金属离子Bi3+掺杂Lu1-xO3: x%Ho3+荧光粉的发光性能

赵海琴; 王林香; 庹娟; 叶颖

doi:10.37188/CO.2019-0222

金属离子Bi³⁺掺杂Lu_1-xO₃: x%Ho³⁺荧光粉的发光性能

doi: 10.37188/CO.2019-0222

赵海琴^{1, 2, 3,},
王林香^{1, 2, 3, ,},
庹娟^{1, 2, 3},
叶颖^{1, 2, 3}

1.
新疆师范大学物理与电子工程学院，新疆乌鲁木齐 830054
2.
新疆师范大学矿物发光及其微结构重点实验室，新疆乌鲁木齐 830054
3.
新疆师范大学新型光源与微纳米光学实验室，新疆乌鲁木齐 830054

基金项目: 新疆维吾尔自治区自然科学基金(No. 2017D01A60)；新疆维吾尔自治区高校科研计划 (No. XJEDU2018Y032)

详细信息

作者简介:
赵海琴（1995—），女，甘肃金昌人，硕士，2020 年于新疆师范大学获得硕士学位，主要从事纳米发光材料的制备及其性能研究。E-mail：zhq0928@mail.ustc.edu.cn

王林香（1979—），女，甘肃秦安人，博士，副教授，2010 年于中国科学技术大学获得博士学位，主要研究纳米发光材料。E-mail：wanglinxiang23@126.com

中图分类号: O482.31
计量
- 文章访问数: 90
- HTML全文浏览量: 35
- PDF下载量: 3
- 被引次数: 0
出版历程
- 收稿日期: 2019-11-26
- 修回日期: 2020-01-21
- 网络出版日期: 2021-04-17

Luminescence properties of Bi³⁺ doped Lu_1-xO₃: x%Ho³⁺ metal ion phosphors

ZHAO Hai-qin^{1, 2, 3
,},
WANG Lin-xiang^{1, 2, 3
, ,},
TUO Juan^{1, 2, 3},
YE Ying^{1, 2, 3}

1.
College of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China
2.
Key Laboratory of Mineral Luminescence and Microstructures, Xinjiang Normal University, Urumqi 830054, China
3.
Laboratory of Novel Light Sources and Micro/Nano-Optics, Xinjiang Normal University, Urumqi 830054, China

Funds: Supported by Natural Science Foundation of Xinjiang (No. 2017D01A60); Scientific Research Plan of Colleges and University in Xinjiang (No. XJEDU2018Y032)

More Information

Corresponding author: wanglinxiang23@126. com

摘要

摘要: 采用高温固相法制备了金属离子Bi³⁺掺杂Lu_1-xO₃: x%Ho³⁺系列荧光粉，研究了不同浓度Bi³⁺掺杂Lu_1-xO₃: x%Ho³⁺荧光粉的晶体结构、Lu₂O₃基质中Bi³⁺→Ho³⁺的能量传递规律及合成粉体的发光性质。X射线衍射结果表明Bi³⁺、Ho³⁺掺杂对Lu₂O₃的立方相结构没有影响。在322 nm激发波长下发射出位于551 nm处Ho³⁺的⁵S₂→⁵I₈跃迁；在551 nm监测下，合成的Ho³⁺、Bi³⁺共掺杂Lu₂O₃荧光粉出现Bi³⁺的322 nm特征激发峰以及Ho³⁺的448 nm处的⁵I₈→⁵F₁跃迁。当Bi³⁺掺杂浓度为1.5%时，Bi³⁺对Ho³⁺的能量传递最有效，比单掺Ho³⁺样品发射强度提高了34.8倍。Lu_98.5%−yO₃:1.5%Ho³⁺, y%Bi³⁺(y=1，1.5，2)样品，随着Bi³⁺掺杂浓度增加，用980 nm激发比322 nm激发在551 nm处获得的光强分别提高了 13.3倍、16.8倍、14.2倍。通过计算得到Bi³⁺和Ho³⁺之间的能量传递临界距离为2.979 nm，且Bi³⁺与Ho³⁺之间的能量传递是通过偶极-四极相互作用实现的。
- 荧光粉 /
- 发光性能 /
- 能量传递 /
- 多极相互作用
Abstract: Bi³⁺ doped Lu_1-xO₃: x%Ho³⁺ metal ion phosphors were prepared using the high-temperature solid-phase method. The crystal structures of Bi³⁺ doped Lu_1-xO₃: x%Ho³⁺ phosphors, the Bi³⁺→Ho³⁺ energy transfer rule in Lu₂O₃ matrix and the luminescent properties of synthetic powders with different doping concentrations were investigated. X-ray diffraction results showed that Bi³⁺ and Ho³⁺ doping had no effect on the cubic phase structure of Lu₂O₃. Lu₂O₃: Ho³⁺, Bi³⁺ phosphor emitted ⁵S₂→⁵I₈ transition of Ho³⁺ at 551 nm under an excitation wavelength of 322 nm, and exhibited ¹S₀→³P₁ characteristic transition of Bi³⁺ at 322 nm and ⁵I₈→⁵F₁ transition of Ho³⁺ at 448 nm under an emission wavelength of 551 nm. When the doping concentration of Bi³⁺ was 1.5%, the effect was most effective for the energy transfer of Ho³⁺, which increased by a factor of 34.8 compared to that of the single-doped Ho³⁺ sample. For Lu_98.5%−yO₃:1.5%Ho³⁺, y%Bi³⁺(y=1, 1.5, 2), with the increase of Bi³⁺ ions concentration, the luminescence intensity at 551 nm under 980-nm excitation increased by a factor of 13.3, 16.8 and 14.2, respectively, compared to that of under 322-nm excitation. The energy transfer critical distance between Bi³⁺ and Ho³⁺ was calculated to be 2.979 nm, and the energy transfer between Bi³⁺ and Ho³⁺ was achieved by dipole-quadrupole interaction.
- phosphor /
- luminescence propertie /
- energy transfer /
- multipolar interaction

HTML全文

图 1 Ho³⁺、Bi³⁺掺杂Lu₂O₃粉末XRD

Figure 1. XRD patterns of Ho³⁺ and Bi³⁺ doped Lu₂O₃ powders

下载: 全尺寸图片幻灯片

图 2 Lu_98.5%O₃:1.5%Bi³⁺和 Lu_98.5%O₃:1.5%Ho³⁺样品的激发和发射光谱

Figure 2. Excitation and emission spectra of Lu_98.5%O₃:1.5%Bi³⁺ and Lu_98.5%O₃:1.5%Ho³⁺phosphor samples

下载: 全尺寸图片幻灯片

图 3 Lu_98.5%-yO₃:1.5%Ho³⁺，y%Bi³⁺样品的激发光谱（a）和发射光谱（b）

Figure 3. Excitation spectra (a) and emission spectrum (b) of Lu_98.5%-yO₃: 1.5% Ho³⁺, y%Bi³⁺ samples

下载: 全尺寸图片幻灯片

图 4 Bi³⁺与Ho³⁺的能级以及能量传递示意图

Figure 4. Schematic diagram of the energy levels and energy transfer of Bi³⁺ and Ho³⁺

下载: 全尺寸图片幻灯片

图 5 980 nm及322 nm激发下Lu_1−x−yO₃:x%Ho³⁺, y%Bi³⁺样品的发射光谱及强度变化

Figure 5. Luminescence spectra and intensity changes of Lu_1−x−yO₃:x%Ho³⁺, y%Bi³⁺ samples at 980 nm and 322 nm excitation

下载: 全尺寸图片幻灯片

图 6 Lu_98.5%-yO₃:1.5%Ho³⁺,y%Bi³⁺荧光粉中Ho³⁺的荧光衰减曲线

Figure 6. Decay curves for the luminescence of Ho³⁺ in Lu_98.5%-yO₃:1.5%Ho³⁺, y%Bi³⁺phosphors

下载: 全尺寸图片幻灯片

图 7 Lu_98.5%-yO₃:1.5%Ho³⁺，y%Bi³⁺荧光粉中Ho³⁺的${{{I}}_{{{{\rm{S}}}}_{0}}}/{I_{\rm{S}}}$与(C_Bi+C_Ho)^6/3，(C_Bi+C_Ho)^8/3和(C_Bi+C_Ho)^10/3关系曲线

Figure 7. Dependence ${{{I}}_{{{{\rm{S}}}}_{0}}}/{I_{\rm{S}}}$ of Ho³⁺ on (C_Bi+C_Ho) ^6/3, (C_Bi+C_Ho) ^8/3 and (C_Bi+C_Ho) ^10/3 in Lu_98.5%-yO₃:1.5%Ho³⁺, y%Bi³⁺ phosphor

下载: 全尺寸图片幻灯片

表 1 不同摩尔分数的Bi³⁺掺杂Lu₂O₃:Ho³⁺荧光粉

Table 1. Bi³⁺ doped Lu₂O₃:Ho³⁺ phosphors at different doping concentrations

sample Lu₂O₃ Ho³⁺ Bi³⁺

1 98.5% 1.5% 0%
2 98.5% 0% 1.5%
3 97.5% 1.5% 1.0%
4 97.0% 1.5% 1.5%
5 96.5% 1.5% 2.0%

下载: 导出CSV

参考文献(31)

[1]	贾玉涛. 稀土离子Ho³⁺掺杂氧化物上转换光致发光的研究[D]. 苏州: 苏州大学, 2010. JIA Y T. Study on up-conversion photo luminescence of rare earth ions Ho³⁺ doped oxides[D]. Suzhou: Soochow University, 2010. (in Chinese)
[2]	FENG L, WU Y S. Optical transitions of Ho³⁺ in oxyfluoride glasses and upconversion luminescence of Ho³⁺/Yb³⁺ -codoped oxyfluoride glasses[J]. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2015, 142: 232-238. doi: 10.1016/j.saa.2015.01.066
[3]	BHARGAVI K, RAO M S, SUDARSAN V, et al. Influence of Al³⁺ ions on self up-conversion in Ho³⁺ doped lead silicate glasses[J]. Optical Materials, 2014, 36(7): 1189-1196. doi: 10.1016/j.optmat.2014.02.027
[4]	SURESH B, ZHYDACHEVSKII Y, BRIK M G, et al. Amplification of green emission of Ho³⁺ ions in lead silicate glasses by sensitizing with Bi³⁺ ions[J]. Journal of Alloys and Compounds, 2016, 683: 114-122. doi: 10.1016/j.jallcom.2016.05.056
[5]	李新跃, 邓建国, 刘东亮. 氧化物掺杂稀土的上转换材料研究进展[J]. 信阳师范学院学报: 自然科学版,2011,24(3):414-420. LI X Y, DENG J G, LIU D L. Research progress of upconversion materials of oxide matrix with doped rare earths[J]. Journal of Xinyang Normal University:Natural Science Edition, 2011, 24(3): 414-420. (in Chinese)
[6]	李佳钰. Bi³⁺和几种稀土离子掺杂新型发光材料的合成及性质研究[D]. 沈阳: 沈阳师范大学, 2018. LI J Y. Study of the synthesis and luminescent properties of Bi³⁺ and several rare earth ions doped new optical materials[D]. Shenyang: Shenyang Normal University, 2018. (in Chinese).
[7]	郭如旺, 郭常新. Lu₂O₃: Bi³⁺粉末晶体发光性能的研究[J]. 中国稀土学报,2007,25(5):533-539. doi: 10.3321/j.issn:1000-4343.2007.05.003 GUO R W, GUO CH X. Luminescent properties of nano- and submicron-crystal Lu₂O₃: Bi³⁺[J]. Journal of the Chinese Rare Earth Society, 2007, 25(5): 533-539. (in Chinese) doi: 10.3321/j.issn:1000-4343.2007.05.003
[8]	RAO T K V, KAMAL C S, SAMUEL T, et al. Color tunable luminescence from LaAlO₃: Bi³⁺, Ho³⁺ doped phosphors for field emission displays[J]. Journal of Materials Science:Materials in Electronics, 2017, 29(2): 1011-1017.
[9]	XUE J P, WANG X F, JEONG J H, et al. Spectral and energy transfer in Bi³⁺–Reⁿ⁺ (n = 2, 3, 4) co-doped phosphors: extended optical applications[J]. Physical Chemistry Chemical Physics, 2018, 20(17): 11516-11541. doi: 10.1039/C8CP00433A
[10]	ZENG L W, LIU Y, LIN B H, et al. Rational design of Bi³⁺/Ln³⁺: GdVO₄ (Ln=Eu, Sm, Dy, Ho) nanophosphor: synthesis, characterization and color-tunable property[J]. Optical Materials, 2018, 77: 204-210. doi: 10.1016/j.optmat.2018.01.040
[11]	赵海琴, 王林香, 庹娟, 等. Li⁺/Bi³⁺掺杂Lu₂O₃: Ho³⁺荧光粉的制备及其发光特性[J]. 激光与光电子学进展,2018,55(8):081602. ZHAO H Q, WANG L X, TUO J, et al. Preparation and luminescent properties of Li⁺/Bi³⁺ co-doped Lu₂O₃: Ho³⁺ phosphors[J]. Laser &Optoelectronics Progress, 2018, 55(8): 081602. (in Chinese)
[12]	肖全兰, 孟建新, 谢丽娟, 等. Bi³⁺掺杂对YVO₄: Yb³⁺近红外发光的敏化作用[J]. 物理化学学报,2011,27(10):2427-2431. doi: 10.3866/PKU.WHXB20110928 XIAO Q L, MENG J X, XIE L J, et al. Near-infrared luminescence enhancement by co-doped Bi³⁺ in YVO₄: Yb³⁺[J]. Acta Physico-Chimica Sinica, 2011, 27(10): 2427-2431. (in Chinese) doi: 10.3866/PKU.WHXB20110928
[13]	KHAN W, ZHOU L LIANG, et al. Luminescence enhancement and energy transfers of Ce³⁺ and Sm³⁺ in CaSrSiO₄ phosphor[J]. Journal of Materials Chemistry C, 2018, 6(28): 7612-7618. doi: 10.1039/C8TC02143K
[14]	TAO ZH X, TSUBOI T, HUANG Y L, et al. Photoluminescence properties of Eu³⁺-doped glaserite-type orthovanadates CsK₂Gd[VO₄]₂[J]. Inorganic Chemistry, 2014, 53(8): 4161-4168. doi: 10.1021/ic500208h
[15]	XIA ZH G, MIAO SH H, CHEN M Y, et al. Structure, crystallographic sites, and tunable luminescence properties of Eu²⁺ and Ce³⁺/Li⁺-activated Ca_1.65Sr_0.35SiO₄ phosphors[J]. Inorganic Chemistry, 2015, 54(16): 7684-7691. doi: 10.1021/acs.inorgchem.5b00455
[16]	GUO Q, WANG Q, JIANG L, et al. A novel apatite, Lu₅(SiO₄)₃N: (Ce, Tb), phosphor material: synthesis, structure and applications for NUV-LEDs[J]. Physical Chemistry Chemical Physics, 2016, 18(23): 15545-15554. doi: 10.1039/C6CP01512C
[17]	胡莲莲, 艾尔肯·斯地克, 万英, 等. Dy³⁺、Tm³⁺共掺杂Ca₂MgSi₂O₇的发光特性[J]. 发光学报,2018,39(7):948-954. doi: 10.3788/fgxb20183907.0948 HU L L, AIERKEN S, WAN Y, et al. Luminescent properties of Dy³⁺, Tm³⁺ co-doped Ca₂MgSi₂O₇[J]. Chinese Journal of Luminescence, 2018, 39(7): 948-954. (in Chinese) doi: 10.3788/fgxb20183907.0948
[18]	DEXTER D L, SCHULMAN J H. Theory of concentration quenching in inorganic phosphors[J]. Journal of Chemical Physics, 1954, 22(6): 1063-1070. doi: 10.1063/1.1740265
[19]	ZHOU H P, JIN Y, JIANG M S, et al. A single-phased tunable emission phosphor MgY₂Si₃O₁₀: Eu³⁺, Bi³⁺ with efficient energy transfer for white LEDs[J]. Dalton Transactions, 2015, 44(3): 1102-1109. doi: 10.1039/C4DT02114B
[20]	杨国辉, 陈凯, 王小军, 等. 基质组成变化及电荷补偿对NaM₄(VO₄)₃: Eu³⁺(M=Mg, Ca)荧光性能的调控[J]. 发光学报,2019,40(6):725-734. doi: 10.3788/fgxb20194006.0725 YANG G H, CHEN K, WANG X J, et al. Controlling emissions of NaM₄(VO₄)₃: Eu³⁺(M=Mg, Ca) phosphor by adjusting base composition and charge compensation[J]. Chinese Journal of Luminescence, 2019, 40(6): 725-734. (in Chinese) doi: 10.3788/fgxb20194006.0725
[21]	糜万鑫, 曹丽丽, 楚司祺, 等. 绿色荧光粉Sr₃P₄O₁₃: Ce³⁺, Tb³⁺的发光特性及Ce³⁺→Tb³⁺能量传递机理[J]. 光学学报,2019,39(8):0816002. doi: 10.3788/AOS201939.0816002 MI W X, CAO L L, CHU S Q, et al. Luminescence properties and energy transfer mechanism of Sr₃P₄O₁₃: Ce³⁺, Tb³⁺ green phosphors[J]. Acta Optica Sinica, 2019, 39(8): 0816002. (in Chinese) doi: 10.3788/AOS201939.0816002
[22]	于汀, 高明燕, 宋岩, 等. Dy³⁺, Eu³⁺共掺的LiGd(MoO₄)₂单一相荧光粉的合成、发光及能量传递[J]. 无机化学学报,2018,34(5):857-863. doi: 10.11862/CJIC.2018.116 YU T, GAO M Y, SONG Y, et al. Synthesis, luminescence and energy transfer of Dy³⁺ and Eu³⁺ co-doped LiGd(MoO₄)₂ single-phase phosphors[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(5): 857-863. (in Chinese) doi: 10.11862/CJIC.2018.116
[23]	苏小娜, 万英, 周芷萱, 等. Na₂CaSiO₄: Sm³⁺, Eu³⁺荧光粉的发光特性和能量传递[J]. 物理学报,2017,66(23):230701. doi: 10.7498/aps.66.230701 SU X N, WAN Y, ZHOU ZH X, et al. Luminescence properties and energy transfer of Na₂CaSiO₄: Sm³⁺, Eu³⁺ phosphor[J]. Acta Physica Sinica, 2017, 66(23): 230701. (in Chinese) doi: 10.7498/aps.66.230701
[24]	BLASSE G. Energy transfer in oxidic phosphors[J]. Physics Letters A, 1968, 28(6): 444-445. doi: 10.1016/0375-9601(68)90486-6
[25]	XIE A, YUAN X M, SHI Y, et al. Photoluminescence characteristics of energy transfer between Eu³⁺ and Bi³⁺ in LiEu_1−xBi_x (WO₄)_0.5(MoO₄)_1.5[J]. Journal of the American Ceramic Society, 2009, 92(10): 2254-2258. doi: 10.1111/j.1551-2916.2009.03195.x
[26]	陈彩花, 杨国辉, 梁利芳, 等. 溶胶凝胶法合成CaYAlO₄: Mn⁴⁺红色荧光粉及其荧光性能研究[J]. 发光学报,2017,38(5):567-573. doi: 10.3788/fgxb20173805.0567 CHEN C H, YANG G H, LIANG L F, et al. Luminescent properties of CaYAlO₄: Mn⁴⁺ red phosphors prepared by sol-gel method[J]. Chinese Journal of Luminescence, 2017, 38(5): 567-573. (in Chinese) doi: 10.3788/fgxb20173805.0567
[27]	ZHANG Y, GONG W T, YU J J, et al. Multi-color luminescence properties and energy transfer behaviour in host-sensitized CaWO₄: Tb³⁺, Eu³⁺ phosphors[J]. RSC Advances, 2016, 6(37): 30886-30894. doi: 10.1039/C6RA01862A
[28]	REISFELD R, LIEBLICH-SOFFER N. Energy transfer from UO₂²⁺ to Sm³⁺ in phosphate glass[J]. Journal of Solid State Chemistry, 1979, 28(3): 391-395. doi: 10.1016/0022-4596(79)90090-2
[29]	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. doi: 10.1021/jp107856d
[30]	JHA K, JAYASIMHADRI M. Effective sensitization of Eu³⁺ and energy transfer in Sm³⁺/Eu³⁺ co-doped ZPBT glasses for CuPc based solar cell and w-LED applications[J]. Journal of Luminescence, 2018, 194: 102-107. doi: 10.1016/j.jlumin.2017.09.049
[31]	PAULOSE P I, JOSE G, THOMAS V, et al. Sensitized fluorescence of Ce³⁺/Mn²⁺ system in phosphate glass[J]. Journal of Physics and Chemistry of Solids, 2003, 64(5): 841-846. doi: 10.1016/S0022-3697(02)00416-X