Yuanqiang Li

Ca 1 −− x Li x Al 1 − x Si 1+1+ x N 3 :Eu 2+ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

Color rendition, luminous efficacy and reliability are three key technical parameters for white light-emitting diodes (wLEDs) that are dominantly determined by down-conversion phosphors. However, there is usually an inevitable trade-off between color rendition and luminescence efficacy because the spectrum of red phosphor (that is, spectral broadness and position) cannot satisfy them simultaneously. In this work, we report a very promising red phosphor that can minimize the aforementioned trade-off via structure and band-gap engineering, achieved by introducing isostructural LiSi2N3 into CaAlSiN3:Eu2+. The solid solution phosphors show both substantial spectra broadening (88→117u2009nm) and blueshift (652→642u2009nm), along with a significant improvement in thermal quenching (only a 6% reduction at 150u2009°C), which are strongly associated with electronic and crystal structure evolutions. The broadband and robust red phosphor thus enables fabrication of super-high color rendering wLEDs (Ra=95 and R9=96) concurrently with the maintenance of a high-luminous efficacy (101u2009lmu2009W−1), validating its superiority in high-performance solid state lightings over currently used red phosphors.

Crystal and Electronic Structures, Photoluminescence Properties of Eu2+-Doped Novel Oxynitride Ba4Si6O16-3x/2Nx

The crystal structure and the photoluminescence properties of novel green Ba4-yEuySi6O16-3x/2Nx phosphors were investigated. The electronic structures of the Ba4Si6O16 host were calculated by first principles pseudopotential method based on density functional theory. The results reveal that the top of the valence bands are dominated by O-2p states hybridized with Ba-6s and Si-3p states, while the conduction bands are mainly determined by Ba-6s states for the host, which is an insulator with a direct energy gap of 4.6 eV at Γ. A small amount of nitrogen can be incorporated into the host to replace oxygen and forms Ba4-yEuySi6O16-3x/2Nx solid solutions crystallized in a monoclinic (space group P21/c, Z = 2) having the lattice parameters a = 12.4663(5) Å, b = 4.6829(2) Å, c = 13.9236(6) Å, and β = 93.61(1)°, with a maximum solubility of nitrogen at about x = 0.1. Ba4Si6O16-3x/2Nx:Eu2+ exhibits efficient green emission centered at 515–525 nm varying with the Eu2+ concentration when excited under UV to 400 nm. Furthermore, the incorporation of nitrogen can slightly enhance the photoluminescence intensity. Excitation in the UV-blue spectral range (λexc = 375 nm), the absorption and quantum efficiency of Ba4-yEuySi6O16-3x/2Nx (x = 0.1, y = 0.2) reach about 80% and 46%, respectively. Through further improvement of the thermal stability, novel green phosphor of Ba4-yEuySi6O16-3x/2Nx is promising for application in white UV-LEDs.

Structural evolutions and significantly reduced thermal degradation of red-emitting Sr2Si5N8:Eu2+via carbon doping

A red-emitting nitridosilicate phosphor, Sr2Si5N8:Eu2+, shows very promising photoluminescence properties but exhibits serious thermal degradation, thus making it difficult to be used practically as a color converter in white light-emitting diodes (wLEDs). To alleviate this problem, we introduce carbon into the Sr2Si5N8 lattice to form thermally robust carbidonitride phosphors (Sr2Si5CxN8−4x/3:Eu2+). The carbon doping, evidenced by a variety of analytical techniques, leads to structural evolutions including lattice shrinkage, shortening of the average bond length of Eu–(C,N), and the removal of Eu3+ ions from the lattice. The photoluminescence intensity and quantum efficiency of phosphors are greatly improved by the carbon doping and reach the maximum at x = 0.5, dominantly owing to the enhanced absorption of Eu2+. Thanks to the increased oxidation resistance of Eu2+ due to the stronger covalency of Si–(C,N) and Sr(Eu)–(C,N) bonds, thermal degradation is significantly reduced from 16 to 0.8% when the carbon doping increases from x = 0 to 1.25. In addition, thermal quenching is also reduced by 10% at 300 °C and the quantum efficiency declines slowly with increasing temperature when carbon is substituted for nitrogen. At 300 °C, the internal quantum efficiencies are 55% and 62% for x = 0 and 0.5, respectively. The enhanced thermal stability of the carbon-doped sample is also confirmed by smaller variations in the luminous efficacy and color coordinates of monochromatic red LEDs.