红色荧光粉Na3La(VO4)2:Eu3+的微波合成及光学温度传感性能

doi:10.3969/j.issn.1000-1565.2025.04.004

摘要/Abstract

摘要： 采用微波法合成了Na₃La_1-x(VO₄)₂:xEu³⁺(0<x≤0.40)系列红色荧光粉,探讨了微波反应时间、Eu³⁺浓度等对荧光粉的结构、形貌和发光性质的影响.结果表明:以MnO₂为微波吸收剂,微波功率约为560 W,中高火,反应时间为15~30 min,可合成正交晶系Na₃La(VO₄)₂:Eu³⁺的纯相,且结晶良好.样品的微观形貌呈不规则块状,尺寸为微米级,且随着反应时间的延长,粒径逐渐增大.Na₃La(VO₄):Eu³⁺主激发峰位于320 nm处,最强发射峰位于620 nm处,呈红光发射.微波反应20 min时,主发射峰强度最大.随着Eu³⁺浓度不断增加,样品的主发射峰强度呈先增强后减弱的趋势,当Eu³⁺摩尔分数x为0.32时,强度达到最大,此后逐渐减弱,主要由电偶极-电四极相互作用引起.Na₃La_0.68(VO₄)₂:0.32Eu³⁺在不同温度下的发射光谱显示,在473 K温度下,样品主发射峰强度约为室温时的68%,说明样品具有良好的热稳定性.基于Eu³⁺在538 nm(⁵D₁→⁷F₁)和594 nm(⁵D₀→⁷F₁)的荧光强度比,计算出样品的最大绝对灵敏度S_a和最大相对灵敏度S_r分别为1.23×10^-3/K和2.94%/K,表现出良好的温度传感特性.

关键词: 钒酸盐, 微波法, 红色荧光粉, 白光LED, 光学温度传感

Abstract: A series of Na₃La_1-x(VO₄)₂:xEu³⁺(0<x≤0.40)red phosphors were synthesized by microwave radiation method. The effects of microwave reaction time and Eu³⁺ concentration on the structure, morphology and luminescence properties of the phosphors were investigated. The results show that the pure phase of orthorhombic Na₃La(VO₄)₂:Eu³⁺ with high crystallinity can be synthesized by selecting MnO₂ as the microwave absorbent, microwave power of about 560 W and reaction time of 15~30 min. The micromorphology of the sample is irregular, the particle size is in the level of micron, and the size increases gradually with the extension of reaction time. The main excitation peak of Na₃La(VO₄)₂: Eu³⁺ is located at 320 nm, and the strongest emission peak is located at 620 nm, showing red emission. When the microwave reaction time is 20 min, the intensity of the main emission peak reaches the maximum.- DOI:10.3969/j.issn.1000-1565.2025.04.004红色荧光粉Na₃La(VO₄)₂:Eu³⁺的微波合成及光学温度传感性能李子璇,陈金润,邸紫萌,王腾越,程飞扬,翟永清(河北大学化学与材料科学学院,河北保定 071002)摘要:采用微波法合成了Na₃La_1-x(VO₄)₂:xEu³⁺(0<x≤0.40)系列红色荧光粉,探讨了微波反应时间、Eu³⁺浓度等对荧光粉的结构、形貌和发光性质的影响.结果表明:以MnO₂为微波吸收剂,微波功率约为560 W,中高火,反应时间为15~30 min,可合成正交晶系Na₃La(VO₄)₂:Eu³⁺的纯相,且结晶良好.样品的微观形貌呈不规则块状,尺寸为微米级,且随着反应时间的延长,粒径逐渐增大.Na₃La(VO₄):Eu³⁺主激发峰位于320 nm处,最强发射峰位于620 nm处,呈红光发射.微波反应20 min时,主发射峰强度最大.随着Eu³⁺浓度不断增加,样品的主发射峰强度呈先增强后减弱的趋势,当Eu³⁺摩尔分数x为0.32时,强度达到最大,此后逐渐减弱,主要由电偶极-电四极相互作用引起.Na₃La_0.68(VO₄)₂:0.32Eu³⁺在不同温度下的发射光谱显示,在473 K温度下,样品主发射峰强度约为室温时的68%,说明样品具有良好的热稳定性.基于Eu³⁺在538 nm(⁵D₁→⁷F₁)和594 nm(⁵D₀→⁷F₁)的荧光强度比,计算出样品的最大绝对灵敏度S_a和最大相对灵敏度S_r分别为1.23×10^-3/K和2.94%/K,表现出良好的温度传感特性.关键词:钒酸盐;微波法;红色荧光粉;白光LED;光学温度传感中图分类号:O611;O614 文献标志码:A 文章编号:1000-1565(2025)04-0361-11Microwave synthesis and optical temperature sensing properties of red phosphors Na₃La(VO₄)₂:Eu³⁺LI Zixuan, CHEN Jinrun, DI Zimeng, WANG Tengyue, CHENG Feiyang, ZHAI Yongqing( College of Chemistry and Materials Science, Hebei University, Baoding 071002, China)Abstract: A series of Na₃La_1-x(VO₄)₂:xEu³⁺(0<x≤0.40)red phosphors were synthesized by microwave radiation method. The effects of microwave reaction time and Eu³⁺ concentration on the structure, morphology and luminescence properties of the phosphors were investigated. The results show that the pure phase of orthorhombic Na₃La(VO₄)₂:Eu³⁺ with high crystallinity can be synthesized by selecting MnO₂ as the microwave absorbent, microwave power of about 560 W and reaction time of 15~30 min. The micromorphology of the sample is irregular, the particle size is in the level of micron, and the size increases gradually with the extension of reaction time. The main excitation peak of Na₃La(VO₄)₂: Eu³⁺ is located at 320 nm, and the strongest emission peak is located at 620 nm, showing red emission. When the microwave reaction time is 20 min, the intensity of the main emission peak reaches the maximum.- 收稿日期:2025-01-10;修回日期:2025-02-06 基金项目:国家自然科学基金项目(22175052);中央引导地方科技发展资金项目(246Z7759G);国家级大学生创新创业训练计划项目(DC2024391;202410075039) 第一作者:李子璇(1998—),女,河北大学在读硕士研究生,主要从事稀土掺杂钒酸盐发光材料的研究.E-mail:likeyzixuan@163.com 通信作者:翟永清(1970—),女,河北大学教授,博士,主要从事稀土发光材料的研究.E-mail:zhaiyongqinghbu@163.com 第4期李子璇等:红色荧光粉Na₃La(VO₄)₂:Eu³⁺的微波合成及光学温度传感性能河北大学学报(自然科学版) 第45卷Increase of Eu³⁺ concentration results in the increase of main emission peak intensity of the sample, followed by the gradual decrease. The highest intensity is achieved at the Eu³⁺ concentration x of 0.32. This is attributed to the electric dipole-electric quadrupole interactions. The emission spectra of Na₃La_0.68(VO₄)₂:0.32Eu³⁺ recorded at different temperatures show that the main emission peak intensity of the sample at 473 K is about 68% of that at room temperature, indicating that the sample has good thermal stability. Based on the fluorescence intensity ratio of Eu³⁺ at 538 nm(⁵D₁→⁷F₁)and 594 nm(⁵D₀→⁷F₁), the maximum absolute sensitivity S_a and relative sensitivity S_r of the sample were calculated to be 1.23×10^-3/K and 2.94%/K, respectively, showing good temperature sensing characteristics.

Key words: vanadate, microwave method, red phosphors, white LED, optical temperature sensing

中图分类号:

O611
O614

李子璇,陈金润,邸紫萌,王腾越,程飞扬,翟永清. 红色荧光粉Na₃La(VO₄)₂:Eu³⁺的微波合成及光学温度传感性能[J]. 河北大学学报(自然科学版), 2025, 45(4): 361-371.

LI Zixuan, CHEN Jinrun, DI Zimeng, WANG Tengyue, CHENG Feiyang, ZHAI Yongqing. Microwave synthesis and optical temperature sensing properties of red phosphors Na₃La(VO₄)₂:Eu³⁺[J]. Journal of Hebei University(Natural Science Edition), 2025, 45(4): 361-371.

参考文献

[1] CHAN M, QIU K H, ZHAN P C, et al. Enhancement of NaSrVO₄:Dy³⁺-white-phosphor photoluminescence via La³⁺ co-doping[J]. Ceram Int, 2019, 45(17):22547-22552. DOI:10.1016/j.ceramint.2019.07.282.
[2] CHENG C, NING L X, KE X X, et al. Designing high-performance LED phosphors by controlling the phase stability via a Heterovalent substitution strategy[J]. Adv Opt Mater, 2020,8:1901608. DOI:10.1002/adom.201901608.
[3] ZHOU J C, CHEN M T, ZHANG J X, et al. Regulating photoluminescence behavior by neighboring-cation-size in Sr₈CaX(PO₄)₇:Eu²⁺(X=Al and Ga)phosphors for high color rendering solid-state lighting source[J]. Chem Eng J, 2021, 426:131869. DOI:10.1016/j.cej.2021.131869.
[4] LIU D J, YUN X H, DANG P P, et al. Yellow/orange-emitting ABZn₂Ga₂O₇:Bi³⁺(A=Ca,Sr;B=Ba, Sr)phosphors: optical temperature sensing and white light-emitting diode applications[J]. Chem Mater, 2020, 32(7):3065-3077. DOI:10.1021/acs.chemmater.0c00054.
[5] REVATHY J S, RAJENDRAN DEEPTHI N. Temperature dependent photoluminescence studies of NUV excited Gd₂O₃:Eu phosphor[J]. Mater Today: Proc, 2021, 47(9):2007-2012. DOI:10.1016/j.matpr.2021.04.161.
[6] KHAI SHENN L, ZAINURIAH H, WAY F L, et al. Synthesis and luminescence enhancement of red-emitting Ca₃Y(AlO)₃(BO₃)₄:Eu³⁺ phosphors via La³⁺ co-doping prepared by microwave solution combustion synthesis[J]. Mater Chem Phys, 2022, 293:126649. DOI: 10.1016/j.matchemphys.2022.126649.
[7] 周红,高文海,张渤琦,等.稀土铕掺杂钒酸钇的荧光温度特性研究[J]. 长春理工大学学报(自然科学版), 2021, 44(1):7-13. DOI:10.3969/j.issn.1672-9870.2021.01.002.
[8] PAVANI K, JAMALAIAH B C, NEVES A J, et al. Realization of sensible peak shift thermometry from multiple site occupied Eu³⁺ ions in magnetically frustrated SrGd₂O₄[J]. J Mater Sci, 2022, 57(18):8530-8543. DOI:10.1007/s10853-022-07034-w.
[9] XIAO Q, DONG X Y, YIN X M, et al. Tunable multicolor upconversion luminescence of Yb³⁺ sensitized Na₃La(VO₄)₂ crystals[J]. J Am Ceram Soc, 2020, 104(3):1415-1423. DOI:10.1111/jace.17548.
[10] ZHOU J C, YAO Y, CHEN Y, et al. Synthesis, energy transfer mechanism, and tunable emissions of novel Na₃La(VO₄)₂:Re³⁺(Re³⁺=Dy³⁺, Eu³⁺ and Sm³⁺)vanadate phosphors for near-UV-excited white LEDs[J]. Ceram Int, 2020, 46(5):6276-6283. DOI:10.1016/j.ceramint.2019.11.098.
[11] LIU Y X, LIU G X, DONG X T, et al. Tunable photoluminescence and magnetic properties of Dy³⁺ and Eu³⁺ doped GdVO₄ multifunctional phosphors[J]. Phys Chem Chem Phys, 2015, 17(40):26638-26644. DOI:10.1039/c5cp04373e.
[12] CAO R P, WANG X T, JIAO Y M, et al. A single-phase NaCa₂Mg₂V₃O₁₂:Sm³⁺ phosphor: synthesis, energy transfer and luminescence properties[J]. J Lumin, 2019, 212:23-28. DOI:10.1016/j.jlumin.2019.04.017.
[13] KACHOU I, SAIDI K, SALHI R, et al. Synthesis and optical spectroscopy of Na₃Y(VO₄)₂:Eu³⁺ phosphors for thermometry and display applications[J]. RSC Adv, 2022, 12(12):7529-7539. DOI:10.1039/d2ra00539e.
[14] XIE M L, HE C, FANG M H, et al. Improvement of luminescence performance of single-phase white-emitting Na₃Gd(PO₄)₂:Dy³⁺ phosphor by co-doping with Eu³⁺[J]. Polyhedron, 2022:222. DOI:10.1016/j.poly.2022.115860.
[15] WANG S Y, WANG T, ZHANG H B, et al. Eu³⁺ doped glass ceramics containing NaLa(MoO₄)₂ crystallite: Preparation, structure and luminescence properties[J]. J Lumin, 2020, 226:117420. DOI:10.1016/j.jlumin.2020.117420.
[16] YANG P X, LI L, DENG Y S, et al. Realizing emission color tuning, ratiometric optical thermometry and temperature-induced redshift investigation in novel Eu³⁺-doped Ba₃La(VO₄)₃ phosphors[J]. Dalton Trans, 2019, 48(29):10824-10833. DOI:10.1039/c9dt01917k.
[17] 陈金润,李子璇,焦立鑫,等.Ba₃(VO₄)₂:Sm³⁺荧光粉的熔盐法合成及其温度传感特性[J]. 功能材料, 2024, 55(2):02207-02214.DOI:10.3969/j.issn.1001-9731.2024.02.026.
[18] XIE W, LIU G X, DONG X T, et al. Doping Eu³⁺/Sm³⁺ into CaWO₄:Tm³⁺, Dy³⁺ phosphors and their luminescence properties, tunable color and energy transfer[J]. RSC Adv, 2016, 6(31):26239-26246. DOI: 10.1039/c6ra02594c.
[19] BLASSE G. Energy transfer in oxidic phosphors[J]. Phys Lett A, 1968, 28(6):444-445.
[20] VAN UNITERT L G. Characterization of energy transfer interactions between rare earth ions[J]. J Electrochem Soc, 1967, 114(10):1048-1053.
[21] DEXTER DAVID L, SCHULMAN JAMES H. Theory of concentration quenching in inorganic phosphors[J]. J Chem Phys, 1954, 22(6):1063-1070.
[22] LI J, SHI R X, CAO Y Q, et al. The synergism between self-activated and impurity-related emissions of LiCa₃ZnV₃O₁₂: lattice distortion, energy transfer and temperature sensing effect[J]. RSC Adv, 2022, 12(55):36063-36071. DOI:10.1039/d2ra06647e.
[23] CAO R P, WANG X T, JIAO Y M, et al. A single-phase NaCa₂Mg₂V₃O₁₂:Sm³⁺ phosphor: synthesis, energy transfer and luminescence properties[J]. J Lumin, 2019, 212:23-28. DOI:10.1016/j.jlumin.2019.04.017.
[24] ZHANG L X, MENG Q Y, SUN W J, et al. Temperature-sensing characteristics of NaGd(MoO₄)₂:Sm³⁺, Tb³⁺ phosphors[J]. Ceram Int, 2021, 47(1):670-676. DOI:10.1016/j.ceramint.2020.08.175.
[25] GE X F, FU Z L. Multiwavelength responsive luminescence for temperature sensing and visualized information encoding/decoding based on Er³⁺/Tb³⁺-doped Ba₂Ga₂GeO₇ phosphors[J]. ACS Sustain Chem Eng, 2023, 11(16):6362-6372. DOI:10.1021/acssuschemeng.3c00207.
[26] GU A H, PAN G H, WU H J, et al. Microstructure and photoluminescence of ZrTiO₄:Eu³⁺ phosphors: host-sensitized energy transfer and optical thermometry[J]. Chemosensors, 2022, 10(12):527. DOI:10.3390/chemosensors10120527.
[27] DU P, WU Y F, YU J S. Synthesis and luminescence properties of Eu³⁺-activated BiF₃ nanoparticles for optical thermometry and fluorescence imaging in rice root[J]. RSC Adv, 2018, 8(12):6419-6424. DOI:10.1039/c8ra00107c.
[28] HOU B F, JIA M C, LI P P, et al. Multifunctional optical thermometry based on the rare-earth-ions-doped up-/down-conversion Ba₂TiGe₂O₈:Ln(Ln=Eu³⁺/Er³⁺/Ho³⁺/Yb³⁺)phosphors[J]. Inorg Chem, 2019, 58:7939-7946. DOI:10.1021/acs.inorgchem.9b00646. (

红色荧光粉Na₃La(VO₄)₂:Eu³⁺的微波合成及光学温度传感性能

Microwave synthesis and optical temperature sensing properties of red phosphors Na₃La(VO₄)₂:Eu³⁺

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

编辑推荐

Metrics

本文评价

[1]	翟永清,王莉莉,陈娟,殷天亮,李蕊. 微波辐射法快速合成Eu3+激活的SrMoO4红色荧光粉[J]. 河北大学学报(自然科学版), 2012, 32(6): 602-607.
[2]	王谦,钱先来. 弱碱性介质下微波法提取灵芝多糖的优化[J]. 河北大学学报(自然科学版), 2010, 30(2): 196-200.
[3]	翟永清,冯仕华,张张,牛强. 白光LED用橙红色荧光体Sr_2MgSi_3O_9:Eu~(3+)的制备和光谱性质[J]. 河北大学学报(自然科学版), 2009, 29(6): 609-613.
[4]	刘冲,杨志平,李旭,关丽,王颖,郭庆林. 燃烧法制备(Ca1-xSrx)S:Eu2+红色荧光粉的发光性能研究[J]. 河北大学学报(自然科学版), 2008, 28(5): 466-470.