Journal Home > Volume 8 , Issue 2
Nano Research 2015, 8(2): 636-648 https://doi.org/10.1007/s12274-014-0548-2
Research Article | Issue | Published: 09 September 2014

Magnetic and optical properties of NaGdF4: Nd3+, Yb3+, Tm3+ nanocrystals with upconversion/downconversion luminescence from visible to the near-infrared second window

Show Author's Information Xianwen Zhang1,§,  Zhi Zhao2,§,  Xin Zhang3,  David B. Cordes4,5,  Brandon Weeks3,  Bensheng Qiu6,  Kailasnath Madanan7,8,  Dhiraj Sardar7,  Jharna Chaudhuri1( )
Department of Mechanical EngineeringTexas Tech UniversityLubbockTexas79409USA
Hefei National Laboratory for Physical Sciences at the MicroscaleUniversity of Science and Technology of ChinaHefeiAnhui230026China
Department of Chemical EngineeringTexas Tech UniversityLubbockTexas79409USA
Department of Chemistry & BiochemistryTexas Tech UniversityLubbockTexas79409USA
EaStCHEM School of Chemistry, University of St. Andrews, St. AndrewsKY16 9STUK
School of Information Science and TechnologyUniversity of Science and Technology of ChinaHefeiAnhui230026China
Department of Physics and AstronomyUniversity of Texas at San AntonioSan AntonioTexas78249USA
International School of PhotonicsCochin University of Science and TechnologyKochi682022India

§These authors contributed equally.

Keywords:
photoluminescence, nanocrystals, window, energy transfer, near-infrared second
Cite this article:
Zhang X, Zhao Z, Zhang X, et al. Magnetic and optical properties of NaGdF4: Nd3+, Yb3+, Tm3+ nanocrystals with upconversion/downconversion luminescence from visible to the near-infrared second window. Nano Research, 2015, 8(2): 636-648. https://doi.org/10.1007/s12274-014-0548-2
Download citation
EndNote(RIS)
BibTeX

566

Views

16

Downloads

Citations

85

Crossref

N/A

WoS

84

Scopus

0

CSCD

Abstract Full text About this article

We have designed and synthesized NaGdF4: Nd3+, Yb3+, Tm3+ magnetic nanophosphors with combined dual-mode downconversion (DC) and upconversion (UC) photoluminescence upon 800 nm excitation. Hexagonal-phase NaGdF4: Nd3+, Yb3+, Tm3+ nanocrystals (NCs) with an average size of 21 nm were synthesized using a solvothermal approach. Nd3+, Yb3+, Tm3+ triple-doped NaGdF4 NCs exhibit a broad range of photoluminescence peaks covering a near infrared first/second window (860–900, 1, 000, and 1, 060 nm), and visible emission including blue (475 nm), green (520 and 542 nm) and yellow (587 nm) after excitation at 800 nm. A mechanism involving circulation of energy over Gd3+ sublattices as bridge ions and final trapping by the initial activator ions (Nd3+) has been proposed. Penetration depth studies indicate that NIR emission is easily detected even at a large tissue thickness of 10 mm. These paramagnetic nanophosphors demonstrate a large magnetization value of 1.88 emu/g at 20 kOe and longitudinal relaxivity value of 1.2537 mM-1·S-1 as a T1-weighted magnetic resonance imaging contrast agent. These NaGdF4: Nd3+, Yb3+, Tm3+ NCs are promising for applications in biological and magnetic resonance imaging.


menu
Abstract
Full text
Outline
About this article

Magnetic and optical properties of NaGdF4: Nd3+, Yb3+, Tm3+ nanocrystals with upconversion/downconversion luminescence from visible to the near-infrared second window

Show Author's information Xianwen Zhang1,§, Zhi Zhao2,§, Xin Zhang3, David B. Cordes4,5, Brandon Weeks3, Bensheng Qiu6, Kailasnath Madanan7,8, Dhiraj Sardar7, Jharna Chaudhuri1( )
Department of Mechanical EngineeringTexas Tech UniversityLubbockTexas79409USA
Hefei National Laboratory for Physical Sciences at the MicroscaleUniversity of Science and Technology of ChinaHefeiAnhui230026China
Department of Chemical EngineeringTexas Tech UniversityLubbockTexas79409USA
Department of Chemistry & BiochemistryTexas Tech UniversityLubbockTexas79409USA
EaStCHEM School of Chemistry, University of St. Andrews, St. AndrewsKY16 9STUK
School of Information Science and TechnologyUniversity of Science and Technology of ChinaHefeiAnhui230026China
Department of Physics and AstronomyUniversity of Texas at San AntonioSan AntonioTexas78249USA
International School of PhotonicsCochin University of Science and TechnologyKochi682022India

§These authors contributed equally.

Abstract

We have designed and synthesized NaGdF4: Nd3+, Yb3+, Tm3+ magnetic nanophosphors with combined dual-mode downconversion (DC) and upconversion (UC) photoluminescence upon 800 nm excitation. Hexagonal-phase NaGdF4: Nd3+, Yb3+, Tm3+ nanocrystals (NCs) with an average size of 21 nm were synthesized using a solvothermal approach. Nd3+, Yb3+, Tm3+ triple-doped NaGdF4 NCs exhibit a broad range of photoluminescence peaks covering a near infrared first/second window (860–900, 1, 000, and 1, 060 nm), and visible emission including blue (475 nm), green (520 and 542 nm) and yellow (587 nm) after excitation at 800 nm. A mechanism involving circulation of energy over Gd3+ sublattices as bridge ions and final trapping by the initial activator ions (Nd3+) has been proposed. Penetration depth studies indicate that NIR emission is easily detected even at a large tissue thickness of 10 mm. These paramagnetic nanophosphors demonstrate a large magnetization value of 1.88 emu/g at 20 kOe and longitudinal relaxivity value of 1.2537 mM-1·S-1 as a T1-weighted magnetic resonance imaging contrast agent. These NaGdF4: Nd3+, Yb3+, Tm3+ NCs are promising for applications in biological and magnetic resonance imaging.

Keywords: photoluminescence, nanocrystals, window, energy transfer, near-infrared second

References(53)

1

Zhou, J.; Liu, Z.; Li, F. Upconversion nanophosphors for small-animal imaging. Chem. Soc. Rev. 2012, 41, 1323-1349.
Google Scholar
2

Wei, J.; Qiu, J; Ren, L.; Zhang, K.; Wang, S.; Weeks, B. Size sorted multicolor fluorescence graphene oxide quantum dots obtained by differential velocity centrifugation. Sci. Adv. Mater. 2014, 6, 1052-1059.
Google Scholar
3

Cai, W.; Shin, D.; Chen, K.; Gheysens, O.; Cao, Q.; Wang, S. X.; Gambhir, S. S.; Chen, X. Peptide-labeled near-infrared quantum dots for imaging tumor vasculature in living subjects. Nano Lett. 2006, 6, 669-676.
Google Scholar
4

Chance, B. Near-infrared images using continuous, phase-modulated, and pulsed light with quantitation of blood and blood oxygenation. Ann. N Y Acad. Sci. 1998, 838, 29-45.
Google Scholar
5

Chen, G.; Ohulchanskyy, T. Y.; Liu, S.; Law, W.; Wu, F.; Swihart, M. T.; Ågren, H.; Prasad, P. N. Core/shell NaGdF4: Nd3+/NaGdF4 nanocrystals with efficient near-infrared to near-infrared downconversion photoluminescence for bioimaging applications. ACS Nano 2012, 6, 2969-2977.
Google Scholar
6

Escobedo, J. O.; Rusin, O.; Lim, S.; Strongin, R. M. NIR dyes for bioimaging applications. Curr. Opin. Chem. Biol. 2010, 14, 64-70.
Google Scholar
7

Michalet, X.; Pinaud, F. F.; Bentolila, L. A.; Tsay, J. M.; Doose, S.; Li, J. J.; Sundaresan, G.; Wu, A. M.; Gambhir, S. S.; Weiss. S. Quantum dots for live cells, in vivo imaging, and diagnostics. Science 2005, 307, 538-544.
Google Scholar
8

Wang, M.; Mi, C. C.; Wang, W. C.; Liu, C. H.; Wu, Y. F.; Xu, Z. R.; Mao, C. B.; Xu, S. K. Immunolabeling and NIR-excited fluorescent imaging of HeLa cells by using NaYF4: Yb, Er upconversion nanoparticles. ACS Nano 2009, 3, 1580-1586.
Google Scholar
9

Welsher, K.; Sherlock, S. P.; Dai, H. Deep-tissue anatomical imaging of mice using carbon nanotube fluorophores in the second near-infrared window. Proc. Natl. Acad. Sci. USA 2011, 108, 8943-8948.
Google Scholar
10

Smith, A. M.; Mancini, M. C.; Nie, S. Bioimaging: Second window for in vivo imaging. Nat. Nanotechnol. 2009, 4, 710-711.
Google Scholar
11

Frangioni, J. V.; Nakayama, A.; Lim, Y. T.; Kim, S.; Stott, N. E.; Bawendi, M. G. Selection of quantum dot wavelengths for biomedical assays and imaging. Mol Imaging 2003, 2, 50-64.
Google Scholar
12

Zhang, Y.; Hong, G.; Zhang, Y.; Chen, G.; Li, F.; Dai, H.; Wang, Q. Ag2S quantum dot: A bright and biocompatible fluorescent nanoprobe in the second near-infrared window. ACS Nano 2012, 6, 3695-3702.
Google Scholar
13

Wehrenberg, B. L.; Wang, C. J.; Guyot-Sionnest, P. Interband and intraband optical studies of PbSe colloidal quantum dots. J. Phys. Chem. B 2002, 106, 10634-10640.
Google Scholar
14

Bakueva, L.; Gorelikov, I.; Musikhin, S.; Zhao, X. S.; Sargent, E. H.; Kumacheva, E. PbS quantum dots with stable efficient luminescence in the near-IR spectral range. Adv. Mater. 2004, 16, 926-929.
Google Scholar
15

Harrison, M. T.; Kershaw, S. V.; Burt, M. G.; Eychmüller, A.; Weller, H.; Rogach, A. L. Wet chemical synthesis and spectroscopic study of CdHgTe nanocrystals with strong near-infrared luminescence. Mater. Sci. Eng. B 2000, 69-70, 355-360.
Google Scholar
16

Yi, H.; Ghosh, D.; Ham, M.; Qi, J.; Barone, P. W.; Strano, M. S.; Belcher, A. M. M13 phage-functionalized single-walled carbon nanotubes as nanoprobes for second near-infrared window fluorescence imaging of targeted tumors. Nano Lett. 2012, 12, 1176-1183.
Google Scholar
17

Welsher, K.; Liu, Z.; Sherlock, S. P.; Robinson, J. T.; Chen, Z.; Daranciang, D.; Dai, H. A route to brightly fluorescent carbon nanotubes for near-infrared imaging in mice. Nat. Nanotechnol. 2009, 4, 773-780.
Google Scholar
18

Robinson, J. T.; Liu, Z.; Sherlock, S. P.; Robinson, J. T.; Chen, Z.; Daranciang, D.; Dai, H. In vivo fluorescence imaging in the second near-infrared window with long circulating carbon nanotubes capable of ultrahigh tumor uptake. J. Am. Chem. Soc. 2012, 134, 10664-10669.
Google Scholar
19

Cheng, L.; Yang, K.; Zhang, S.; Shao, M.; Lee, S.; Liu, Z. Highly-sensitive multiplexed in vivo imaging using PEGylated upconversion nanoparticles. Nano Res. 2010, 3, 722-732.
Google Scholar
20

An, M.; Cui, J.; He, Q.; Wang, L. Down-/up-conversion luminescence nanocomposites for dual-modal cell imaging. J. Mater. Chem. B 2013, 1, 1333-1339.
Google Scholar
21

Xing, H.; Bu, W.; Zhang, S.; Zheng, X.; Li, M.; Chen, F.; He, Q.; Zhou, L.; Peng, W.; Hua, Y. Multifunctional nanoprobes for upconversion fluorescence, MR and CT trimodal imaging. Biomaterials 2012, 33, 1079-1089.
Google Scholar
22

Liu, K.; Liu, X.; Zeng, Q.; Zhang, Y.; Tu, L.; Liu, T.; Kong, X.; Wang, Y.; Cao, F.; Lambrechts, S. G.; et al. Covalently assembled NIR nanoplatform for simultaneous fluorescence imaging and photodynamic therapy of cancer cells. ACS Nano 2012, 6, 4054-4062.
Google Scholar
23

Wu, S.; Milliron, D. J.; Aloni, S.; Altoea, V.; Talapin, D. V.; Cohen, B. E.; Schuck, P. J. Non-blinking and photostable upconverted luminescence from single lanthanide-doped nanocrystals. Proc. Natl. Acad. Sci. USA 2009, 106, 10917-10921.
Google Scholar
24

Li, P.; Peng, Q.; Li, Y. D. Dual-mode luminescent colloidal spheres from monodisperse rare-earth fluoride nanocrystals. Adv. Mater. 2009, 21, 1945-1948.
Google Scholar
25

Liu, Y.; Tu, D.; Zhu, H.; Li, R.; Luo, W.; Chen, X. A strategy to achieve efficient dual-mode luminescence of Eu3+ in lanthanides doped multifunctional NaGdF4 nanocrystals. Adv. Mater. 2010, 22, 3266-3271.
Google Scholar
26

Bai, X.; Li, D.; Liu, Q.; Dong, B.; Xu, S.; Song, H. Concentration-controlled emission in LaF3: Yb3+/Tm3+ nanocrystals: Switching from UV to NIR regions. J. Mater. Chem. 2012, 22, 24698-24704.
Google Scholar
27

Kumar, R.; Nyk, M.; Ohulchanskyy, T. Y.; Flask, C. A.; Prasad, P. N. Combined optical and MR bioimaging using rare earth ion doped NaYF4 nanocrystals. Adv. Funct. Mater. 2009, 19, 853-859.
Google Scholar
28

Liu, Y.; Wang, D.; Shi, J.; Peng, Q.; Li, Y. D. Magnetic tuning of upconversion luminescence in lanthanide-doped bifunctional nanocrystals. Angew. Chem. Int. Ed. 2013, 52, 4366-4369.
Google Scholar
29

Zhang, X. W.; Zhi, Z.; Zhang, X.; Marathe, A.; Cordes, D. B.; Weeks, B.; Chaudhuri, J. Tunable photoluminescence and energy transfer of YBO3: Tb3+, Eu3+ for white light emitting diodes. J. Mater. Chem. C 2013, 1, 7202-7207.
Google Scholar
30

Zhang, X. W.; Marathe, A.; Sandeep, S.; Holtz, M.; Davis, M.; Hope-Weeks, L. J. Synthesis and photoluminescence properties of hierarchical architectures of YBO3: Eu3+. J. Mater. Chem. 2012, 22, 6485-6490.
Google Scholar
31

Zhang, X. W.; Zhang, M. F.; Zhu, Y. C.; Wang, P. F.; Xue, F.; Gu, J.; Bi, H. Y.; Qian, Y. T. Hydrothermal synthesis and luminescent properties of LaPO4: Eu 3D microstructures with controllable phase and morphology. Mater. Res. Bull. 2011, 45, 1324-1329.
Google Scholar
32

Pokhrel, M.; Mimun, L. C.; Yust, B.; Kumar, G. A.; Dhanale, A.; Tang, L.; Sardar, D. K. Stokes emission in GdF3: Nd3+ nanoparticles for bioimaging probes. Nanoscale 2014, 6, 1667-1674.
Google Scholar
33

Li, X.; Wang, R.; Zhang, F.; Zhou, L.; Shen, D.; Yao, C.; Zhao, D. Nd3+ sensitized up/down converting dual-mode nanomaterials for efficient in vitro and in vivo bioimaging excited at 800 nm. Sci Rep. 2013, 3, 3536
Google Scholar
34

Wang, Y.; Liu, G.; Sun, L.; Xiao, J.; Zhou, J.; Yan, C. Nd3+-sensitized upconversion nanophosphors: Efficient in vivo bioimaging probes with minimized heating effect. ACS Nano 2013, 7, 7200-7206.
Google Scholar
35

Wang, X.; Yan, X.; Kan, C.; Ma, K.; Xiao, Y.; Xiao, S. Enhancement of blue emission in β-NaYbF4: Tm3+/Nd3+ nanophosphors synthesized by nonclosed hydrothermal synthesis method. Appl. Phys. B-Lasers Opt. 2010, 101, 623-629.
Google Scholar
36

Wang, X.; Xiao, S.; Bu, Y.; Ding, J. Upconversion properties of Nd3+-Yb3+-Ho3+-doped β-Na(Y1.5Na0.5)F6 powders. J. Alloy. Compd. 2009, 477, 941-945.
Google Scholar
37

Wang, Z.; Hao, J. H.; Chan, H. L. W. Down- and up-conversion photoluminescence, cathodoluminescence and paramagnetic properties of NaGdF4: Yb3+, Er3+ submicrondisks. J. Mater. Chem. 2010, 20, 3178-3185.
Google Scholar
38

Gouveia-Netoa, A. S.; Costa, E. B. Sensitized thulium blue upconversion emission in Nd3+/Tm3+/Yb3+ triply doped lead and cadmium germanate glass excited around 800 nm. J. Appl. Phys. 2003, 94, 5678-5681.
Google Scholar
39

Lupei, V.; Lupei, A.; Ikesue, A. Transparent Nd and (Nd, Yb)-doped Sc2O3 ceramics as potential new laser materials. Appl. Phys. Lett. 2005, 86, 111118.
Google Scholar
40

Qiu, J.; Kawamoto, Y. Blue up-conversion luminescence and energy transfer process in Nd3+-Yb3+-Tm3+ Co-doped ZrF4-based glasses. J. Appl. Phys. 2002, 91, 954-959.
Google Scholar
41

Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 1953, 21, 836-850.
Google Scholar
42

Balda, R.; Fernández, J. Infrared to visible upconversion of Nd3+ ions in KPb2Br5 low photon crystal. Opt. Express 2006, 14, 3993-4004.
Google Scholar
43

Fernández, J.; Balda, R.; Iparraguirr, I.; Sanz, M.; Voda, M.; Al-Saleh, M.; Lobera, G. Upconversion processes and laser action in K5Nd(MoO4)4 stoichiometric crystal. Proc. of SPIE 2001, 4282, 258-265.
Google Scholar
44

Wang, F.; Deng, R.; Wang, J.; Wang, Q.; Han, Y.; Zhu, H.; Chen, X.; Liu, X. Tuning upconversion through energy migration in core-shell nanoparticles. Nat. Mater. 2011, 10, 968-973.
Google Scholar
45

Su, Q.; Han, S.; Xie, X.; Zhu, H.; Chen, H.; Chen, C.; Liu, R.; Chen, X.; Wang, F.; Liu, X. The effect of surface coating on energy migration-mediated upconversion. J. Am. Chem. Soc. 2012, 134, 20849-20857.
Google Scholar
46

Meijer, J.; Aarts, L.; Van der Ende, B. M.; Vlugt, T. J. H.; Meijerink, A. Downconversion for solar cells in YF3: Nd3+, Yb3+. Phys. Rev. B 2010, 81, 035107.
Google Scholar
47

Song, F.; Han, L.; Zou, C.; Su, J.; Zhang, K.; Yan, L.; Tian, J. Upconversion blue emission dependence on the pump mechanism for Tm3+-heavy-doped NaY(WO4)2 crystal. Appl. Phys. B 2007, 86, 653-660.
Google Scholar
48

Wu, Y.; Shi, M.; Zhao, L.; Feng, W.; Li, F.; Huang, C. Visible-light-excited and europium-emissive nanoparticles for highly-luminescent bioimaging in vivo. Biomaterials 2014, 35, 5830-5839.
Google Scholar
49

Boyer, J. C.; van Veggel, F. C. J. M. Absolute quantum yield measurements of colloidal NaYF4: Er3+, Yb3+ upconverting nanoparticles. Nanoscale 2010, 2, 1417-1419.
Google Scholar
50

Wen, H.; Zhu, H.; Chen, X.; Hung, T. F.; Wang, B.; Zhu, G.; Yu, S. F.; Wang, F. Upconverting near-infrared light through energy management in core-shell-shell nanoparticles. Angew. Chem. Int. Ed. 2013, 52, 13419-13423.
Google Scholar
51

Wong, H. T.; Chan, H. L. W.; Hao, J. H. Magnetic and luminescent properties of multifunctional GdF3: Eu3+ nanoparticles. Appl. Phys. Lett. 2009, 95, 022512.
Google Scholar
52

Zeng, S.; Ren, G.; Xu, C.; Yang, Q. Modifying crystal phase, shape, size, optical and magnetic properties of monodispersed multifunctional NaYbF4 nanocrystals through lanthanide doping. CrystEngComm 2011, 13, 4276-4281.
Google Scholar
53

Ren, G.; Zeng, S.; Hao, J. Tunable multicolor upconversion emissions and paramagnetic property of monodispersed bifunctional lanthanide-doped NaGdF4 nanorods. J. Phys. Chem. C 2011, 115, 20141-20147.
Google Scholar
Publication history
Copyright
Acknowledgements

Publication history

Received: 16 April 2014
Revised: 23 July 2014
Accepted: 26 July 2014
Published: 09 September 2014
Issue date: February 2015

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2014

Acknowledgements

Acknowledgements

We would like to acknowledge the support of the National Science Foundation (NSF) (Grant No. MRI0922898) for the TEM work. We also acknowledge the support from the Anhui Provincial Natural Science Foundation of China (No. 1308085QA06) and the National Science Foundation Partnership for Research and Education in Materials (NSF-PREM) (grant No. DMR-0934218). We also thank Archis Marathe for assistance with preparation of the manuscript.

Return