Abstract
Laboratory discovery of new phosphors for white-light light-emitting diodes (WLEDs) is still an imperative challenge. A new yellow-emitting Sr9MgLi(PO4)7:Eu2+ phosphor was discovered based on the mineral-inspired prototype evolution and new phase construction strategy proposed by our group. Sr9MgLi(PO4)7:Eu2+ has been synthesized by using a high temperature solid-state method, and its phase structure and luminescence properties have been investigated in detail, and applied in WLED lamp. Sr9MgLi(PO4)7 phase is derived from the β-Ca3(PO4)2-type mineral structure. Upon 365 nm UV light excitation, the Sr9MgLi(PO4)7:Eu2+ phosphor exhibits a broad emission band from 450 nm to 700 nm. The white-light LED lamp was fabricated based on the phosphor blends of the composition-optimized yellow-emitting Sr9MgLi(PO4)7:Eu2+ and commercial blue-emitting BaMgAl10O17:Eu2+, and a 365 nm UV chip was used as the excitation source. The Ra, CCT value and CIE of the as-fabricated LEDs were found to be 83, 5,612 K, and (0.324, 0.358), respectively. All the results indicate that Sr9MgLi(PO4)7:Eu2+ could be potential in the development of UV-pumped white-light LEDs.
摘要
发现新型白光LED用荧光粉一直是材料科学领域一项重要的挑战. 采用本课题组提出的矿物结构模型, 高效设计了稀土发光材料新物相, 并解析、 确定新物相的晶体结构. 本论文用黄色荧光粉Sr9MgLi(PO4)7:Eu2+设计合成了一种新型白光LED, 并对其结构和发光特性进行了分析表征. 研究发现: 其物相结构是源于β-Ca3(PO4)2矿物模型. 在365 nm近紫外光激发下, Sr9MgLi(PO4)7:Eu2+呈现出一个从450 nm到700 nm的宽带发射. 通过把Sr9MgLi(PO4)7:Eu2+黄粉与商用蓝粉BaMgAl10O17:Eu2+混合涂敷在蓝光芯片表面, 制作得到了白光LED器件. 测试结果显示, LED的Ra, CCT, CIE值分别为83, 5612 K, (0.324, 0.358), 表明Sr9MgLi(PO4)7:Eu2+可作为白光LED用黄光荧光粉.
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References
Luo W, Liu Y, Chen X. Lanthanide-doped semiconductor nanocrystals: electronic structures and optical properties. Sci China Mater, 2015, 58: 819–850
Huang P, Tu D, Zheng W, et al. Inorganic lanthanide nanoprobes for background-free luminescent bioassays. Sci China Mater, 2015, 58: 156–177
Wang D, Wang R, Liu L, et al. Down-shifting luminescence of water soluble NaYF4:Eu3+@Ag core-shell nanocrystals for fluorescence turn-on detection of glucose. Sci China Mater, 2017, 60: 68–74
Xia Z, Liu Q. Progress in discovery and structural design of color conversion phosphors for LEDs. Prog Mater Sci, 2016, 84: 59–117
Xia Z, Liu G, Wen J, et al. Tuning of photoluminescence by cation nanosegregation in the (CaMg)x(NaSc)1–xSi2O6 solid solution. J Am Chem Soc, 2016, 138: 1158–1161
Pimputkar S, Speck JS, Denbaars SP, et al. Prospects for LED lighting. Nat Photonics, 2009, 3: 180–182
Zhao M, Xia Z, Molokeev MS, et al. Temperature and Eu2+-doping induced phase selection in NaAlSiO4 polymorphs and the controlled yellow/blue emission. Chem Mater, 2017, 29: 6552–6559
Bachmann V, Ronda C, Meijerink A. Temperature quenching of yellow Ce3+ luminescence in YAG:Ce. Chem Mater, 2009, 21: 2077–2084
Xia Z, Zhang Y, Molokeev MS, et al. Structural and luminescence properties of yellow-emitting NaScSi2O6:Eu2+ phosphors: Eu2+ site preference analysis and generation of red emission by codoping Mn2+ for white-light-emitting diode applications. J Phys Chem C, 2013, 117: 20847–20854
Xia Y, Chen J, Liu Y, et al. Crystal structure evolution and luminescence properties of color tunable solid solution phosphors Ca2+xLa8-x(SiO4)6-x(PO4)xO2:Eu2+. Dalton Trans, 2016, 45: 1007–1015
Huang L, Zhu Y, Zhang X, et al. HF-free hydrothermal route for synthesis of highly efficient narrow-band red emitting phosphor K2Si1–xF6:xMn4+ for warm white light-emitting diodes. Chem Mater, 2016, 28: 1495–1502
Xuan T, Yang X, Lou S, et al. Highly stable CsPbBr3 quantum dots coated with alkyl phosphate for white light-emitting diodes. Nanoscale, 2017, 9: 15286–15290
Ji H, Huang Z, Xia Z, et al. Discovery of new solid solution phosphors via cation substitution-dependent phase transition in M3(PO4)2:Eu2+ (M = Ca/Sr/Ba) quasi-binary sets. J Phys Chem C, 2015, 119: 2038–2045
Xia Z, Liu H, Li X, et al. Identification of the crystallographic sites of Eu2+ in Ca9NaMg(PO4)7: structure and luminescence properties study. Dalton Trans, 2013, 42: 16588–16595
Chen M, Xia Z, Molokeev MS, et al. Probing Eu2+ luminescence from different crystallographic sites in Ca10M(PO4)7:Eu2+ (M = Li, Na, and K) with β-Ca3(PO4)2-type structure. Chem Mater, 2017, 29: 7563–7570
Morozov VA, Belik AA, Kotov RN, et al. Crystal structures of double calcium and alkali metal phosphates Ca10M(PO4)7 (M = Li, Na, K). Crystallogr Rep, 2000, 45: 13–20
Wang J, Zhang Z, Zhang M, et al. The energy transfer from Eu2+ to Tb3+ in Ca10K(PO4)7 and its application in green light emitting diode. J Alloys Compd, 2009, 488: 582–585
Zhao J, Wu Y, Liang Y, et al. A novel green-emitting phosphor Ca10Na(PO4)7:Eu2+ for near ultraviolet white light-emitting diodes. Optical Mater, 2013, 35: 1675–1678
Wang Y, Li H, Zhang R, et al. Investigations on the luminescence of emission-tunable Ca10K(PO4)7:Eu2+, Sr2+, Mg2+ phosphors for white LEDs. RSC Adv, 2015, 5: 2689–2693
Huang CH, Chen TM. Ca9La(PO4)7:Eu2+,Mn2+: an emission-tunable phosphor through efficient energy transfer for white lightemitting diodes. Opt Express, 2010, 18: 5089–5099
Guo N, You H, Song Y, et al. White-light emission from a singleemitting-component Ca9Gd(PO4)7:Eu2+,Mn2+ phosphor with tunable luminescent properties for near-UV light-emitting diodes. J Mater Chem, 2010, 20: 9061–9067
Huang CH, Chen TM, Liu WR, et al. A single-phased emissiontunable phosphor Ca9Y(PO4)7:Eu2+,Mn2+ with efficient energy transfer for white-light-emitting diodes. ACS Appl Mater Interfaces, 2010, 2: 259–264
Guo N, Huang Y, You H, et al. Ca9Lu(PO4)7:Eu2+,Mn2+: a potential single-phased white-light-emitting phosphor suitable for whitelight-emitting diodes. Inorg Chem, 2010, 49: 10907–10913
Xie F, Li J, Dong Z, et al. Energy transfer and luminescent properties of Ca8MgLu(PO4)7:Tb3+/Eu3+ as a green-to-red color tunable phosphor under NUV excitation. RSC Adv, 2015, 5: 59830–59836
Xue YN, Xiao F, Zhang QY. A red-emitting Ca8MgLa(PO4)7:Ce3+, Mn2+ phosphor for UV-based white LEDs application. Spectro-Chim Acta Part A-Mol Biomol Spectr, 2011, 78: 1445–1448
Huang Y, Ding H, Jang K, et al. Luminescence properties of triple phosphate Ca8MgGd(PO4)7:Eu2+ for white light-emitting diodes. J Phys D-Appl Phys, 2008, 41: 095110
Wang Y, Zhang J, Shi J, et al. Luminescence properties of (Sr0.86 Mg0.14)3(PO4)2:Eu2+,Mn2+ phosphors for LEDs application. J Mater Sci-Mater Electron, 2017, 28: 8895–8900
Bruker A. TOPAS V3: General Profile and Structure Analysis Software for Powder Diffraction Data. User’s Manual, Karlsruhe: Bruker AXS, 2005
Zhou J, Xia Z, Molokeev MS, et al. Composition design, optical gap and stability investigations of lead-free halide double perovskite Cs2AgInCl6. J Mater Chem A, 2017, 5: 15031–15037
Blasse G. Energy transfer between inequivalent Eu2+ ions. J Solid State Chem, 1986, 62: 207–211
Xia Z, Liu RS, Huang KW, et al. Ca2Al3O6F:Eu2+: a green-emitting oxyfluoride phosphor for white light-emitting diodes. J Mater Chem, 2012, 22: 15183–15189
Dexter DL. A theory of sensitized luminescence in solids. J Chem Phys, 1953, 21: 836–850
Zhang X, Zhou L, Pang Q, et al. Synthesis, photoluminescence and Judd–Ofelt analysis of red LiGd5P2O13:Eu3+ phosphors for white LEDs. RSC Adv, 2015, 5: 54622–54628
Chen M, Xia Z, Molokeev MS, et al. Tuning of photoluminescence and local structures of substituted cations in xSr2Ca(PO4)2–(1–x) Ca10Li(PO4)7:Eu2+ phosphors. Chem Mater, 2017, 29: 1430–1438
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The present work was supported by the National Natural Science Foundation of China (51722202, 91622125 and 51572023) and Natural Science Foundation of Beijing (2172036).
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Jianwei Qiao is a PhD student in University of Science and Technology Beijing. He completed his bachelor degree at Taiyuan Normal University in 2014 and received the master degree from Taiyuan University of Technology in 2017. His research is mainly focused on the rare earth ions activated phosphate luminescent materials for white LEDs.
Zhiguo Xia is a professor of materials chemistry and physics in University of Science and Technology Beijing (USTB). He obtained his bachelor degree in 2002 and master degree in 2005 from Beijing Technology and Business University, and he received his PhD degree from Tsinghua University in 2008. Since then he has been working as an assistant and associate Professor in China University of Geosciences, Beijing (CUGB), 2008–2014. After that, he joined USTB as a full professor. His research interests are in designing of new rare earth phosphors for white LED by integrating structural discovery, modification and structure-property relation studies.
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Qiao, J., Xia, Z., Zhang, Z. et al. Near UV-pumped yellow-emitting Sr9MgLi(PO4)7:Eu2+ phosphor for white-light LEDs. Sci. China Mater. 61, 985–992 (2018). https://doi.org/10.1007/s40843-017-9207-2
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DOI: https://doi.org/10.1007/s40843-017-9207-2