Hostname: page-component-78c5997874-v9fdk Total loading time: 0 Render date: 2024-11-15T13:21:53.357Z Has data issue: false hasContentIssue false
  • English
  • Français

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

Published online by Cambridge University Press:  14 May 2015

Shu-Xing Li ,
Xue-Jian Liu ,
Jia-Qing Liu ,
Huili Li ,
Ri-Hua Mao ,
Zheng-Ren Huang  and
Rong-Jun Xie
Shu-Xing Li
Affiliation:
The State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; and University of Chinese Academy of Sciences, Beijing 100049, China
Xue-Jian Liu*
Affiliation:
The State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
Jia-Qing Liu
Affiliation:
Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062, China
Huili Li
Affiliation:
Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062, China
Ri-Hua Mao
Affiliation:
Analysis and Testing Center for Inorganic Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
Zheng-Ren Huang
Affiliation:
The State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
Rong-Jun Xie*
Affiliation:
Sialon Group, Sialon Unit, National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan
*
a)Address all correspondence to these authors. e-mail: [email protected]
b)e-mail: [email protected]
Get access

Abstract

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 Ra of 91 at a low correlated color temperature of 3500 K with a luminous efficiency of 79 lm/W.

Keywords

preparationblueshiftenergy transferdecay behaviorwarm white LED
Type
Articles
Information
Journal of Materials Research , Volume 30 , Issue 19: Focus Issue: Nitrides and Oxynitride Materials , 14 October 2015 , pp. 2919 - 2927
Copyright
Copyright © Materials Research Society 2015 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Schubert, E-F. and Kim, J-K.: Solid-state light sources getting smart. Science 308, 1274 (2005).Google Scholar
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).Google Scholar
Pimputkar, S., Speck, J-S., DenBaars, S-P., Nakamura, S., and Nakamura, S.: Prospects for LED lighting. Nat. Photonics 3, 180 (2009).Google Scholar
Xie, R-J. and Hirosaki, N.: Silicon-based oxynitride and nitride phosphors for white LEDs—A review. Sci. Technol. Adv. Mater. 8, 588 (2007).Google Scholar
Xie, R-J., Hirosaki, N., Li, Y-Q., and Takeda, T.: Rare-earth activated nitride phosphors: Synthesis, luminescence and applications. Materials 3, 3777 (2010).Google Scholar
Xie, R-J. and Hintzen, H-T.: Optical properties of (oxy)nitride materials: A review. J. Am. Ceram. Soc. 93, 665 (2013).CrossRefGoogle Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar
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).Google Scholar