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Synthesis, composition optimization, and tunable red emission of CaAlSiN3:Eu2+ phosphors for white light-emitting diodes

  • Shu-Xing Li (a1), Xue-Jian Liu (a2), Jia-Qing Liu (a3), Huili Li (a3), Ri-Hua Mao (a4), Zheng-Ren Huang (a5) and Rong-Jun Xie (a6)...


Ca0.98Eu0.02Al1−4δ/3Si1+δN3 (δ = 0–0.36) red-emitting phosphors were prepared by carbothermal reduction and nitridation method with stable and inexpensive CaCO3 as Ca source. Optimal nominal composition was obtained at δ = 0.18, showing intense emission peaked at 625 nm and high external quantum efficiency of 71%. The emission wave length could be successfully tuned from 630 to 606 nm with increasing δ value. Ca0.98Eu0.02Al1−4δ/3Si1+δN3 phosphors provided two coordinated environments for Eu2+ ions, resulting in two fitted Gaussian peaks. Energy transfer from Eu2+ sites in Si-rich environments to those in Si/Al-equivalent modes has been confirmed by analysis of the decay curve of each peak. The decay behaviors suggested that energy transfer effect slowed with higher δ value. Finally, warm white light was created by combining as-prepared red-emitting Ca0.98Eu0.02Al0.76Si1.18N3 and yellow-emitting YAG:Ce3+ phosphors with a blue-emitting chip, exhibiting a color rendering index R a of 91 at a low correlated color temperature of 3500 K with a luminous efficiency of 79 lm/W.


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1. Schubert, E-F. and Kim, J-K.: Solid-state light sources getting smart. Science 308, 1274 (2005).
2. Hashimoto, T., Wu, F., Speck, J-S., and Nakamura, S.: A GaN bulk crystal with improved structural quality grown by the ammonothermal method. Nat. Mater. 6, 568 (2007).
3. Pimputkar, S., Speck, J-S., DenBaars, S-P., Nakamura, S., and Nakamura, S.: Prospects for LED lighting. Nat. Photonics 3, 180 (2009).
4. Xie, R-J. and Hirosaki, N.: Silicon-based oxynitride and nitride phosphors for white LEDs—A review. Sci. Technol. Adv. Mater. 8, 588 (2007).
5. Xie, R-J., Hirosaki, N., Li, Y-Q., and Takeda, T.: Rare-earth activated nitride phosphors: Synthesis, luminescence and applications. Materials 3, 3777 (2010).
6. Xie, R-J. and Hintzen, H-T.: Optical properties of (oxy)nitride materials: A review. J. Am. Ceram. Soc. 93, 665 (2013).
7. Xie, R-J., Hirosaki, N., Kimura, N., Sakuma, K., and Mitomo, M.: 2-phosphor-converted white light-emitting diodes using oxynitride/nitride phosphors. Appl. Phys. Lett. 90, 191101 (2007).
8. Piao, X-Q., Horikawa, T., Hanzawa, H., and Machida, K.: Characterization and luminescence properties of Sr2Si5N8:Eu2+ phosphor for white light-emitting-diode illumination. Appl. Phys. Lett. 88, 161908 (2006).
9. Piao, X-Q., Machida, K., Horikawa, T., and Hanzawa, H.: Self-propagating high temperature synthesis of yellow-emitting Ba2Si5N8:Eu2+ phosphors for white light-emitting diodes. Appl. Phys. Lett. 91, 041908 (2007).
10. Sohn, K-S., Lee, S-J., Xie, R-J., and Hirosaki, N.: Time-resolved photoluminescence analysis of two-peak emission behavior in Sr2Si5N8:Eu2+ . Appl. Phys. Lett. 95, 121903 (2009).
11. Brinkley, S-E., Pfaff, N., Denault, K-A., Zhang, Z-J., Hintzen, H-T., Seshadri, R., Nakamura, S., and DenBaars, S-P.: Robust thermal performance of Sr2Si5N8:Eu2+: An efficient red emitting phosphor for light emitting diode based white lighting. Appl. Phys. Lett. 99, 241106 (2011).
12. Yeh, C-W., Chen, W-T., Liu, R-S., Hu, S-F., Sheu, H-S., Chen, J-M., and Hintzen, H-T.: Origin of thermal degradation of Sr2-x Si5N8:Eu x phosphors in air for light-emitting diodes. J. Am. Chem. Soc. 134, 14108 (2012).
13. ten Kate, O-M., Zhang, Z., Dorenbos, P., Hintzen, H-T., and van der Kolk, E.: 4f and 5d energy levels of the divalent and trivalent lanthanide ions in M 2Si5N8 (M = Ca, Sr, Ba). J. Solid State Chem. 197, 209 (2013).
14. Wang, T., Zheng, P., Liu, X-L., Chen, H-F., Bian, L., and Liu, Q-L.: Effects of replacement of AlO+ for SiN+ on the structure and optical properties of Sr2Si5N8:Eu2+ phosphors. J. Lumin. 147, 173 (2014).
15. Uheda, K., Hirosaki, N., and Yamamoto, H.: Host lattice materials in the system Ca3N2-AlN-Si3N4 for white light emitting diode. Phys. Status Solidi A 203, 2712 (2006).
16. Li, J-W., Watanabe, T., Wada, H., Setoyama, T., and Yoshimura, M.: Low-temperature crystallization of Eu-doped red-emitting CaAlSiN3 from alloy-derived ammonometallates. Chem. Mater. 19, 3592 (2007).
17. Piao, X-Q., Machida, K., Horikawa, T., Hanzawa, H., Shimomura, Y., and Kijima, N.: Preparation of CaAlSiN3:Eu2+ phosphors by the self-propagating high-temperature synthesis and their luminescent properties. Chem. Mater. 19, 4592 (2007).
18. Li, Y-Q., Hirosaki, N., Xie, R-J., Takeda, T., and Mitomo, M.: Yellow-orange-emitting CaAlSiN3:Ce3+ phosphor: Structure, photoluminescence, and application in white LEDs. Chem. Mater. 20, 6704 (2008).
19. Watanabe, H., Imai, M., and Kijimaz, N.: Nitridation of AEAlSi for production of AEAlSiN3:Eu2+ nitride phosphors (AE = Ca, Sr). J. Am. Ceram. Soc. 92, 641 (2009).
20. Zhang, Z-J., ten Kate, O-M., Delsing, A., van der Kolk, E., Notten, P-H-L., Dorenbos, P., Zhao, J-T., and Hintzen, H-T.: Photoluminescence properties and energy level locations of RE3+ (RE = Pr, Sm, Tb, Tb/Ce) in CaAlSiN3 phosphors. J. Mater. Chem. 22, 9813 (2012).
21. Suehiro, T., Xie, R-J., and Hirosaki, N.: Gas-reduction-nitridation synthesis of CaAlSiN3:Eu2+ fine powder phosphors for solid-state lighting. Ind. Eng. Chem. Res. 53, 2713 (2014).
22. Pust, P., Weiler, V., Hecht, C., Tücks, A., Wochnik, A.S., Henß, A-K., Wiechert, D., Scheu, C., Schmidt, P-J., and Schnick, W.: Narrow-band red-emitting Sr[LiAl3N4]:Eu2+ next-generation LED-phosphor material. Nat. Mater. 13, 891 (2014).
23. Watanabe, H. and Kijima, N.: Crystal structure and luminescence properties of Sr x Ca1-x AlSiN3:Eu2+ mixed nitride phosphors. J. Alloys Compd. 475, 434 (2009).
24. Wang, T., Yang, J-J., Mo, Y., Bian, L., Song, Z., and Liu, Q-L.: Synthesis, structure and tunable red emissions of Ca(Al/Si)2N2(N1-x O x ):Eu2+ prepared by alloy-nitridation method. J. Lumin. 137, 173 (2013).
25. Li, S-X., Peng, X., Liu, X-J., and Huang, Z-R.: Photoluminescence of CaAlSiN3:Eu2+-based fine red-emitting phosphors synthesized by carbothermal reduction and nitridation method. Opt. Mater. 38, 242 (2014).
26. Uheda, K., Yamamoto, H., Yamane, H., Inami, W., Tsuda, K., Yamamoto, Y., and Hirosaki, N.: An analysis of crystal structure of Ca-deficient oxonitridoaluminosilicate, Ca0.88Al0.91Si1.09N2.85O0.15 . J. Ceram. Soc. Jpn. 117, 94 (2009).
27. Mikami, M., Watanabe, H., Uheda, K., and Kijima, N.: Nitridoaluminosilicate CaAlSiN3 and its derivatives - Theory and experiment. Mater. Res. Soc. Symp. Proc. 1040, Q10-09 (2008).
28. Shen, Y., Zhuang, W-D., Liu, Y-H., He, H-Q., and He, T.: Preparation and luminescence properties of Eu2+-doped CASN-sinoite multiphase system for LED. J. Rare Earths 28, 289 (2010).
29. Wang, S-S., Chen, W-T., Li, Y., Wang, J., Sheu, H-S., and Liu, R-S.: Neighboring-cation substitution tuning of photoluminescence by remote-controlled activator in phosphor lattice. J. Am. Chem. Soc. 135, 12504 (2013).
30. Jung, Y-W., Lee, B., Singh, S-P., and Sohn, K-S.: Particle-swarm-optimization-assisted rate equation modeling of the two-peak emission behavior of non-stoichiometric CaAl x Si(7-3x)/4N3:Eu2+ phosphors. Opt. Express 18, 17805 (2010).
31. Kulshreshtha, C., Kwak, J-H., Park, Y-J., and Sohn, K-S.: Photoluminescent and decay behaviors of Mn2+ and Ce3+ coactivated MgSiN2 phosphors for use in light-emitting-diode applications. Opt. Lett. 34(6), 794 (2009).
32. Wang, T., Zheng, P., Liu, X-L., Chen, H-F., Yang, S-S., and Liu, Q.L.: Decay behavior analysis of two-peak emission in Ca(Al/Si)2N2(N1-x O x ):Eu2+ Phosphors. J. Electrochem. Soc. 161(1), H25 (2014).
33. Wang, X-J., Zhou, G-H., Zhang, H-L., Li, H-L., Zhang, Z-J., and Sun, Z.: Luminescent properties of yellowish orange Y3Al5-x Si x O12-x N x :Ce phosphors and their applications in warm white light-emitting diodes. J. Alloys Compd. 519, 149 (2012).



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