Emission from Bi2+and Alkaline Earth Codoped Strontium Borate Phosphors for White Light Emitting Diodes , 2010 .

[34]  M. Peng,et al.  Bi2+-doped strontium borates for white-light-emitting diodes. , 2009, Optics letters.

[35]  W. Schnick,et al.  Sr(5)Al(5+x)Si(21-x)N(35-x)O(2+x):Eu2+ (x approximately 0)--a novel green phosphor for white-light pcLEDs with disordered intergrowth structure. , 2009, Chemistry.

[36]  Liping Li,et al.  Generation of tunable wavelength lights in core-shell CaWO4 microspheres via co-doping with Na+ and Ln3+ (Ln = Tb, Sm, Dy, Eu) , 2009 .

[37]  Liping Li,et al.  Synthesis and Optimum Luminescence of CaWO4-Based Red Phosphors with Codoping of Eu3+ and Na+ , 2008 .

[38]  Ping Huang,et al.  Bright upconversion white light emission in transparent glass ceramic embedding Tm3+/Er3+/Yb3+ : β-YF3 nanocrystals , 2007 .

[39]  Xiaojun Wang,et al.  Enhanced Red Emission in CaMoO4:Bi3+,Eu3+ , 2007 .

[40]  R. Xie,et al.  A Simple, Efficient Synthetic Route to Sr2Si5N8:Eu2+-Based Red Phosphors for White Light-Emitting Diodes , 2006 .

[41]  P. Jia,et al.  Sol–gel synthesis and characterization of SiO2@CaWO4,SiO2@CaWO4:Eu3+/Tb3+ core–shell structured spherical particles , 2006 .

[42]  Htjm Bert Hintzen,et al.  Luminescence properties of Eu2+ - activated alkaline-earth silicon-oxynitride MSi2O2-deltaN2+2/3delta (M = Ca, Sr, Ba) : A promising class of novel LED conversion phosphors , 2005 .

[43]  K. Kimoto,et al.  Characterization and properties of green-emitting β-SiAlON:Eu2+ powder phosphors for white light-emitting diodes , 2005 .

[44]  W. Zhuang,et al.  A novel red phosphor for white light emitting diodes , 2005 .

[45]  Jun Lin,et al.  Silica Spheres Coated with YVO4:Eu3+ Layers via Sol−Gel Process: A Simple Method To Obtain Spherical Core−Shell Phosphors , 2005 .

[46]  A. Patra,et al.  Luminescence of Ce3+ in Y2SiO5 nanocrystals: Role of crystal structure and crystal size. , 2005, The journal of physical chemistry. B.

[47]  Tae Whan Kim,et al.  White-light generation through ultraviolet-emitting diode and white-emitting phosphor , 2004 .

[48]  R. Xie,et al.  Eu2+-doped Ca-α-SiAlON: A yellow phosphor for white light-emitting diodes , 2004 .

[49]  J. Silver,et al.  Cathodoluminescence studies of yttrium silicate:cerium phosphors synthesised by a sol–gel process , 2002 .

[50]  K. Nonaka,et al.  Strong blue, green and red light emission at elevated temperatures from Y2SiO5 doped by the rare-earth ions , 2001 .

[51]  D. Jeon,et al.  Emission Band Shift of the Cathodoluminescence of Y2SiO5:Ce Phosphor Affected by Its Activator Concentration , 2001 .

[52]  C. Duan,et al.  Site selectively excited luminescence and energy transfer of X1-Y2SiO5:Eu at nanometric scale , 1999 .

[53]  K. Okuyama,et al.  Luminescence characteristics of Y2SiO5 : Tb phosphor particles directly prepared by the spray pyrolysis method , 1999 .

[54]  S. Nakamura Blue-Green Light-Emitting Diodes and Violet Laser Diodes , 1997 .

[55]  Q. Su,et al.  Influence of crystal structure on the luminescence properties of bismuth(III), europium(III) and dysprosium(III) in Y2SiO5 , 1996 .

[56]  Bruce H. T. Chai,et al.  Laser performance of Cr4+:Y2SiO5 , 1992 .