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锰离子对镥基纳米晶体的荧光调控与增强

何恩节 郑海荣 高伟 鹿盈 李俊娜 魏映 王灯 朱刚强

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锰离子对镥基纳米晶体的荧光调控与增强

何恩节, 郑海荣, 高伟, 鹿盈, 李俊娜, 魏映, 王灯, 朱刚强

Mn2+ induced luminescence regulation and enhancement of Lu-based nanocrystals

He En-Jie, Zheng Hai-Rong, Gao Wei, Lu Ying, Li Jun-Na, Wei Ying, Wang Deng, Zhu Gang-Qiang
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  • 通过调控Mn2+的掺杂浓度,在镥基纳米晶体成功地实现了六方、四方混合相到纯四方相的相位转变,并详细讨论了其相变机理. 时域和频域光谱的分析表明,立方相Na5Lu9F32:40% Mn2+,20% Yb3+,2% Ln3+(Ln=Er3+,Ho3+)纳米晶体内的准纯红色荧光发射主要由Mn2+和Ln3+之间的两步能量转移引起. Mn2+掺杂后引起了发光离子附近局域对称性的降低,使得电偶极跃迁的辐射速率明显增加,进而导致了上转换、下转换荧光的极大增强. 该研究结果在生物荧光成像、太阳能电池效率的提高方面具备潜在的、广阔的应用前景.
    Transformation from Lu-based nanocrystals in hexagonal and cubic mixed phases to pure cubic phase was observed through adjusting the doping concentration of Mn2+. The mechanism for the phase transformation was discussed in detail. Studies on the time and frequency domain spectra indicated that the semi-pure red emissions in cubic Na5Lu9F32: 40% Mn2+, 20% Yb3+, 2% Ln3+ (Ln=Er3+, Ho3+) nanocrystals were caused by a two-step energy transfer between Mn2+ and Ln3+ ions. After incorporating of Mn2+ ions into the host lattices, the local symmetry around the luminescent ion was reduced, which induced the increase of radiative rates for transitions that were mainly contributed by electric dipole radiations. Considerable enhancements in upconversion and downconversion luminescence were accompanied. The result of the current study has great application potential in bioimaging and solar cells.
    • 基金项目: 国家自然科学基金(批准号:11174190)和安徽省高等学校省级自然科学研究项目(批准号:KJ2011Z082)资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11174190), and the Natural Science Foundation of University in Anhui Province, China (Grant No. KJ2011Z082).
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    Chen D Q, Yu Y L, Huang F, Huang P, Yang A P, Wang Y S 2010 J. Am. Chem. Soc. 132 9976

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    Wang F, Han Y, Lim C S, Lu Y H, Wang J, Xu J, Chen H Y, Zhang C, Hong M H, Liu X G 2010 Nature 463 1061

    [27]

    Pan L Y, He M, Ma J B, Tang W, Gao G, He R, Su H C, Cui D X 2013 Theranostics 3 210

    [28]

    Chen D Q, Yu Y L, Huang F, Wang Y S 2011 Chem. Commun. 47 2601

    [29]

    Pollnau M, Gamelin D R, Lthi S R, Gdel H U 2000 Phys. Rev. B 61 3337

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    Renero-Lecuna C, Martín-Rodríguez R, Valiente R 2011 Chem. Mater. 23 3442

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    Sell D D, Greene R L, White R M 1967 Phys. Rev. 158 489

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    Zeng J H, Xie T, Li Z H, Li Y D 2007 Cryst. Growth Des. 7 2774

    [33]

    Xie M Y, Peng X N, Fu X F, Zhang J J, Li G L, Yu X F 2009 Scr. Mater. 60 190

    [34]

    Ghosh P, Patra A 2008 J. Phys. Chem. C 112 19283

    [35]

    He E J, Zheng H R, Zhang Z L, Zhang X S, Xu L M, Fu Z X, Lei Y 2010 J. Nanosci. Nanotechnol. 10 1908

    [36]

    Wang F, Liu X G 2008 J. Am. Chem. Soc. 130 5642

    [37]

    Myint T, Gunawidjaja R, Eilers H 2011 Appl. Phys. Lett. 98 171906

    [38]

    Judd B R 1962 Phys. Rev. 127 750

    [39]

    Ofelt G S 1962 J. Chem. Phys. 37 511

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    Ebendorff-Heidepriema H, Ehrta D, Bettinellib, Speghinib A 1998 J. Non-Cryst. Solids 240 66

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  • [1]

    van Sark W GJHM, de Wild J, Meijerink A, Schropp R EI 2013 Nanoscale Res. Lett. 8 81

    [2]

    Li Z Q, Li X D, Liu Q Q, Chen X H, Sun Z, Liu C, Ye X J, Huang S M 2012 Nanotechnology 23 025402

    [3]

    Liu Q, Sun Y, Yang T S, Feng W, Li C G, Li F Y 2011 J. Am. Chem. Soc. 133 17122

    [4]

    Sun Y, Peng J J, Feng W, Li F Y 2013 Theranostics 3 346

    [5]

    Psuja P, Hreniak D, Strek W 2007 J. Nanomater. 2007 81350

    [6]

    Krut’ko V A, Ryabova A V, Komova M G, Popov A V, Volkov V V, Kargin Y F, Loshchenov V B 2013 Inorg. Mater. 49 76

    [7]

    Zhou W L, Zhang Q Li, Gao J Y, Liu W P, Ding L H, Yin S T 2011 Chin. Phys. B 20 016101

    [8]

    He E J, Liu N, Zhang M L, Qin Y Fu, Guan B G, Li Y, Guo M 2012 Chin. Phys. B 21 073201

    [9]

    Zhang J C, Qin Q S, Yu M H, Sun J Y, Shi L R, Ma X L 2011 Chin. Phys. Lett. 28 027802

    [10]

    Wang F, Banerjee D, Liu Y S, Chen X Y, Liu X G 2010 Analyst 135 1839

    [11]

    Shi F, Wang J S, Zhai X S, Zhao D, Qin W P 2011 Crystengcomm 13 3782

    [12]

    Yu X F, Li M, Xie M Y, Chen L D, Li Y, Wang Q Q 2010 Nano Res. 3 51

    [13]

    Liu S, Chen G Y, Ohulchanskyy T Y, Swihart M T, Prasad P N 2013 Theranostics 3 275

    [14]

    Wang Q, Tan M C, Zhuo R, Kumar G A, Riman R E 2010 J. Nanosci. Nanotechnol. 10 1685

    [15]

    Krämer K W, Biner D, Frei G, Gdel H U, Hehlen M P, Lthi S R 2004 Chem. Mat. 16 1244

    [16]

    Cheng L, Yang K, Shao M M, Lee S T, Liu Z 2011 J. Phys. Chem. C 115 2686

    [17]

    Niu N, Yang P P, He F, Zhang X, Gai S L, Li C X, Lin J 2012 J. Mater. Chem. 22 10889

    [18]

    Boyer J C, Vetrone F, Cuccia L A, Capobianco J A 2006 J. Am. Chem. Soc. 128 7444

    [19]

    Chang J, Liu Y, Li J, Wu S L, Niu W B, Zhang S F 2013 J. Mater. Chem. C 1 1168

    [20]

    Wang J, Wang F, Wang C, Liu Z, Liu X G 2011 Angew. Chem. Int. Ed. 50 10369

    [21]

    Tian G, Gu Z J, Zhou L J, Yin W Y, Liu X X, Yan L, Jin S, Ren W L, Xing G M, Li S J, Zhao Y L 2012 Adv. Mater. 24 1226

    [22]

    Wang L L, Lan M, Liu Z Y, Qin G S, Wu C F, Wang X, Qin W P, Huang W, Huang L 2013 J. Mater. Chem. C 1 2485

    [23]

    He E J, Zheng H R, Gao W, Tu Y X, Lu Y, Li G A 2013 Mater. Res. Bull. 48 3505

    [24]

    Zhang F, Wan Y, Yu T, Zhang F Q, Shi Y F, Xie S H, Li Y G, Xu L, Tu B, Zhao D Y 2007 Angew. Chem. Int. Ed. 46 7976

    [25]

    Chen D Q, Yu Y L, Huang F, Huang P, Yang A P, Wang Y S 2010 J. Am. Chem. Soc. 132 9976

    [26]

    Wang F, Han Y, Lim C S, Lu Y H, Wang J, Xu J, Chen H Y, Zhang C, Hong M H, Liu X G 2010 Nature 463 1061

    [27]

    Pan L Y, He M, Ma J B, Tang W, Gao G, He R, Su H C, Cui D X 2013 Theranostics 3 210

    [28]

    Chen D Q, Yu Y L, Huang F, Wang Y S 2011 Chem. Commun. 47 2601

    [29]

    Pollnau M, Gamelin D R, Lthi S R, Gdel H U 2000 Phys. Rev. B 61 3337

    [30]

    Renero-Lecuna C, Martín-Rodríguez R, Valiente R 2011 Chem. Mater. 23 3442

    [31]

    Sell D D, Greene R L, White R M 1967 Phys. Rev. 158 489

    [32]

    Zeng J H, Xie T, Li Z H, Li Y D 2007 Cryst. Growth Des. 7 2774

    [33]

    Xie M Y, Peng X N, Fu X F, Zhang J J, Li G L, Yu X F 2009 Scr. Mater. 60 190

    [34]

    Ghosh P, Patra A 2008 J. Phys. Chem. C 112 19283

    [35]

    He E J, Zheng H R, Zhang Z L, Zhang X S, Xu L M, Fu Z X, Lei Y 2010 J. Nanosci. Nanotechnol. 10 1908

    [36]

    Wang F, Liu X G 2008 J. Am. Chem. Soc. 130 5642

    [37]

    Myint T, Gunawidjaja R, Eilers H 2011 Appl. Phys. Lett. 98 171906

    [38]

    Judd B R 1962 Phys. Rev. 127 750

    [39]

    Ofelt G S 1962 J. Chem. Phys. 37 511

    [40]

    Ebendorff-Heidepriema H, Ehrta D, Bettinellib, Speghinib A 1998 J. Non-Cryst. Solids 240 66

    [41]

    Weber M J 1967 Phys. Rev. 157 262

    [42]

    Carnall W T, Fields P R, Sarup R 1972 J. Chem. Phy. 57 43

计量
  • 文章访问数:  1831
  • PDF下载量:  675
  • 被引次数: 0
出版历程
  • 收稿日期:  2013-08-04
  • 修回日期:  2013-08-25
  • 刊出日期:  2013-12-05

锰离子对镥基纳米晶体的荧光调控与增强

  • 1. 陕西师范大学物理学与信息技术学院, 西安 710062;
  • 2. 安徽科技学院理学院, 蚌埠 233100
    基金项目: 

    国家自然科学基金(批准号:11174190)和安徽省高等学校省级自然科学研究项目(批准号:KJ2011Z082)资助的课题.

摘要: 通过调控Mn2+的掺杂浓度,在镥基纳米晶体成功地实现了六方、四方混合相到纯四方相的相位转变,并详细讨论了其相变机理. 时域和频域光谱的分析表明,立方相Na5Lu9F32:40% Mn2+,20% Yb3+,2% Ln3+(Ln=Er3+,Ho3+)纳米晶体内的准纯红色荧光发射主要由Mn2+和Ln3+之间的两步能量转移引起. Mn2+掺杂后引起了发光离子附近局域对称性的降低,使得电偶极跃迁的辐射速率明显增加,进而导致了上转换、下转换荧光的极大增强. 该研究结果在生物荧光成像、太阳能电池效率的提高方面具备潜在的、广阔的应用前景.

English Abstract

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