Yb3+-Tm3+共掺BiOBr纳米晶的近红外上转换发光特性研究

doi:10.15541/jim20150389

摘要/Abstract

摘要：

采用水热法合成了Yb³⁺-Tm³⁺共掺BiOBr纳米晶, 研究了其上转换发光性能。在980 nm光激发下, 样品中Tm³⁺离子实现了³H₄→³H₆、¹G₄→³F₄和¹G₄→³H₆跃迁, 进而发出强烈的近红外光(801 nm)和较弱的红光(655 nm)与蓝光(485 nm)。探讨了样品的上转换发光机理, 上转换发光强度与激发功率的关系表明在980 nm激发下Tm³⁺的蓝光和红光发射为三光子过程, 而近红外发光为双光子过程。随着Yb³⁺浓度增加, 近红外发光显著增强, 近红外光与蓝光(I_{801 nm}/I_{485 nm})的发光强度比高达71.4。研究结果表明, Yb³⁺-Tm³⁺共掺BiOBr纳米晶在生物荧光标记领域具有潜在的应用前景。

关键词: BiOBr: Yb³⁺, Tm³⁺, 上转换发光, 近红外发光

Abstract:

Yb³⁺-Tm³⁺ co-doped BiOBr nanocrystals were successfully prepared by hydrothermal method, and its upconversion luminescence properties was investigated. Under excitation at 980 nm light, an intense near-infrared (801 nm) accompanied by weak red (655 nm) and blue emissions (485 nm) were observed, which were attributed to the ³H₄→³H₆, ¹G₄→³F₄ and ¹G₄→³H₆transitions of Tm³⁺ions, respectively. Power dependence studies revealed that blue and red emission resulted from a three-photon process, while the near-infrared emission resulted from a two-photon process, and a possible upconversion mechanism is discussed. As the Yb³⁺ ions concentration increasing, the overall emission intensity increases and near infrared emission is much stronger than red and blue ones. Consequently, the ratios of near-infrared to visible (I_{801 nm}/I_{485 nm}) reaches 71.4. These results indicate that the Yb³⁺-Tm³⁺ co-doped BiOBr nanocrystals have potential applications in biological field as luminescence labeling probers.

Key words: BiOBr: Yb³⁺, Tm³⁺, upconversion luminescence, near infrared emission

中图分类号:

TQ174

李永进, 刘群, 周玉婷, 邱建备, 宋志国. Yb³⁺-Tm³⁺共掺BiOBr纳米晶的近红外上转换发光特性研究[J]. 无机材料学报, 2016, 31(3): 279-284.

LI Yong-Jin, LIU Qun, ZHOU Yu-Ting, QIU Jian-Bei, SONG Zhi-Guo. Near-infrared Upconversion Luminescences Properties of Yb³⁺-Tm³⁺ Co-doped BiOBr Nanocrystals[J]. Journal of Inorganic Materials, 2016, 31(3): 279-284.

图/表 8

图1 Yb3+-Tm3+共掺BiOBr纳米晶随Yb3+离子浓度变化的XRD图谱

Fig. 1 XRD patterns of Yb3+-Tm3+ co-doped BiOBr nanocrystals with different Yb3+ concentrations

表1 Yb3+-Tm3+共掺BiOBr纳米晶随Yb3+浓度变化的晶格常数和晶胞体积

Table1 Lattice constants and cell volume of Yb3+-Tm3+ co-doped BiOBr nanocrystals with different Yb3+ concentrations

Yb³⁺/ mol%	Lattice constant/nm		Cell volume /nm³
Yb³⁺/ mol%	a=b	c	Cell volume /nm³
1	0.3936	0.8141	0.12615
3	0.3931	0.8112	0.12535
5	0.3930	0.8111	0.12530
7	0.3926	0.8121	0.12519
10	0.3915	0.8095	0.12407

图2 Yb3+-Tm3+共掺BiOBr纳米晶的TEM照片

Fig. 2 TEM images of Yb3+-Tm3+ co-doped BiOBr nanocrystals

图3 BiOBr: Yb3+, Tm3+纳米晶的FT-IR图谱

Fig. 3 FT-IR spectrum of BiOBr: Yb3+, Tm3+ nanocrystals

图4 980 nm激发下BiOBr: Yb3+, Tm3+ (1.0/0.5mol% )纳米晶的上转换光谱图

Fig. 4 Upconversion emission spectrum of BiOBr: Yb3+, Tm3+ (1.0/0.5mol% ) nanocrystals under excitation at 980 nm

图5 BiOBr: Yb3+, Tm3+ (1.0/0.5mol% ) 纳米晶(a)上转换发光强度与激发功率的对数曲线图和(b)上转换发光机制图

Fig. 5 (a) Power dependence of the UC emission intensities of BiOBr: Yb3+, Tm3+ (1.0/0.5mol% ); (b) Energy level diagrams of BiOBr nanocrystals and possible UC mechanisms under 980 nm excitation.

图6 (a)980 nm激发下BiOBr: Yb3+, Tm3+纳米晶随Yb3+离子浓度变化的上转换光谱图; (b)485、655 和801 nm波长发光强度与Yb3+离子浓度变化的关系图

Fig. 6 (a) Upconversion emission spectra of BiOBr: Yb3+, Tm3+ nanocrystals with different Yb3+ concentration under excitation at 980 nm and (b) the intensity of 485, 655 and 801 nm wavelength vs Yb3+ ions concentration

表2 随Yb3+离子浓度变化的近红外与蓝光的峰值比(I801 nm/I485 nm)

Table 2 Intensity ratio of near-infrared to blue (I801 nm/ I485 nm) variation in Yb3+ doping concentration

Yb³⁺/mol%	1.0	3.0	5.0	7.0	10.0
I_{801 nm}/I_{485 nm}	34.8	38.1	62.0	71.4	70.3

参考文献 24

[1]	CHEN G Y, QIU H L, PRASAD P N, et al. Upconversion nanoparticles: design, nanochemistry, and applications in theranostics. Chem. Rev., 2014, 114(10): 5161-5214.
[2]	ZHENG W, HUANG P, TU D T, et al. Lanthanide-doped upconversion nano-bioprobes: electronic structures, optical properties, and biodetection. Chem. Soc. Rev., 2015, 44(6): 1379-1415.
[3]	LIU Y S, TU D T, ZHU H M, et al. Lanthanide-doped luminescent nanoprobes: controlled synthesis, optical spectroscopy, and bioapplications. Chem. Soc. Rev., 2013, 42(16): 6924-6958.
[4]	CHUNG J H, LEE S Y, SHIM K B, et al. Blue upconversion luminescence of CaMoO4: Li+/Yb3+/Tm3+ phosphors prepared by complex citrate method. Appl. Phys. A, 2012, 108(2): 369-373.
[5]	WONG H T, CHAN H W L, HAO J H. Towards pure near-infrared to near-infrared upconversion of multifunctional GdF3:Yb3+, Tm3+ nanoparticles.Opt. Express, 2010, 18(6): 6123-6130.
[6]	WANG Z F, LI Y Z, JIANG Q, et al. Pure near-infrared to near-infrared upconversion of multifunctional Tm3+ and Yb3+ co- doped NaGd(WO4)2 nanoparticles. J. Mater. Chem. C, 2014, 2(22): 4495-4501.
[7]	LI Y J, SONG Z G, LI C, et al. Pure NIR to NIR upconverting Bi5O7I:Tm3+, Yb3+ nanophosphors. ECS Solid State Letters, 2013, 2(11): R45-R47.
[8]	CHEN G Y, OHULCHANSKYY T Y, KUMAR R, et al. Ultrasmall monodisperse NaYF4:Yb3+/Tm3+ nanocrystals with enhanced near-infrared to near-infrared upconversion photoluminescence. ACS Nano, 2010, 4(6): 3163-3168.
[9]	LIU Q, SUN Y, YANG T S, et al. Sub-10 nm hexagonal lanthanide- doped NaLuF4 upconversion nanocrystals for sensitive bioimaging in vivo. J. Am. Chem. Soc., 2011, 133(43): 17122-17125.
[10]	DONG N N, PEDRONI M, PICCINELLI F, et al. NIR-to-NIR two- photon excited CaF2:Tm3+,Yb3+ nanoparticles: multifunctional nanoprobes for highly penetrating fluorescence bio-imaging. ACS Nano, 2011, 5(11): 8665-8671.
[11]	WONG H T, VETRONE F, NACCACHE R, et al. Water dispersible ultra-small multifunctional KGdF4:Tm3+, Yb3+ nanoparticles with near-infrared to near-infrared upconversion. J. Mater. Chem., 2011, 21: 16589-16596.
[12]	HILDERBRAND S A, SHAO F W, SALTHOUSE C, et al. Upconverting luminescent nanomaterials: application to in vivo bioimaging. Chem. Commun., 2009, 28: 4188-4190.
[13]	YE L Q, SU Y R, JIN X L, et al. Recent advances in BiOX (X= Cl, Br and I) photocatalysts: synthesis, modification, facet effects and mechanisms. Environmental Science: Nano, 2014, 1(2): 90-112.
[14]	ZHANG D, LI J, WANG Q G, et al. High {001} facets dominated BiOBr lamellas: facile hydrolysis preparation and selective visible-light photocatalytic activity. J. Mater. Chem. A, 2013, 1(30): 8622-8629.
[15]	LI Y J, SONG Z G, YIN Z Y, et al. Investigation on the upconversion emission in 2D BiOBr:Yb3+/Ho3+ nanosheets. Spectrochim. Acta Part A Mol. Biomol. Spectrosc., 2015, 150: 135-141.
[16]	SARAF R, SHIVAKUMARA C, BEHERA S, et al. Synthesis of Eu3+-activated BiOF and BiOBr phosphors: photoluminescence, Judd-Ofelt analysis and photocatalytic properties. RSC Adv., 2015, 5(12): 9241-9254.
[17]	LI Y J, SONG Z G, LI C, et al. High multi-photon visible upconversion emissions of Er3+ singly doped BiOCl microcrystals: a photon avalanche of Er3+ induced by 980 nm excitation. Appl. Phys. Lett., 2013, 103(23): 231104.
[18]	LI Y J, SONG Z G, WAN R H, et al. Multi-band photon avalanche controlling performance of BiOCl: Er3+ crystals through facile Yb3+ doping. J. Mater. Chem. C, 2015, 3(33): 8559-8565.
[19]	LI Y J, ZHAO Z Y, SONG Z G, et al. Far-red-emitting BiOCl: Eu3+ phosphor with excellent broadband NUV-excitation for white- light-emitting diodes. J. Am. Ceram. Soc., 2015, 98(7): 2170-2176.
[20]	邝庆亮,李永进,邱建备,等.近紫外激发 BiOCl:Dy3+ 白光 LED 荧光粉的制备及发光性能研究.光谱学与光谱分析,2015, 35(4): 889-893.
[21]	DASH A, SARKAR S, ADUSUMALLI V N, et al. Microwave synthesis, photoluminescence, and photocatalytic activity of PVA-Functionalized Eu3+-Doped BIOX (X= Cl, Br, I) nanoflakes. Langmuir, 2014, 30(5): 1401-1409.
[22]	SARAF R, SHIVAKUMARA C, BEHERA S, et al. Photoluminescence, photocatalysis and Judd-Ofelt analysis of Eu3+-activated layered BiOCl phosphors. RSC Adv., 2015, 5(6): 4109-4120.
[23]	AVRAM D, COJOCARU B, FLOREA M, et al. NIR to Vis-NIR up-conversion and X-ray excited emission of Er doped high Z BiOCl. Opt. Mater. Express, 2015, 5(5): 951-962.
[24]	LIU Q, LI Y J, KUANG Q L, et al. Unusual effect of cerium codoping on stokes and anti-stokes luminescence of BiOCl:Er3+ crystal. IEEE Photon. J., 2015, 7(5): 1601108.

Yb³⁺-Tm³⁺共掺BiOBr纳米晶的近红外上转换发光特性研究

Near-infrared Upconversion Luminescences Properties of Yb³⁺-Tm³⁺ Co-doped BiOBr Nanocrystals

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	于嫚, 高荣耀, 秦玉军, 艾希成. 上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响[J]. 无机材料学报, 2024, 39(4): 359-366.
[2]	王马超, 唐扬敏, 邓明雪, 周真真, 刘小峰, 王家成, 刘茜. 共沉淀法制备Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿及其近红外发光性能[J]. 无机材料学报, 2023, 38(9): 1083-1088.
[3]	彭跃红,任韦舟,邱建备,韩缙,杨正文,宋志国. 1550 nm激发层状BiOCl:Er³⁺上转换发光及温度传感特性[J]. 无机材料学报, 2020, 35(8): 902-908.
[4]	张志洁,黄海瑞,程昆,郭少柯. 高效碳量子点/BiOCl纳米复合材料用于光催化污染物降解[J]. 无机材料学报, 2020, 35(4): 491-496.
[5]	吕喜庆, 张环宇, 李瑞, 张梅, 郭敏. Nb₂O₅包覆对TiO₂纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响[J]. 无机材料学报, 2019, 34(6): 590-598.
[6]	焦志伟, 段翠翠, 周伟, 刘峰斌, 杨越, 赵攀, 项俊帆. Ni²⁺掺杂尖晶石相透明微晶玻璃制备及光学性能[J]. 无机材料学报, 2018, 33(6): 673-677.
[7]	史忠祥, 王晶, 关昕. Er³⁺掺杂调控NaY(WO₄)₂: Dy³⁺的上转换发光性能[J]. 无机材料学报, 2018, 33(5): 521-527.
[8]	周佳佳, 邱建荣. 单个纳米颗粒的上转换光谱现象研究[J]. 无机材料学报, 2016, 31(10): 1023-1030.
[9]	杨广武, 杨瑞霞, 张守超, 朱飞. Ce³⁺浓度对YVO₄: Ce³⁺晶体发光性能的影响[J]. 无机材料学报, 2016, 31(10): 1073-1080.
[10]	朱美娟, 余建定, 张明辉, 谷彦静, 李勤, 方必军, 赵洪阳, 沈清. 无容器制备Er³⁺/Yb³⁺共掺La₂O₃-TiO₂-ZrO₂玻璃及其上转换发光研究[J]. 无机材料学报, 2015, 30(4): 391-396.
[11]	张继红, 陶海征, 顾少轩, 张高科, 刘超, 赵修建. 面向太阳光全光谱应用铒掺杂硫卤玻璃上转换发光特性研究[J]. 无机材料学报, 2015, 30(3): 245-248.
[12]	向军涛, 杜鹏, 罗来慧, 方义权, 赵学洋, 胡旭波, 陈红兵. Er³⁺掺杂弛豫铁电材料PMNT的单晶生长与性能表征[J]. 无机材料学报, 2015, 30(2): 135-140.
[13]	刘军芳, 苏良碧, 徐军. Bi₂O₃-SiO₂玻璃及玻璃陶瓷近红外发光性能的研究[J]. 无机材料学报, 2014, 29(8): 859-863.
[14]	耿志明, 李坤, 施东良, 施瑕玉, 黄海涛, 陈王丽华. 铌酸钾钠基透明上转换陶瓷材料制备及性能[J]. 无机材料学报, 2014, 29(12): 1265-1269.
[15]	张明辉，余建定，潘秀红，程愉悻，刘岩. Nd³⁺/Yb³⁺共掺La₂O₃-TiO₂-ZrO₂微晶玻璃的制备及上转换发光研究[J]. 无机材料学报, 2013, 28(8): 896-900.