Tm<SUP>3+</SUP>掺杂的NaYF<SUB>4</SUB>微米颗粒中强烈的单带下转换荧光发射

引用本文: 徐春龙, 王晋国, 张翔宇. Tm³⁺掺杂的NaYF₄微米颗粒中强烈的单带下转换荧光发射[J]. 物理化学学报, 2015, 31(11): 2183-2190. doi: 10.3866/PKU.WHXB201509142 shu

Citation: XU Chun-Long, WANG Jin-Guo, ZHANG Xiang-Yu. Strong Single-Band Down-Conversion Emission in Tm³⁺-Doped NaYF₄ Microparticles[J]. Acta Physico-Chimica Sinica, 2015, 31(11): 2183-2190. doi: 10.3866/PKU.WHXB201509142 shu

Tm³⁺掺杂的NaYF₄微米颗粒中强烈的单带下转换荧光发射

1.
长安大学理学院, 西安 710064

通讯作者: 张翔宇

基金项目:
中央高校基本科研业务费专项资金(2013G1121085, 310812152001) (2013G1121085, 310812152001)

国家自然科学基金(51101022)资助项目 (51101022)

摘要: 采用柠檬酸钠辅助的水热方法合成了一系列具有不同长径比的Tm³⁺掺杂的β-NaYF₄ (NaYF:Tm³⁺)微米棒(盘). 通过X射线衍射(XRD), 扫描电子显微镜(SEM), 能量色散X射线荧光光谱(EDX), 傅里叶变换红外(FTIR)光谱和激光光谱学等手段对所制备的系列β-NaYF₄微米棒(盘)进行了表征. XRD和SEM分析表明β-NaYF₄微米棒(盘)的长径比依赖于前驱液的pH值, 随着前驱液的pH值的增加, 从长棒逐渐过渡到六角盘. 光谱测量结果表明: 一系列NaYF₄:Tm³⁺微米晶体在656 nm脉冲激光选择激发下, 均获得了强烈的单带近红外下转换荧光发射. 系统研究了激发波长、环境温度和颗粒长径比对NaYF₄:Tm³⁺微米晶体中单带近红外荧光强度的调控. 结果表明: 颗粒长径比越大, 荧光强度越强. 进一步探索了颗粒长径比调控的荧光增强机理, 并提出了基于长径比控制的缺陷空位机理.

关键词:

English

Strong Single-Band Down-Conversion Emission in Tm³⁺-Doped NaYF₄ Microparticles

1.
College of Science, Chang'an University, Xi'an 710064, P. R. China

Corresponding author: 张翔宇

Received Date: 15 June 2015
Fund Project:
中央高校基本科研业务费专项资金(2013G1121085, 310812152001)

国家自然科学基金(51101022)资助项目

Abstract: We synthesized Tm³⁺-doped NaYF₄ microcrystals with various length-to-diameter ratios by using a facile hydrothermal method assisted with sodium citrate from precursor solutions with various pH values. The β-NaYF₄:Tm³⁺ samples were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FT-IR) spectroscopy, and photoluminescence spectroscopy. XRD and SEM show that as the pH of the precursor solutions increased, the morphology of the microcrystals changed from long rods to short microprisms to microplates. We also investigated the luminescence properties of the β-NaYF₄:Tm³⁺ hexagonal microdisks and microrods. By selectively exciting the NaYF₄:Tm³⁺ microcrystals with a 656-nm pulsed laser at a pulse duration of 10 ns, they exhibited a strong single-band down-conversion emission at 800 nm. We systematically studied how the excitation wavelength, temperature, and length-to-diameter ratio of the particles affected the luminescence intensity of their near-infrared (NIR) single-band emission. As the length-to-diameter ratio of the NaYF₄:Tm³⁺ microcrystals increased, their luminescence intensity strengthened. Exploring the reason for this luminescence enhancement, we propose a mechanism based on vacancy defects.

Key words:

1. [1]
  (1) Chen, X. Y.; Liu, Y. S.; Tu, D. T. Lanthanide-doped Luminescent Nanomaterials: from Fundamentals to Bioapplications; Springer-Verlag Press: Heidelberg, 2014; pp 125-187.(1) Chen, X. Y.; Liu, Y. S.; Tu, D. T. Lanthanide-doped Luminescent Nanomaterials: from Fundamentals to Bioapplications; Springer-Verlag Press: Heidelberg, 2014; pp 125-187.
2. [2]
  (2) MacDougall, S. K. W.; Ivaturi, A.; Marques-Hueso, J.; Krä mer, K. W.; Richards, B. S. Sol. Energy Mater. Sol. Cells 2014, No. 128, 18. doi: 10.1016/j.solmat.2014.05.004(2) MacDougall, S. K. W.; Ivaturi, A.; Marques-Hueso, J.; Krä mer, K. W.; Richards, B. S. Sol. Energy Mater. Sol. Cells 2014, No. 128, 18. doi: 10.1016/j.solmat.2014.05.004
3. [3]
  (3) Chen, G. Y.; Qiu, H. L.; Prasad, P. N.; Chen, X. Y. Chem. Rev. 2014, 114 (10), 5161. doi: 10.1021/cr400425h(3) Chen, G. Y.; Qiu, H. L.; Prasad, P. N.; Chen, X. Y. Chem. Rev. 2014, 114 (10), 5161. doi: 10.1021/cr400425h
4. [4]
  (4) Zheng, W.; Tu, D. T.; Liu, Y. S.; Luo, W. Q.; Ma, E.; Zhu, H. M.; Chen, X. Y. Scientia Sinica Chimica 2014, 44 (2), 168. [郑伟, 涂大涛, 刘永升, 罗文钦, 马恩, 朱浩淼, 陈学元. 中国科学: 化学, 2014, 44 (2), 168.] doi: 10.1360/N032013-00041(4) Zheng, W.; Tu, D. T.; Liu, Y. S.; Luo, W. Q.; Ma, E.; Zhu, H. M.; Chen, X. Y. Scientia Sinica Chimica 2014, 44 (2), 168. [郑伟, 涂大涛, 刘永升, 罗文钦, 马恩, 朱浩淼, 陈学元. 中国科学: 化学, 2014, 44 (2), 168.] doi: 10.1360/N032013-00041
5. [5]
  (5) Wang, F.; Banerjee, D.; Liu, Y. S.; Chen, X. Y.; Liu, X. G. Analyst 2010, 135 (8), 1839. doi: 10.1039/C0AN00144A(5) Wang, F.; Banerjee, D.; Liu, Y. S.; Chen, X. Y.; Liu, X. G. Analyst 2010, 135 (8), 1839. doi: 10.1039/C0AN00144A
6. [6]
  (6) Ge, X. Y.; Yuan, Q. J. Wuhan Univ. (Nat. Sci. Ed.) 2015, 61, 10. [葛雪莹, 袁荃. 武汉大学学报: 理学版, 2015, 61, 10.](6) Ge, X. Y.; Yuan, Q. J. Wuhan Univ. (Nat. Sci. Ed.) 2015, 61, 10. [葛雪莹, 袁荃. 武汉大学学报: 理学版, 2015, 61, 10.]
7. [7]
  (7) Hampl, J.; Hall, M.; Mufti, N. A.; Yao, Y. M.; MacQueen, D. B.; Wright, W. H.; Cooper, D. E. Anal. Biochem. 2001, 288 (2), 176. doi: 10.1006/abio.2000.4902(7) Hampl, J.; Hall, M.; Mufti, N. A.; Yao, Y. M.; MacQueen, D. B.; Wright, W. H.; Cooper, D. E. Anal. Biochem. 2001, 288 (2), 176. doi: 10.1006/abio.2000.4902
8. [8]
  (8) Zou, W. Q.; Visser, C.; Maduro, J. A.; Pshenichnikov, M. S.; Hummelen, J. C. Nat. Photonics 2012, 6 (8), 560. doi: 10.1038/nphoton.2012.158(8) Zou, W. Q.; Visser, C.; Maduro, J. A.; Pshenichnikov, M. S.; Hummelen, J. C. Nat. Photonics 2012, 6 (8), 560. doi: 10.1038/nphoton.2012.158
9. [9]
  (9) Xie, X. J.; Liu, X. G. Nat. Mater. 2012, 11 (10), 842. doi: 10.1038/nmat3426(9) Xie, X. J.; Liu, X. G. Nat. Mater. 2012, 11 (10), 842. doi: 10.1038/nmat3426
10. [10]
  (10) Kumar, R. A.; Arivanandhan, M.; Hayakawa, Y. Progress in Crystal Growth and Characterization of Materials 2013, 59 (3), 113. doi: 10.1016/j.pcrysgrow.2013.07.001(10) Kumar, R. A.; Arivanandhan, M.; Hayakawa, Y. Progress in Crystal Growth and Characterization of Materials 2013, 59 (3), 113. doi: 10.1016/j.pcrysgrow.2013.07.001
11. [11]
  (11) Karaveli, S.; Zia, R. Phys. Rev. Lett. 2011, 106 (19), 193004. doi: 10.1103/PhysRevLett.106.193004(11) Karaveli, S.; Zia, R. Phys. Rev. Lett. 2011, 106 (19), 193004. doi: 10.1103/PhysRevLett.106.193004
12. [12]
  (12) Wang, F.; Liu, X. Accounts Chem. Res. 2014, 47 (4), 1378. doi: 10.1021/ar5000067(12) Wang, F.; Liu, X. Accounts Chem. Res. 2014, 47 (4), 1378. doi: 10.1021/ar5000067
13. [13]
  (13) Lu, Q.; Hou, Y.; Tang, A.; Wu, H.; Teng, F. Appl. Phys. Lett. 2013, 102 (23), 233103. doi: 10.1063/1.4811175(13) Lu, Q.; Hou, Y.; Tang, A.; Wu, H.; Teng, F. Appl. Phys. Lett. 2013, 102 (23), 233103. doi: 10.1063/1.4811175
14. [14]
  (14) Gao, D.; Zhang, X.; Gao, W. J. Appl. Phys. 2012, 111 (3), 033505. doi: 10.1063/1.3681293(14) Gao, D.; Zhang, X.; Gao, W. J. Appl. Phys. 2012, 111 (3), 033505. doi: 10.1063/1.3681293
15. [15]
  (15) Tian, D. P.; Gao, D. L.; Chong, B.; Liu, X. Z. Dalton Trans. 2015, 44 (9), 4133. doi: 10.1039/C4DT03735A(15) Tian, D. P.; Gao, D. L.; Chong, B.; Liu, X. Z. Dalton Trans. 2015, 44 (9), 4133. doi: 10.1039/C4DT03735A
16. [16]
  (16) Deng, T. L.; Yan, S. R.; Hu, J. G. Acta Phys. -Chim. Sin. 2014, 30 (4), 773. [邓陶丽, 闫世润, 胡建国. 物理化学学报, 2014, 30 (4), 773.] doi: 10.3866/PKU.WHXB201402201(16) Deng, T. L.; Yan, S. R.; Hu, J. G. Acta Phys. -Chim. Sin. 2014, 30 (4), 773. [邓陶丽, 闫世润, 胡建国. 物理化学学报, 2014, 30 (4), 773.] doi: 10.3866/PKU.WHXB201402201
17. [17]
  (17) Zhang, X. Y.; Li, L.; Gao, D. L.; Zheng, H. R. Spectrosc. Spect. Anal. 2009, 29, 2738. [张翔宇, 李林, 高当丽, 郑海荣. 光谱学与光谱分析, 2009, 29, 2738.](17) Zhang, X. Y.; Li, L.; Gao, D. L.; Zheng, H. R. Spectrosc. Spect. Anal. 2009, 29, 2738. [张翔宇, 李林, 高当丽, 郑海荣. 光谱学与光谱分析, 2009, 29, 2738.]
18. [18]
  (18) Nasim, H.; Jamil, Y. Optics & Laser Technology 2014, 56, 211. doi: 10.1016/j.optlastec.2013.08.012(18) Nasim, H.; Jamil, Y. Optics & Laser Technology 2014, 56, 211. doi: 10.1016/j.optlastec.2013.08.012
19. [19]
  (19) Wu, J.; Yao, Z.; Zong, J.; Jiang, S. Opt. Lett. 2007, 32 (6), 638. doi: 10.1364/OL.32.000638(19) Wu, J.; Yao, Z.; Zong, J.; Jiang, S. Opt. Lett. 2007, 32 (6), 638. doi: 10.1364/OL.32.000638
20. [20]
  (20) Zheng, L. J.; Li, Y. X.; Liu, H. L.; Xu, W.; Zhang, Z. G. Acta Phys. Sin. 2013, 62 (24), 240701. [郑龙江, 李雅新, 刘海龙, 徐伟, 张治国. 物理学报, 2013, 62 (24), 240701.] doi: 10.7498/aps.62.240701(20) Zheng, L. J.; Li, Y. X.; Liu, H. L.; Xu, W.; Zhang, Z. G. Acta Phys. Sin. 2013, 62 (24), 240701. [郑龙江, 李雅新, 刘海龙, 徐伟, 张治国. 物理学报, 2013, 62 (24), 240701.] doi: 10.7498/aps.62.240701
21. [21]
  (21) Zhang, X. Y.; Gao, D. L.; Zheng, H. R. Chin. Phys. B 2008, 17 (11), 4328. doi: 10.1088/1674-1056/17/11/061(21) Zhang, X. Y.; Gao, D. L.; Zheng, H. R. Chin. Phys. B 2008, 17 (11), 4328. doi: 10.1088/1674-1056/17/11/061
22. [22]
  (22) Gao, D. L.; Tian, D. P.; Xiao, G. Q.; Chong, B.; Yu, G. H.; Pang, Q. Opt. Lett. 2015, 40 (15), 3580. doi: 10.1364/OL.40.003580(22) Gao, D. L.; Tian, D. P.; Xiao, G. Q.; Chong, B.; Yu, G. H.; Pang, Q. Opt. Lett. 2015, 40 (15), 3580. doi: 10.1364/OL.40.003580
23. [23]
  (23) Krä mer, K. W.; Biner, D.; Frei, G.; Gü del, H. U.; Hehlen, M. P.; Lü thi, S. R. Chem. Mater. 2004, 16 (7), 1244. doi: 10.1021/cm031124o(23) Krä mer, K. W.; Biner, D.; Frei, G.; Gü del, H. U.; Hehlen, M. P.; Lü thi, S. R. Chem. Mater. 2004, 16 (7), 1244. doi: 10.1021/cm031124o
24. [24]
  (24) Gao, D. L.; Gao, W.; Shi, P.; Li, L. RSC Adv. 2013, 3 (34), 14757. doi: 10.1039/C3RA40517F(24) Gao, D. L.; Gao, W.; Shi, P.; Li, L. RSC Adv. 2013, 3 (34), 14757. doi: 10.1039/C3RA40517F
25. [25]
  (25) Gao, D. L.; Zhang, X. Y.; Zheng, H. R.; Shi, P.; Li, L.; Ling, Y. W. Dalton Trans. 2013, 42 (5), 1834. doi: 10.1039/C2DT31814H(25) Gao, D. L.; Zhang, X. Y.; Zheng, H. R.; Shi, P.; Li, L.; Ling, Y. W. Dalton Trans. 2013, 42 (5), 1834. doi: 10.1039/C2DT31814H
26. [26]
  (26) Yi, G.; Lu, H.; Zhao, S.; Ge, Y.; Yang, W.; Chen, D.; Guo, L. H. Nano Lett. 2004, 4 (11), 2191. doi: 10.1021/nl048680h(26) Yi, G.; Lu, H.; Zhao, S.; Ge, Y.; Yang, W.; Chen, D.; Guo, L. H. Nano Lett. 2004, 4 (11), 2191. doi: 10.1021/nl048680h
27. [27]
  (27) Gao, D.; Zhang, X.; Gao, W. ACS Appl. Mater. Interfaces 2013, 5 (19), 9732. doi: 10.1021/am402843h(27) Gao, D.; Zhang, X.; Gao, W. ACS Appl. Mater. Interfaces 2013, 5 (19), 9732. doi: 10.1021/am402843h
28. [28]
  (28) Zhang, X. Y.; Gao, D. L.; Li, L. J. Appl. Phys. 2010, 107 (12), 123528. doi: 10.1063/1.3436569(28) Zhang, X. Y.; Gao, D. L.; Li, L. J. Appl. Phys. 2010, 107 (12), 123528. doi: 10.1063/1.3436569
29. [29]
  (29) Gao, D. L.; Zhang, X. Y.; Zhang, Z. L.; Xu, L. M.; Lei, Y.; Zheng, H. R. Acta Phys. Sin. 2009, 58 (9), 6108. [ 高当丽, 张翔宇, 张正龙, 徐良敏, 雷瑜, 郑海荣. 物理学报, 2009, 58 (9), 6108.] doi: 10.7498/aps.58.6108(29) Gao, D. L.; Zhang, X. Y.; Zhang, Z. L.; Xu, L. M.; Lei, Y.; Zheng, H. R. Acta Phys. Sin. 2009, 58 (9), 6108. [ 高当丽, 张翔宇, 张正龙, 徐良敏, 雷瑜, 郑海荣. 物理学报, 2009, 58 (9), 6108.] doi: 10.7498/aps.58.6108
30. [30]
  (30) Gao, D. L.; Zheng, H. R.; Tian, Y.; Cui, M.; Lei, Y.; He, E. J.; Zhang, X. S. J. Nanosci. Nanotech. 2010, 10 (11), 7694. doi: 10.1166/jnn.2010.2787(30) Gao, D. L.; Zheng, H. R.; Tian, Y.; Cui, M.; Lei, Y.; He, E. J.; Zhang, X. S. J. Nanosci. Nanotech. 2010, 10 (11), 7694. doi: 10.1166/jnn.2010.2787
31. [31]
  (31) Miyakawa, T.; Dexter, D. L. Phys. Rev. B 1970, 1 (7), 2961. doi: 10.1103/PhysRevB.1.2961(31) Miyakawa, T.; Dexter, D. L. Phys. Rev. B 1970, 1 (7), 2961. doi: 10.1103/PhysRevB.1.2961
32. [32]
  (32) Liu, G. K. Chem. Soc. Rev. 2015, 44 (6), 163. doi: 10.1039/c4cs00187g(32) Liu, G. K. Chem. Soc. Rev. 2015, 44 (6), 163. doi: 10.1039/c4cs00187g
33. [33]
  (33) Zhang, S. Y. Spectroscopy of Rare Earth Ions: Spectral Property and Spectral Theory; Science Press: Beijing, 2008; pp 138-153. [张思远. 稀土离子的光谱学: 光谱性质和光谱理论. 北京: 科学出版社, 2008: 138-153.](33) Zhang, S. Y. Spectroscopy of Rare Earth Ions: Spectral Property and Spectral Theory; Science Press: Beijing, 2008; pp 138-153. [张思远. 稀土离子的光谱学: 光谱性质和光谱理论. 北京: 科学出版社, 2008: 138-153.]
34. [34]
  (34) Fu, J. X.; Fu, X. H.; Wang, C. M.; Yang, X. F.; Zhuang, J. L.; Zhang, G. G.; Lai, B. Y.; Wu, M. M.; Wang, J. Eur. J. Inorg. Chem. 2013, 2013 (8), 1269. doi: 10.1002/ejic.201201278(34) Fu, J. X.; Fu, X. H.; Wang, C. M.; Yang, X. F.; Zhuang, J. L.; Zhang, G. G.; Lai, B. Y.; Wu, M. M.; Wang, J. Eur. J. Inorg. Chem. 2013, 2013 (8), 1269. doi: 10.1002/ejic.201201278
35. [35]
  (35) Wu, Z.; Lin, M.; Liang, S.; Liu, Y.; Zhang, H.; Yang, B. Part. Part. Syst. Charact. 2013, 30 (4), 311. doi: 10.1002/ppsc.201200106(35) Wu, Z.; Lin, M.; Liang, S.; Liu, Y.; Zhang, H.; Yang, B. Part. Part. Syst. Charact. 2013, 30 (4), 311. doi: 10.1002/ppsc.201200106

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Tm³⁺掺杂的NaYF₄微米颗粒中强烈的单带下转换荧光发射

通讯作者: 张翔宇

English

Strong Single-Band Down-Conversion Emission in Tm³⁺-Doped NaYF₄ Microparticles

Corresponding author: 张翔宇

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Tm3+掺杂的NaYF4微米颗粒中强烈的单带下转换荧光发射

通讯作者: 张翔宇

English

Strong Single-Band Down-Conversion Emission in Tm3+-Doped NaYF4 Microparticles

Corresponding author: 张翔宇

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Tm³⁺掺杂的NaYF₄微米颗粒中强烈的单带下转换荧光发射

Strong Single-Band Down-Conversion Emission in Tm³⁺-Doped NaYF₄ Microparticles

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