ZrSiO4∶Mn4+荧光粉的制备及光谱性能

摘要/Abstract

摘要： 采用固相反应制备了不同浓度Mn⁴⁺掺杂的硅酸锆粉末,研究了Mn⁴⁺对硅酸锆光致发光性能的影响。采用XRD表征 ZrSiO₄∶Mn⁴⁺的结构,结果显示在1 400 ℃粉末已被完全合成。研究了不同掺杂浓度下ZrSiO₄∶Mn⁴⁺粉末的光谱性能,在0.3%Mn⁴⁺掺杂浓度(摩尔分数)下,其发光性能最好。在激发谱中,位于363 nm的峰是由O^2--Mn⁴⁺的电荷迁移带和自旋允许的Mn⁴⁺的⁴A₂-⁴T₁的能级跃迁叠加产生的,而450 nm的激发峰则是因为Mn⁴⁺的⁴A₂-⁴T₂能级跃迁导致的。发射谱中的最强峰位于667 nm,这是由Mn⁴⁺的²E-⁴A₂的能级跃迁产生的,还有一个位于698 nm的峰则是由于反斯托克斯声子边带发射造成的。测试了ZrSiO₄∶Mn⁴⁺粉末的荧光衰减曲线,Mn⁴⁺离子浓度为0.1%时寿命为0.204 1 ms。结果表明,ZrSiO₄∶Mn⁴⁺粉末拥有良好的发光性能,是一种有望应用于白光LED的荧光粉。

关键词: 红色荧光粉, 硅酸锆, 光谱性能, 发光材料, 高温固相法

Abstract: Zirconium silicate (ZrSiO₄) powders with different doping concentrations of Mn⁴⁺ were prepared by solid-state reactions. The effect on the photoluminescence properties of ZrSiO₄∶Mn⁴⁺ was studied. The structure of ZrSiO₄∶Mn⁴⁺ was analyzed by X-ray powder diffractometer (XRD). The result shows that the powder was completely synthesized at 1 400 ℃. The spectral properties of ZrSiO₄∶Mn⁴⁺ powders at different doping concentrations were studied. The best luminescence performance was obtained at 0.3%Mn⁴⁺ doping concentration. In the excitation spectrum, the peak at 363 nm is caused by the superposition of the charge transfer band of O^2--Mn⁴⁺ and the ⁴A₂-⁴T₁ energy level transition of the spin-allowed Mn⁴⁺, while the peak at 450 nm is caused by the ⁴A₂-⁴T₂ energy level transition of the Mn⁴⁺. The main emission peaking at 667 nm was due to the spin-forbidden transitions ²E-⁴A₂ of Mn⁴⁺. The other peak located at 698 nm was caused by anti-stokes vibronic sidebands associated with the excited state ²E of Mn⁴⁺. The decay curves show that the lifetime of ZrSiO₄∶0.1% Mn⁴⁺ powders is 0.204 1 ms. The results show that ZrSiO₄∶Mn⁴⁺ powders have good luminescent properties, they have the potential to be used in LED lighting industry.

Key words: red phosphor, zirconium silicate, spectroscopic property, luminescent material, solid-state reaction

中图分类号:

张少伯, 杨秋红, 胡娟. ZrSiO₄∶Mn⁴⁺荧光粉的制备及光谱性能[J]. 人工晶体学报, 2021, 50(8): 1438-1443.

ZHANG Shaobo, YANG Qiuhong, HU Juan. Synthesis and Spectroscopic Properties of ZrSiO₄∶Mn⁴⁺ Phosphor[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(8): 1438-1443.

参考文献

[1] LIU T C, ZHANG G G, QIAO X B, et al. Near-infrared quantum cutting platform in thermally stable phosphate phosphors for solar cells[J]. Inorganic Chemistry, 2013, 52(13): 7352-7357.
[2] CHEN J Y, GUO C F, YANG Z, et al. Li₂SrSiO₄∶Ce³⁺, Pr³⁺ phosphor with blue, red, and near-infrared emissions used for plant growth LED[J]. Journal of the American Ceramic Society, 2016, 99(1): 218-225.
[3] HUANG X Y, LIANG J, LI B, et al. High-efficiency and thermally stable far-red-emitting NaLaMgWO₆∶Mn⁴⁺ phosphorsfor indoor plant growth light-emitting diodes[J]. Optics Letters, 2018, 43(14): 3305.
[4] GUO H, DEVAKUMAR B, LI B, et al. Novel Na₃Sc₂(PO₄)₃∶Ce³⁺, Tb³⁺ phosphors for white LEDs: tunable blue-green color emission, high quantum efficiency and excellent thermal stability[J]. Dyes and Pigments, 2018, 151: 81-88.
[5] JI H P, ZHANG Z T, XU J, et al. Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors[J]. Journal of Inorganic Materials, 2020, 35(8): 847.
[6] 阮文科, 谢木标. 白光LED用钨/钼酸盐红色发光材料研究进展[J]. 人工晶体学报, 2021, 50(1): 167-178.
RUAN W K, XIE M B. Recent Research Progress on Tungsten and Molybdate Red Luminescent For White LED[J]. Journal of Synthetic Crystals, 2021, 50(1): 167-178(in Chinese).
[7] Watanabe Y, Sato H, Nishino Y, et al. Effects of training temperature on damping capacity in thermally cycled Fe-20mass%Mn alloy[J]. Materials Science and Engineering: A, 2009, 521/522: 376-379.
[8] 李晴, 王林香, 柏云凤, 等. Na⁺, Dy³⁺, Eu³⁺掺杂YAG荧光粉的光学性能[J]. 人工晶体学报, 2021, 50(1): 43-52.
LI Q, WANG L X, BAI Y F, et al. Optical Properties of Na⁺, Dy³⁺and Eu³⁺ Doped YAG Phosphors[J]. Journal of Synthetic Crystals, 2021, 50(1): 43-52(in Chinese).
[9] XUAN Y, WANG X F, LIU C S, et al. Structure and luminescence properties of single-phased BaCa₂Y₆O₁₂∶Eu³⁺, Dy³⁺[J]. ECS Journal of Solid State Science and Technology, 2014, 3(11): R216-R221.
[10] TSAI Y T, CHIANG C Y, ZHOU W Z, et al. Structural ordering and charge variation induced by cation substitution in (Sr, Ca)AlSiN₃∶Eu phosphor[J]. Journal of the American Chemical Society, 2015, 137(28): 8936-8939.
[11] FANG S Q, LANG T C, HAN T, et al. Zero-thermal-quenching of Mn⁴⁺ far-red-emitting in LaAlO₃ perovskite phosphor via energy compensation of electrons' traps[J]. Chemical Engineering Journal, 2020, 389: 124297.
[12] ZHANG Y L, LIU Y L, YANG L, et al. Preparation and luminescence properties of thermally stable Mn⁴⁺ doped spinel red-emitting ceramic phosphors[J]. Journal of Luminescence, 2020, 220: 117016.
[13] OU J H, YANG X L, XIAO S G, Luminescence performance of Cr³⁺ doped and Cr³⁺, Mn⁴⁺ co-doped La₂ZnTiO₆ phosphors[J]. Materials Research Bulletin, 2020, 124: 110764.
[14] GORE R C, MCDONALD R S, WILLIAMS V Z, et al. Comparison of LiF and CaF₂ prisms for infra-red use[J]. Journal of the Optical Society of America, 1947, 37(1): 23.
[15] KEMENY G, HAAKE C, Activator center in magnesium fluorogermanate phosphors[J]. The Journal of Chemical Physics, 1960, 33(3): 783-789.
[16] FU A J, GUAN A X, YU D Y, et al. Synthesis, structure, and luminescence properties of a novel double-perovskite Sr₂LaNbO₆∶Mn⁴⁺ phosphor[J]. Materials Research Bulletin, 2017, 88: 258-265.
[17] ZHANG X W, NIE J M, LIU S S, et al. Deep-red photoluminescence and long persistent luminescence in double perovstkite-type La₂MgGeO₆∶Mn⁴⁺[J]. Journal of the American Ceramic Society, 2018, 101(4): 1576-1584.
[18] XIANG J M, CHEN J Y, ZHANG N M, et al. Far red and near infrared double-wavelength emitting phosphor Gd₂ZnTiO₆∶Mn⁴⁺, Yb³⁺ for plant cultivation LEDs[J]. Dyes and Pigments, 2018, 154: 257-262.
[19] RIESEN H, MONKS-CORRIGAN T, MANSON N B. Temperature dependence of the R1 linewidth in Al₂O₃∶Mn⁴⁺: a spectral hole-burning and FLN study[J]. Chemical Physics Letters, 2011, 515(4/5/6): 241-244.
[20] LV L F, CHEN Z, LIU G K, et al. Optimized photoluminescence of red phosphor K₂TiF₆:Mn⁴⁺ synthesized at room temperature and its formation mechanism[J]. Journal of Materials Chemistry C, 2015, 3(9): 1935-1941.
[21] ZHU H M, LIN C C, LUO W Q, et al. Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes[J]. Nature Communications, 2014, 5(1): 4312.
[22] HUANG C H, CHEN T M. A novel single-composition trichromatic white-light Ca₃Y(GaO)₃(BO₃)₄∶Ce³⁺, Mn²⁺, Tb³⁺ phosphor for UV-light emitting diodes[J]. The Journal of Physical Chemistry C, 2011, 115(5): 2349-2355.
[23] ZHOU J, XIA Z G. Synthesis and near-infrared luminescence of La₃GaGe₅O₁₆∶Cr³⁺ phosphors[J]. RSC Adv, 2014, 4(86): 46313-46318.

ZrSiO₄∶Mn⁴⁺荧光粉的制备及光谱性能

Synthesis and Spectroscopic Properties of ZrSiO₄∶Mn⁴⁺ Phosphor

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	徐杰, 宋青松, 刘坚, 丁雨憧, 李东振, 徐晓东, 徐军. Sm∶YAG/Sm∶Y₃ScAl₄O₁₂单晶光纤的生长及光谱性能[J]. 人工晶体学报, 2021, 50(7): 1391-1396.
[2]	李晴, 王林香, 柏云凤, 阿热帕提·夏克尔. Na⁺,Dy³⁺,Eu³⁺掺杂YAG荧光粉的光学性能[J]. 人工晶体学报, 2021, 50(1): 43-52.
[3]	阮文科, 谢木标. 白光LED用钨/钼酸盐红色发光材料研究进展[J]. 人工晶体学报, 2021, 50(1): 167-178.
[4]	郭屹坚;吴冬妮. SrCaMoO4:Eu3+A+(A=Na+,K+,Li+)荧光粉的制备及发光性能研究[J]. 人工晶体学报, 2020, 49(9): 1620-1624.
[5]	唐庆;陈尧;颜晓东;左芬;程菊. 高热稳定性的SrAl2Si2O8:Eu2+荧光粉的制备与发光性能研究[J]. 人工晶体学报, 2020, 49(9): 1625-1630.
[6]	张岚;王喜贵. SiO2对Eu3+∶ZnO1-xSx红色发光材料的影响[J]. 人工晶体学报, 2020, 49(3): 457-461.
[7]	孔丽;刘莹莹;乔露;吴晶;陈丽;潘宵;王文生;于海辉;魏奇业. 白光LED用近紫外光激发的蓝绿色荧光粉Sr5(PO4)3F∶Eu2+的光谱性能及助熔剂的影响[J]. 人工晶体学报, 2020, 49(1): 33-38.
[8]	曾飘飘;吴冬妮. CaGd2(MoO4)4:Sm3+,La3+荧光粉的制备及发光性能研究[J]. 人工晶体学报, 2019, 48(8): 1412-1417.
[9]	陈亚萍;孙志刚;赵艳;廖凡;陈红兵. Nd3+∶YCa4O(BO3)3单晶的坩埚下降法生长与光谱性能[J]. 人工晶体学报, 2019, 48(11): 2008-2013.
[10]	涂朝阳;朱昭捷;李坚富;游振宇;王燕;Brenier Alain. GdAl3(BO3)4和Nd离子掺杂的倍频与自变频激光晶体研究[J]. 人工晶体学报, 2019, 48(10): 1843-1853.
[11]	孔丽;乔露;刘莹莹;潘宵;于海辉;王文生;魏奇业. 白光LED用绿色荧光粉Ba3(PO4)2∶Tb3+的发光性能研究[J]. 人工晶体学报, 2019, 48(10): 1869-1872.
[12]	靳天雨;崔瑞瑞;张弛;邓朝勇. CaAl2Si2O8:Eu荧光粉发光性能及自还原现象的研究[J]. 人工晶体学报, 2018, 47(8): 1637-1641.
[13]	张磊;范亚蕾;黄月霞;王德强. Ba2+,Al3+,Sr2+掺杂YF3∶Ho3+,Yb3+上转换发光的研究[J]. 人工晶体学报, 2018, 47(5): 885-893.
[14]	张涛;穆冬迪;欧阳艳;何晓燕. 超声辅助共沉淀法合成CaMoO4:Eu3+红色荧光粉及其发光性能研究[J]. 人工晶体学报, 2018, 47(1): 207-212.
[15]	海热古·吐逊;吐沙姑·阿不都吾甫;美合日古丽·麦麦提;艾尔肯·斯地克. Sm3+掺杂天然钠长石(NaAlSi3O8)荧光粉的发光性质研究[J]. 人工晶体学报, 2017, 46(9): 1697-1702.