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控制激发光功率密度是一种调控红绿荧光比率的简单方法.然而,大多数上转换系统对功率的调控并不敏感.本文通过柠檬酸钠辅助的水热法,合成了一系列具有不同Yb浓度掺杂的NaYF4:Yb/Ho微米棒.通过激光共聚焦显微镜系统,研究了Yb浓度和激发功率密度依赖的NaYF4:Yb/Ho微米棒的上转换荧光特性.发射谱和同步荧光成像图案表明:荧光红绿比率不仅敏感于激发功率,而且敏感度依赖于Yb浓度.随着Yb浓度的增加,功率调控的红绿比率的敏感度增加,这暗示了功率调控的红绿比率的敏感度可以作为一种度量和评估Yb掺杂浓度的有效途径和方法.通过上/下转换发射谱、激发谱和功率依赖关系,揭示了功率调控红绿比率的机理,并提出了荧光色彩敏感于功率调控的上转换系统具有的特征和判据.本研究为设计和合成高敏感度的功率调控的上转换材料提供了理论基础和实验数据.Controlling the power density of exciting light is a widely applied technological approach to dynamically tuning emission spectra to yield desirable luminescence properties, which is essential for various applications in laser devices, cancer cell imaging, biomarker molecule detections, thermometers and optoelectronic devices. However, most of upconversion systems are insensitive to power regulation. In this study, a series of Yb/Ho doped NaYF4 microrods with different Yb concentrations was synthesized by using a sodium citrate-assisted hydrothermal method. The dependence of upconversion characteristics of NaYF4:Yb/Ho microrods on Yb concentration and excitation power density are investigated in detail by a laser confocal microscopy system. The emission spectra exhibit discrete upconversion emission characteristic peaks that can easily be assigned to 5F3→5I8 (at about 488 nm), 5F4, 5S2→5I8 (at about 543 nm), 3K7, 5G4→5I8 (at about 580 nm) and 5F5→5I8 (at about 648 nm) transitions of Ho, respectively. The upconversion spectra and synchronous luminescence imaging patterns show that the luminescence ratio of red to green is not only dependent on the Yb concentration, but also sensitive to the excitation power. With Yb concentration increasing from 5% to 60%, the sensitivity of the power-controlled red to green luminescence ratio largely increases from 0.1% to 13.0%, corresponding to a clear luminescent color modification from green to red. These results indicate that the power-tuned red-to-green-luminescence ratio can be used as a method of measuring and evaluating Yb doping concentration. We attribute the sensitivity tuned by Yb concentration to the differences in population approach and upconversion mechanism for the red and green luminescence. By recording the slope of luminescence intensity versus exciting power density in a double-logarithmic presentation, we detect a small slope for the green emission relative to that for the red emission, especially at a high Yb concentration. These results indicate that the red upconversion process may be a three-photon process. The exciting power induced color adjusting is therefore explained by preferential three-photon population of the red emission due to the high 5S2→5G4 excitation rate, which is verified by down-conversions of emission spectra. Our present study provides a theoretical basis for the spectral tailoring of rare-earth micro/nano materials and supplies a foundation for the applications in rare-earth materials.
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Keywords:
- Yb concentration /
- upconversion /
- luminescence color /
- sensitivity regulation
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[1] Auzel F 1966 CR Acad. Sci. Paris 263 819
[2] Wang F, Banerjee D, Liu Y, Chen X, Liu X 2010 Analyst 135 1839
[3] Ai X Z, Ho C J H, Aw J X, Attia A B E, Mu J, Wang Y, Wang X Y, Wang Y, Liu X G, Chen H B, Gao M Y, Chen X Y, Yeow E K L, Liu G, Olivo M, Xing B J 2016 Nat. Commun. 7 10432
[4] Zheng S H, Chen W B, Tan D Z, Zhou J J, Guo Q B, Jiang W, Xu C, Liu X F, Qiu J R 2014 Nanoscale 6 5675
[5] Wickberg A, Mueller J B, Mange Y J, Fischer J, Nann T, Wegener M 2015 Appl. Phys. Lett. 106 133103
[6] Dey R, Rai V K 2014 Dalton Trans. 43 111
[7] Azam M, Rai V K 2017 Solid State Sci. 66 7
[8] Chen G Y, Shen J, Ohulchanskyy T Y, Patel N J, Kutikov A, Li Z P, Song J, Pandey R K, Ågren H, Prasad P N, Han G 2012 ACS Nano 6 8280
[9] Hong G, Antaris A L, Dai H 2017 Nat. Biomed. Engineer. 1 0010
[10] Pepin P A, Diroll B T, Choi H J, Murray C B, Vohs J M 2017 J. Phys. Chem. C 121 11488
[11] Erogbogbo F, Yong K T, Roy I, Hu R, Law W C, Zhao W, Prasad P N, Ding H, Wu F, Kumar R, Swihart M T 2010 ACS Nano 5 413
[12] Yang Y, Mi C, Jiao F Y, Su X Y, Li X D, Liu L L, Zhang J, Yu F, Liu Y Z, Mai Y H 2014 J. Am. Ceram. Soc. 97 1769
[13] Zhang Z Y, Suo H, Zhao X Q, Sun D, Fan L, Guo C F 2018 ACS Appl. Mater. Interfaces 10 14570
[14] Suo H, Zhao X, Zhang Z, Shi R, Wu Y, Xiang J, Guo C 2018 Nanoscale 10 9245
[15] Wang L, Li Y 2007 Chem. Mater. 19 727
[16] Gao D L, Wang D, Zhang X Y, Feng X Y, Xin H, Yun S N, Tian D P 2018 J. Mater. Chem. C 6 622
[17] Zhang X Y, Wang D, Shi H W, Wang J G, Hou Z Y, Zhang L D, Gao D L 2018 Acta Phys. Sin. 67 84203 (in Chinese) [张翔宇, 王丹, 石焕文, 王晋国, 侯兆阳, 张力东, 高当丽 2018 物理学报 67 84203]
[18] Gao D L, Zhang X Y, Chong B, Xiao G Q, Tian D P 2017 Phys. Chem. Chem. Phys. 19 4288
[19] Zhou B, Shi B, Jin D, Liu X 2015 Nat. Nanotech. 10 924
[20] Gao D L, Zhang X Y, Zheng H R, Shi P, Li L, Ling Y W 2013 Dalton Trans. 42 1834
[21] Gao D L, Zhang X Y, Zheng H R, Gao W, He E J 2013 J. Alloys Compd. 554 395
[22] Shao W, Chen G, Kuzmin A, Kutscher H L, Pliss A, Ohulchanskyy T Y, Prasad P N 2016 J. Am. Chem. Soc. 138 16192
[23] Gao D L, Zhang X Y, Gao W 2013 ACS Appl. Mater. Interfaces 5 9732
[24] Gao D L, Tian D P, Zhang X Y, Gao W 2016 Sci. Rep. 6 22433
[25] Yi G S, Chow G M 2005 J. Mater. Chem. 15 4460
[26] Chen B, Liu Y, Xiao Y, Chen X, Li Y, Li M Y, Qiao X S, Fan X P, Wang F 2016 J. Phys. Chem. Lett. 7 4916
[27] Gao W, Wang R, Han Q, Dong J, Yan L, Zheng H 2015 J. Phys. Chem. C 119 2349
[28] Gao D, Zhang X, Pang Q, Zhao J, Xiao G, Tian D 2018 J. Mater. Chem. C 6 8011
[29] Deng K, Gong T, Hu L, Wei X, Chen Y, Yin M 2011 Opt. Exp. 19 1749
[30] Wang L, Lan M, Liu Z, Qin G, Wu C, Wang X, Qin W, Huang W, Huang L 2013 J. Mater. Chem. C 1 2485
[31] Wang M Y, Tian Y, Zhao F Y, Li R F, You W W, Fang Z L, Chen X Y, Huang W, Ju Q 2017 J. Mater. Chem. C 5 1537
[32] Zhang J H, Hao Z D, Li J, Zhang X, Luo Y S, Pan G H 2015 Light: Sci. Appl. 4 e239
[33] Gamelin D R, Gudel H U 2001 Transition Metal and Rare Earth Compounds (Vol. 214) (Berlin, Heidelberg: Springer) p1
[34] Luthi S R, Pollnau M, Gudel H U, Hehlen M P 1999 Phys. Rev. B 60 162
[35] Pollnau M, Gamelin D R, Luthi S R, Gudel H U, Hehlen M P 2000 Phys. Rev. B 61 3337
[36] Yang Y M, Jiao F Y, Su H X, Li Z Q, Liu Y F, Li Z Q, Yang Z P 2012 Spectrosc. Spect. Anal. 32 2637 (in Chinese) [杨艳民, 焦福运, 苏红新, 李自强, 刘云峰, 李志强, 杨志平 2012 光谱学与光谱分析 32 2637]
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