Abstract
This paper briefly reviews the recent progress in alkaline earth silicate host luminescent materials with broad excitation band for phosphor-convered white LED. Among them, the Sr-rich binary phases (Sr, Ba, Ca, Mg)2SiO4:Eu2+ and (Sr, Ba, Ca, Mg)3SiO5:Eu2+ are excellent phosphors for blue LED chip white LED. They have very broad excitation bands and exhibit strong absorption of blue radiation in the range of 450–480 nm. And they exhibit green and yellow-orange emission under the InGaN blue LED chip radiation, respectively. The luminous efficiency of InGaN-based (Sr, Ba, Ca, Mg)2SiO4:Eu2+ and (Sr, Ba, Ca, Mg)3SiO5:Eu2+ is about 70–80 lm/W, about 95%–105% that of the InGaN-based YAG:Ce, while the correlated color temperature is between 4600–11000 K. Trinary alkaline earth silicate host luminescent materials MO(M=Sr, Ca, Ba)-Mg(Zn)O-SiO2 show strong absorption of deep blue/near-ultraviolet radiation in the range of 370–440 nm. They can convert the deep blue/near-ultraviolet radiation into blue, green, and red emissions to generate white light. The realization of high-performance white-light LEDs by this approach presents excellent chromaticity and high color rendering index, and the application disadvantages caused by the mixture of various matrixes can be avoided. Moreover, the application prospects and the trends of research and development of alkaline earth silicate phosphors are also discussed.
Similar content being viewed by others
References
Schubert E F, Kim J K. Solid-state light sources getting smart. Science, 2005, 308: 1274
Schlotter P, Baur J, Hielscher Ch, et al. Fabrication and characterization of GaN:InGaN:AlGaN double heterostructure LEDs and their application in luminescence conversion LEDs. Mater Sci Eng B, 1999, 59: 390–394
Jüstel T, Nikol H, Ronda C. New developments in the field of luminescent materials for lighting and displays. Angew Chem Int Ed, 1998, 37(22): 3084
Colvin V, Schlamp M, Alivisatos A. Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer. Nature, 1994, 370: 354–357
Lin J, Shi Y J, Yang Y. Improving the performance of polymer light-emitting diodes using polymer solid solutions. Appl Phys Lett, 2001, 79(5): 578–580
Li Y Q, Delsing C A, With de G, et al. Luminescence properties of Eu2+-activated alkaline-earth silicon-oxynitride MSi2O2−δN2+2/3δ(M = Ca, Sr, Ba): A promising class of novel LED conversion phosphors. Chem Mater, 2005, 17: 3242–3248
Klasens H A, Hoekstra A H, Cox A P M. Ultraviolet fluorescence of some ternary silicates activated with lead. J Electrochem Soc, 1957, 104: 93
Moore P B, Araki T. Atomic arrangement of merwinite, Ca3Mg[SiO4]2, an unusual dense-packed structure of geophysical interest. Am Mineral, 1972, 57: 1355
Barry T L. Equilibria and Eu2+ luminescence of subsolidus phase bounded by Ba3MgSi2O8, Sr3MgSi2O8, Ca3MgSi2O8. J Electrochem Soc, 1968, 115(7): 733–738
Barry T L. Luminescent properties of Eu2+ and Eu2++Mn2+ activated BaMg2Si2O7. J Electrochem Soc, 1968, 117(3): 381–385
Blasse G, Wanmaker W L, Vrugt J W, et al. Fluorescence of Eu2+ activated silicates. Philips Res Rep, 1968, 23: 189–193
Poort S H M, Mererink A, Blasse G. Lifetime measurements in Eu2+-doped host lattices. J Phys Chem Solids, 1997, 58(9): 1451–1456
Blasse G, Wanmaker W L, Vrugt J W. Some new classes of efficient Eu2+-activated phosphors. J Electrochem Soc, 1968, 115: 673
Dorenbos P. Energy of the first 4f7→4f65d transition of Eu2+ in inorganic compounds. J Lumin, 2003, 104: 239–260
**ao Z G, Luo X X. Long Afterglow Luminescence Materials and the Related Applications (in Chinese). 2nd ed. Bei**g: Chemical Industry Press, 2005. 197–220
**ao Z G, **ao Z Q. Long afterglow silicate phosphor and its manufacturing method. US Patent, 6093346, 2000-7-25
**ao Z G, Luo X X, Shi C S. Luminescence Material for Semiconducting Illumination (in Chinese). Bei**g: Chemical Industry Press, 2008, in press
Fields Jr J M, Dear P S, Brown Jr J J. Phase equilibria in the system BaO-SrO-SiO2. J Am Ceram Soc, 1972, 55: 585–588
Pieper G, Eysel W, Hahn Th. Solid solubility and polymorphism in the system Sr2SiO4-Sr2GeO4-Ba2GeO4-Ba2SiO4. J Am Ceram Soc, 1972, 55: 619–622
Catti M, Gazzoni G, Ivaldi G. Structures of twinned β-Sr2SiO4 and of α′-Sr1.9Ba0.1SiO4. Acta Cryst, 1983, C39: 29–34
Kim J S, Jeon P E, Choi J C, et al. Emission color variation of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for light-emitting diode. Solid State Comm, 2005, 133: 187–190
Lim M A, Park J K, Kim C H, et al. Luminescence characteristics of green light emitting Ba2SiO4:Eu2+ phosphor. J Mater Sci Lett, 2003, 22: 1351–1353
Poort S H M, Janssen W, Blasse G. Optical properties of Eu2+-activated orthosilicates and orthophosphates. J Alloys Comp, 1997, 260: 93–97
Kim J S, Park Y H, Kim S M, et al. Temperature-dependent emission spectra of M2SiO4:Eu2+ (M=Ca, Sr, Ba) phosphors for green and greenish white LEDs. Solid State Comm, 2005, 133: 445–448
Barry T L. Fluorescence of Eu2+ activated phase in binary alkaline earth orthosilicate systems. J Electrochem Soc, 1968, 115(11): 1181–1183
Park J K, Lim M A, Kim C H, et al. White light-emitting diodes of GaN-based Sr2SiO4:Eu and the luminescent properties. Appl Phys Lett, 2003, 82: 683–685
Park J K, Choi K J, Kim C H, et al. Optical properties of Eu2+-activated Sr2SiO4 phosphor for light-emitting diodes. Electrochem Solid State Lett, 2004, 7(5): H15–H17
Yoo J S, Kim S H, Yoo W T, et al. Control of spectral properties of strontium-alkaline earth-silicate-europium phosphors for LED applications. J Electrochem Soc, 2005, 152(5): G382–G385
Kang H S, Kang Y C, Jung K Y, et al. Eu-doped barium strontium silicate phosphor particles prepared from spray solution containing NH4Cl flux by spray pyrolysis. Mater Sci Eng B, 2005, 121: 81–85
Qiu J, Miura K, Sugimoto N, et al. Preparation and fluorescence properties of fluoroaluminate glasses containing Eu2+ ions. J Non-Cryst Solids, 1997, 213-214: 266–270
Poort S H M, van Krevel J W H, Stomphorst R, et al. Luminescence of Eu2+ in host lattices with three alkaline earth ions in a row. J Solid State Chem, 1996, 122: 432–435
Park J K, Han C H, Kim C H, et al. Luminescence properties of YOBr: Eu phosphors. Electrochem Solid State Lett, 2002, 5: H11–H13
Park J K, Choi K J, Park S H, et al. Application of Ba2+-Mg2+ co-doped Sr2SiO4:Eu yellow phosphor for white-light-emitting diodes. J Electrochem Soc, 2005, 152(8): H121–H123
Luo X X. Silicate matrix phosphors with broad excitation band for white LED. In: 10th National Symposium on LED, Dalian, 2006
**ao Z G, Luo X X, Yu J J, et al. New silicate phosphor activated by rare earth and the related applications. Second-Class National Invention Award, China, 2006
Park J K, Lim M, Choi K J, et al. Luminescence characteristics of yellow emitting Ba3SiO5:Eu2+ phosphor. J Mater Sci, 2005, 40: 2069–2071
Park J K, Kim C H, Park S H, et al. Application of strontium silicate yellow phosphor for white light-emitting diodes. Appl Phys Lett, 2004, 84: 1647–1649
Park J K, Choi K J, Kim K N, et al. Investigation of strontium silicate yellow phosphors for white light emitting diodes from a combinatorial chemistry. Appl Phys Lett, 2005, 87(3): 031108
Li P L, Yang Z P, Wang Z J, et al. Preparation and luminescence characteristics of Sr3SiO5:Eu2+ phosphor for white LED. Chin Sci Bull, 2008, 53(7): 974–977
Park J K, Choi K J, Yeon J H, et al. Embodiment of the warm whitelight-emitting diodes by using a Ba2+ codoped Sr3SiO5:Eu phosphor. Appl Phys Lett, 2006, 88: 043511
Liu J, Lian H Z, Shi C S. A new luminescent material: Li2CaSiO4: Eu2+. Mater Lett, 2006, 60: 2830–2833
Haferkorn B, Meyer G Z. Li2EuSiO4, ein europium(II)-dilithosilicat: Eu[(Li2Si)O4]. Anorg Allg Chem, 1998, 624(7): 1079–1081
Pardha S M, Varadaraju U V. Photoluminescence studies on Eu2+-activated Li2SrSiO4—a potential orange-yellow phosphor for solid-state lighting. Chem Mater, 2006, 18: 5267–5272
Setlur A A, Heward W J, Gao Y, et al. Crystal chemistry and luminescence of Ce3+-doped Lu2CaMg2(Si,Ge)3O12 and its use in LED based lighting. Chem Mater, 2006, 18: 3314–3322
Yang W J, Luo L Y, Chen T M, et al. Luminescence and energy transfer of Eu-and Mn-coactivated CaAl2Si2O8 as a potential phosphor for white-light UVLED. Chem Mater, 2005, 17: 3883–3888
Liu J, Lian H Z, Shi C S, et al. Eu2+-doped high-temperature phase Ca3SiO4Cl2—A yellowish orange phosphor for white light-emitting diodes. J Electrochem Soc, 2005, 152(11): G880–G884
Liu J, Lian H Z, Sun J Y, et al. Characterization and properties of green emitting Ca3SiO4Cl2:Eu2+ powder phosphor for white lightemitting diodes. Chem Lett, 2005, 34(10): 1340–1341
Akella A, Keszler D A. Sr2LiSiO4F: Synthesis, structure, and Eu2+ luminescence. Chem Mater, 1995, 7: 1229–1302
Lakshminarasimhan N, Varadaraju U V. White-light generation in Sr2SiO4:Eu2+,Ce3+ under near-UV excitation—A novel phosphor for solid-state lighting. J Electrochem Soc, 2005, 152(9): H152–H156
Jang H S, Jeon D Y. Yellow-emitting Sr3SiO5:Ce3+,Li+ phosphor for white-light-emitting diodes and yellow-light-emitting diodes. Appl Phys Lett, 2007, 90: 041906
Muthu S, Schuurmans F J, Pashley M D. Red, green, and blue LEDs for white light illumination. IEEE Trans Quant Electr, 2002, 8: 333–338
Poort S H M, Blokpoel P W, Blasse G. Luminescence of Eu2+ in barium and strontium aluminate and gallate. Chem Mater, 1995, 7(8): 1547–1551
Poort S H M, Reijnhoudt H M, van der Kuip H O T, et al. Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row. J Alloys Comp, 1996, 241: 75–81
Luo X X, Duan J X, Lin G X, et al. New type silicate long afterglow phosphors (in Chinese). Chin J Lumin, 2003, 24(2): 165–170
Luo X X, Yu J J, Lin G X, et al. Development of long afterglow phosphors (in Chinese). Chin J Lumin, 2002, 23(5): 497–502
**a W, Lei M K, Luo X X, et al. M2MgSi2O7:Eu,Re (M=Ca,Sr) phosphor with with broad excitation band. Spectr Spectr Anal, 2008, 28(1): 41–46
Kuo C H, Sheu J K, Chang S J, et al. n-UV+blue/green/red white light emitting diode lamps. Jpn J Appl Phys, 2003, 42: 2284–2287
Huh Y D, Shim J H, Kim Y H, et al. Optical properties of three-band white light emitting diodes. J Electrochem Soc, 2003, 150(2): H57–H60
Kim J S, Jeon P E, Choi J C, et al. Warm-white-light emitting diode utilizing a single-phase full-color Ba3MgSi2O8:Eu2+,Mn2+ phosphor. Appl Phys Lett, 2004, 84: 2931
Kim J S, Lim K T, Jeong Y S, et al. Full-color Ba3MgSi2O8:Eu2+,Mn2+ phosphors for white-light-emitting diodes. Solid State Comm, 2005, 135(1–2): 21–24
Kim J S, Park Y H, Choi J C, et al. Temperature-dependent emission spectrum of Ba3MgSi2O8:Eu2+, Mn2+ phosphor for white-light-emitting diode. Electrochem Solid State Lett, 2005, 8(8): H65–H67
Kim J S, Jeon P E, Park Y H, et al. White-light generation through ultraviolet-emitting diode and white-emitting phosphor. Appl Phys Lett, 2004, 85(17): 3696–3698
Author information
Authors and Affiliations
Corresponding author
Additional information
Supported by the High-Tech Research and Development Program of China (Grant Nos. 2004AA001530 and 2006AA03A137) and Dalian Maritime University Youth Teacher Foundation Program (Grant No. DLMU-ZL-200713)
About this article
Cite this article
Luo, X., Cao, W. & Sun, F. The development of silicate matrix phosphors with broad excitation band for phosphor-convered white LED. Chin. Sci. Bull. 53, 2923–2930 (2008). https://doi.org/10.1007/s11434-008-0392-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11434-008-0392-4