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Nano Research 2018, 11(12): 6360-6374 https://doi.org/10.1007/s12274-018-2159-9
Research Article | Issue | Published: 16 August 2018

Particle-size-dependent upconversion luminescence of NaYF4: Yb, Er nanoparticles in organic solvents and water at different excitation power densities

Show Author's Information Marco Kraft1,  Christian Würth1,  Verena Muhr2,  Thomas Hirsch2,  Ute Resch-Genger1( )
Federal Institute for Materials Research and Testing (BAM)Division 1.2 BiophotonicsRichard-Willstaetter-Str. 1112489Berlin, Germany
Institute of Analytical ChemistryChemo- and BiosensorsUniversity of Regensburg93040Regensburg, Germany
Keywords:
nanoparticle, upconversion, water, quenching, diameter, cyclohexane
Cite this article:
Kraft M, Würth C, Muhr V, et al. Particle-size-dependent upconversion luminescence of NaYF4: Yb, Er nanoparticles in organic solvents and water at different excitation power densities. Nano Research, 2018, 11(12): 6360-6374. https://doi.org/10.1007/s12274-018-2159-9
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Abstract Full text Electronic supplementary material About this article

A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12-43 nm is presented utilizing steady-state and time-resolved fluorometry. Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by high-energy O-H and C-H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated population pathways of the 4F9/2 energy level of Er3+ were examined. Our results highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under "strongly quenched" conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.


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About this article

Particle-size-dependent upconversion luminescence of NaYF4: Yb, Er nanoparticles in organic solvents and water at different excitation power densities

Show Author's information Marco Kraft1, Christian Würth1, Verena Muhr2, Thomas Hirsch2, Ute Resch-Genger1( )
Federal Institute for Materials Research and Testing (BAM)Division 1.2 BiophotonicsRichard-Willstaetter-Str. 1112489Berlin, Germany
Institute of Analytical ChemistryChemo- and BiosensorsUniversity of Regensburg93040Regensburg, Germany

Abstract

A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12-43 nm is presented utilizing steady-state and time-resolved fluorometry. Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by high-energy O-H and C-H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated population pathways of the 4F9/2 energy level of Er3+ were examined. Our results highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under "strongly quenched" conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.

Keywords: nanoparticle, upconversion, water, quenching, diameter, cyclohexane

References(57)

1

Wilhelm, S. Perspectives for upconverting nanoparticles. ACS Nano 2017, 11, 10644-10653.
DOI Google Scholar
2

Pichaandi, J.; Boyer, J. C.; Delaney, K. R.; van Veggel, F. C. J. M. Two-photon upconversion laser (scanning and wide- field) microscopy using Ln3+-doped NaYF4 upconverting nanocrystals: A critical evaluation of their performance and potential in bioimaging. J. Phys. Chem. C 2011, 115, 19054-19064.
DOI Google Scholar
3

Yang, Y. M.; Shao, Q.; Deng, R. R.; Wang, C.; Teng, X.; Cheng, K.; Cheng, Z.; Huang, L.; Liu, Z.; Liu, X. G. et al. In vitro and in vivo uncaging and bioluminescence imaging by using photocaged upconversion nanoparticles. Angew. Chem., Int. Ed. 2012, 51, 3125-3129.
DOI Google Scholar
4

Zhan, Q. Q.; Qian, J.; Liang, H. J.; Somesfalean, G.; Wang, D.; He, S. L.; Zhang, Z. G.; Andersson-Engels, S. Using 915 nm laser excited Tm3+/Er3+/Ho3+-doped NaYbF4 upconversion nanoparticles for in vitro and deeper in vivo bioimaging without overheating irradiation. ACS Nano 2011, 5, 3744-3757.
DOI Google Scholar
5

Resch-Genger, U.; Grabolle, M.; Cavaliere-Jaricot, S.; Nitschke, R.; Nann, T. Quantum dots versus organic dyes as fluorescent labels. Nat. Methods 2008, 5, 763-775.
DOI Google Scholar
6

Haase, M.; Schäfer, H. Upconverting nanoparticles. Angew. Chem., Int. Ed. 2011, 50, 5808-5829.
DOI Google Scholar
7

Xu, C. T.; Zhan, Q. Q.; Liu, H. C.; Somesfalean, G.; Qian, J.; He, S. L.; Andersson-Engels, S. Upconverting nanoparticles for pre-clinical diffuse optical imaging, microscopy and sensing: Current trends and future challenges. Laser Photonics Rev. 2013, 7, 663-697.
DOI Google Scholar
8

Resch-Genger, U.; Gorris, H. H. Perspectives and challenges of photon-upconversion nanoparticles - Part I: Routes to brighter particles and quantitative spectroscopic studies. Anal. Bioanal. Chem. 2017, 409, 5855-5874.
DOI Google Scholar
9

Gorris, H. H.; Resch-Genger, U. Perspectives and challenges of photon-upconversion nanoparticles - Part Ⅱ: Bioanalytical applications. Anal. Bioanal. Chem. 2017, 409, 5875-5890.
DOI Google Scholar
10

Menyuk, N.; Dwight, K.; Pierce, J. W. NaYF4: Yb, Er—An efficient upconversion phosphor. Appl. Phys. Lett. 1972, 21, 159-161.
DOI Google Scholar
11

Pierce, J. W.; Delaney, E. J.; Dwight, K.; Menyuk, N. Preparation of infrared to visible upconversion phosphors based on hexagonal NaYF4. Abstr. Pap. Am. Chem. Soc. 1972, 164, 18.
Google Scholar
12

Fischer, S.; Bronstein, N. D.; Swabeck, J. K.; Chan, E. M.; Alivisatos, A. P. Precise tuning of surface quenching for luminescence enhancement in core-shell lanthanide-doped nanocrystals. Nano Lett. 2016, 16, 7241-7247.
DOI Google Scholar
13

Xiang, G. T.; Zhang, J. H.; Hao, Z. D.; Zhang, X.; Pan, G. H.; Luo, Y. S.; Lu, W.; Zhao, H. F. Importance of suppression of Yb3+ de-excitation to upconversion enhancement in β-NaYF4: Yb3+/Er3+@β-NaYF4 sandwiched structure nanocrystals. Inorg. Chem. 2015, 54, 3921-3928.
DOI Google Scholar
14

Hossan, M. Y.; Hor, A.; Luu, Q.; Smith, S. J.; May, P. S.; Berry, M. T. Explaining the nanoscale effect in the upconversion dynamics of β-NaYF4: Yb3+, Er3+ core and core-shell nanocrystals. J. Phys. Chem. C 2017, 121, 16592-16606.
DOI Google Scholar
15

Chen, G. Y.; Shen, J.; Ohulchanskyy, T. Y.; Patel, N. J.; Kutikov, A.; Li, Z. P.; Song, J.; Pandey, R. K.; Agren, H.; Prasad, P. N. et al. (α-NaYbF4: Tm3+)/CaF2 core/shell nanoparticles with efficient near-infrared to near-infrared upconversion for high-contrast deep tissue bioimaging. ACS Nano 2012, 6, 8280-8287.
DOI Google Scholar
16

Arppe, R.; Hyppänen, I.; Perälä, N.; Peltomaa, R.; Kaiser, M.; Würth, C.; Christ, S.; Resch-Genger, U.; Schaferling, M.; Soukka, T. Quenching of the upconversion luminescence of NayF4: Yb3+, Er3+ and NaYF4: Yb3+, Tm3+ nanophosphors by water: The role of the sensitizer Yb3+ in non-radiative relaxation. Nanoscale 2015, 7, 11746-1157.
DOI Google Scholar
17

Scatena, L. F.; Brown, M. G.; Richmond, G. L. Water at hydrophobic surfaces: Weak hydrogen bonding and strong orientation effects. Science 2001, 292, 908-912.
DOI Google Scholar
18

Hyppänen, I.; Höysniemi, N.; Arppe, R.; Schäferling, M.; Soukka, T. Environmental impact on the excitation path of the red upconversion emission of nanocrystalline NaYF4: Yb3+, Er3+. J. Phys. Chem. C 2017, 121, 6924-6929.
DOI Google Scholar
19

Xue, X. J.; Uechi, S.; Tiwari, R. N.; Duan, Z. C.; Liao, M. S.; Yoshimura, M.; Suzuki, T.; Ohishi, Y. Size-dependent upconversion luminescence and quenching mechanism of LiYF4: Er3+/Yb3+ nanocrystals with oleate ligand adsorbed. Opt. Mater. Express 2013, 3, 989-999.
DOI Google Scholar
20

Muhr, V.; Würth, C.; Kraft, M.; Buchner, M.; Baeumner, A. J.; Resch-Genger, U.; Hirsch, T. Particle-size-dependent Förster resonance energy transfer from upconversion nanoparticles to organic dyes. Anal. Chem. 2017, 89, 4868- 4874.
DOI Google Scholar
21

Lim, S. F.; Ryu, W. S.; Austin, R. H. Particle size dependence of the dynamic photophysical properties of NaYF4: Yb, Er nanocrystals. Opt. Express 2010, 18, 2309-2316.
DOI Google Scholar
22

Johnson, N. J. J.; He, S.; Diao, S.; Chan, E. M.; Dai, H. J.; Almutairi, A. Direct evidence for coupled surface and concentration quenching dynamics in lanthanide-doped nanocrystals. J. Am. Chem. Soc. 2017, 139, 3275-3282.
DOI Google Scholar
23

Gargas, D. J.; Chan, E. M.; Ostrowski, A. D.; Aloni, S.; Altoe, M. V. P.; Barnard, E. S.; Sanii, B.; Urban, J. J.; Milliron, D. J.; Cohen, B. E. et al. Engineering bright sub-10-nm upconverting nanocrystals for single-molecule imaging. Nat. Nanotechnol. 2014, 9, 300-305.
DOI Google Scholar
24

Zhao, J. B.; Lu, Z. D.; Yin, Y. D.; McRae, C.; Piper, J. A.; Dawes, J. M.; Jin, D. Y.; Goldys, E. M. Upconversion luminescence with tunable lifetime in NaYF4: Yb, Er nanocrystals: Role of nanocrystal size. Nanoscale 2013, 5, 944-952.
DOI Google Scholar
25

Yuan, D.; Tan, M. C.; Riman, R. E.; Chow, G. M. Comprehensive study on the size effects of the optical properties of NaYF4: Yb, Er nanocrystals. J. Phys. Chem. C 2013, 117, 13297-13304.
DOI Google Scholar
26

Anderson, R. B.; Smith, S. J.; May, P. S.; Berry, M. T. Revisiting the NIR-to-visible upconversion mechanism in β-NaYF4: Yb3+, Er3+. J. Phys. Chem. Lett. 2014, 5, 36-42.
DOI Google Scholar
27

Berry, M. T.; May, P. S. Disputed mechanism for NIR- to-red upconversion luminescence in NaYF4: Yb3+, Er3+. J. Phys. Chem. A 2015, 119, 9805-9811.
DOI Google Scholar
28

Jung, T.; Jo, H. L.; Nam, S. H.; Yoo, B.; Cho, Y.; Kim, J.; Kim, H. M.; Hyeon, T.; Suh, Y. D.; Lee, H. et al. The preferred upconversion pathway for the red emission of lanthanide-doped upconverting nanoparticles, NaYF4: Yb3+, Er3+. Phys. Chem. Chem. Phys. 2015, 17, 13201-13205.
DOI Google Scholar
29

Kaiser, M.; Wurth, C.; Kraft, M.; Hyppänen, I.; Soukka, T.; Resch-Genger, U. Power-dependent upconversion quantum yield of NaYF4: Yb3+, Er3+ nano- and micrometer-sized particles-measurements and simulations. Nanoscale 2017, 9, 10051-10058.
DOI Google Scholar
30

Würth, C.; Kaiser, M.; Wilhelm, S.; Grauel, B.; Hirsch, T.; Resch-Genger, U. Excitation power dependent population pathways and absolute quantum yields of upconversion nanoparticles in different solvents. Nanoscale 2017, 9, 4283-4294.
DOI Google Scholar
31

Rabouw, F. T.; Meijerink, A. Modeling the cooperative energy transfer dynamics of quantum cutting for solar cells. J. Phys. Chem. C 2015, 119, 2364-2370.
DOI Google Scholar
32

Martín-Rodríguez, R.; Rabouw, F. T.; Trevisani, M.; Bettinelli, M.; Meijerink, A. Upconversion dynamics in Er3+-doped Gd2O2S: Influence of excitation power, Er3+ concentration, and defects. Adv. Opt. Mater. 2015, 3, 558-567.
DOI Google Scholar
33

Würth, C.; Fischer, S.; Grauel, B.; Alivisatos, A. P.; Resch-Genger, U. Quantum yields, surface quenching, and passivation efficiency for ultrasmall core/shell upconverting nanoparticles. J. Am. Chem. Soc. 2018, 140, 4922-4928.
DOI Google Scholar
34

Hudry, D.; Busko, D.; Popescu, R.; Gerthsen, D.; Abeykoon, A. M. M.; Kubel, C.; Bergfeldt, T.; Richards, B. S. Direct evidence of significant cation intermixing in upconverting core@shell nanocrystals: Toward a new crystallochemical model. Chem. Mater. 2017, 29, 9238-9246.
DOI Google Scholar
35

Klier, D. T.; Kumke, M. U. Upconversion luminescence properties of NaYF4: Yb: Er nanoparticles codoped with Gd3+. J. Phys. Chem. C 2015, 119, 3363-3373.
DOI Google Scholar
36

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. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping. Nature 2010, 463, 1061-1065.
DOI Google Scholar
37

Chen, F.; Bu, W. B.; Zhang, S. J.; Liu, X. H.; Liu, J. N.; Xing, H. Y.; Xiao, Q. F.; Zhou, L. P.; Peng, W. J.; Wang, L. Z. et al. Positive and negative lattice shielding effects Co-existing in Gd (Ⅲ) ion doped bifunctional upconversion nanoprobes. Adv. Funct. Mater. 2011, 21, 4285-4294.
DOI Google Scholar
38

Wilhelm, S.; Kaiser, M.; Würth, C.; Heiland, J.; Carrillo- Carrion, C.; Muhr, V.; Wolfbeis, O. S.; Parak, W. J.; Resch- Genger, U.; Hirsch, T. Water dispersible upconverting nanoparticles: Effects of surface modification on their luminescence and colloidal stability. Nanoscale 2015, 7, 1403-1410.
DOI Google Scholar
39

Päkkila, H.; Yliharsilä, M.; Lahtinen, S.; Hattara, L.; Salminen, N.; Arppe, R.; Lastusaari, M.; Saviranta, P.; Soukka, T. Quantitative multianalyte microarray immunoassay utilizing upconverting phosphor technology. Anal. Chem. 2012, 84, 8628-8634.
DOI Google Scholar
40

Wilhelm, S.; del Barrio, M.; Heiland, J.; Himmelstoss, S. F.; Galbán, J.; Wolfbeis, O. S.; Hirsch, T. Spectrally matched upconverting luminescent nanoparticles for monitoring enzymatic reactions. ACS Appl. Mater. Interfaces 2014, 6, 15427-15433.
DOI Google Scholar
41

Wilhelm, S.; Hirsch, T.; Patterson, W. M.; Scheucher, E.; Mayr, T.; Wolfbeis, O. S. Multicolor upconversion nanoparticles for protein conjugation. Theranostics 2013, 3, 239-248.
DOI Google Scholar
42

Zhao, J. B.; Jin, D. Y.; Schartner, E. P.; Lu, Y. Q.; Liu, Y. J.; Zvyagin, A. V.; Zhang, L. X.; Dawes, J. M.; Xi, P.; Piper, J. A. et al. Single-nanocrystal sensitivity achieved by enhanced upconversion luminescence. Nat. Nanotechnol. 2013, 8, 729-734.
DOI Google Scholar
43

Liu, H. C.; Xu, C. T.; Lindgren, D.; Xie, H. Y.; Thomas, D.; Gundlach, C.; Andersson-Engels, S. Balancing power density based quantum yield characterization of upconverting nanoparticles for arbitrary excitation intensities. Nanoscale 2013, 5, 4770-4775.
DOI Google Scholar
44

Shan, J. N.; Uddi, M.; Yao, N.; Ju, Y. G. Anomalous Raman scattering of colloidal Yb3+, Er3+ codoped NaYF4 nanophosphors and dynamic probing of the upconversion luminescence. Adv. Funct. Mater. 2010, 20, 3530-3537.
DOI Google Scholar
45

Wang, Y.; Deng, R. R.; Xie, X. J.; Huang, L.; Liu, X. G. Nonlinear spectral and lifetime management in upconversion nanoparticles by controlling energy distribution. Nanoscale 2016, 8, 6666-6673.
DOI Google Scholar
46

Cao, T. Y.; Yang, Y.; Gao, Y. A.; Zhou, J.; Li, Z. Q.; Li, F. Y. High-quality water-soluble and surface-functionalized upconversion nanocrystals as luminescent probes for bioimaging. Biomaterials 2011, 32, 2959-2968.
DOI Google Scholar
47

Ju, Q.; Luo, W. Q.; Liu, Y. S.; Zhu, H. M.; Li, R. F.; Chen, X. Y. Poly (acrylic acid)-capped lanthanide-doped BaFCl nanocrystals: Synthesis and optical properties. Nanoscale 2010, 2, 1208-1212.
DOI Google Scholar
48

Guan, Y.; Zhang, Y. J.; Zhou, T.; Zhou, S. Q. Stability of hydrogen-bonded hydroxypropylcellulose/poly(acrylic acid) microcapsules in aqueous solutions. Soft Matter 2009, 5, 842-849.
DOI Google Scholar
49

Liu, F.; Ma, E.; Chen, D. Q.; Wang, Y. S.; Yu, Y. L.; Huang, P. Infrared luminescence of transparent glass ceramic containing Er3+: NaYF4 nanocrystals. J. Alloys Compounds 2009, 467, 317-321.
DOI Google Scholar
50

Ostrowski, A. D.; Chan, E. M.; Gargas, D. J.; Katz, E. M.; Han, G.; Schuck, P. J.; Milliron, D. J.; Cohen, B. E. Controlled synthesis and single-particle imaging of bright, sub-10 nm lanthanide-doped upconverting nanocrystals. ACS Nano 2012, 6, 2686-2692.
DOI Google Scholar
51

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.
DOI Google Scholar
52

Li, X. M.; Shen, D. K.; Yang, J. P.; Yao, C.; Che, R. C.; Zhang, F.; Zhao, D. Y. Successive layer-by-layer strategy for multi-shell epitaxial growth: Shell thickness and doping position dependence in upconverting optical properties. Chem. Mater. 2013, 25, 106-112.
DOI Google Scholar
53

Mousavi, M.; Thomasson, B.; Li, M.; Kraft, M.; Würth, C.; Resch-Genger, U.; Andersson-Engels, S. Beam-profile- compensated quantum yield measurements of upconverting nanoparticles. Phys. Chem. Chem. Phys. 2017, 19, 22016- 22022.
DOI Google Scholar
54

Homann, C.; Krukewitt, L.; Frenzel, F.; Grauel, B.; Würth, C. NaYF4: Yb, Er/NaYF4 core/shell nanocrystals with high upconversion luminescence quantum yield. Angew. Chem., Int. Ed. 2018, 57, 8765-8769.
DOI Google Scholar
55

Würth, C.; Pauli, J.; Lochmann, C.; Spieles, M.; Resch- Genger, U. Integrating sphere setup for the traceable measurement of absolute photoluminescence quantum yields in the near infrared. Anal. Chem. 2012, 84, 1345-1352.
DOI Google Scholar
56

Resch-Genger, U.; Bremser, W.; Pfeifer, D.; Spieles, M.; Hoffmann, A.; DeRose, P. C.; Zwinkels, J. C.; Gauthier, F.; Ebert, B.; Taubert, R. D. et al. State-of-the art comparability of corrected emission spectra. 1. Spectral correction with physical transfer standards and spectral fluorescence standards by expert laboratories. Anal. Chem. 2012, 84, 3889-3898.
DOI Google Scholar
57

Ahrar, K.; Gowda, A.; Javadi, S.; Borne, A.; Fox, M.; McNichols, R.; Ahrar, J. U.; Stephens, C.; Stafford, R. J. Preclinical assessment of a 980-nm diode laser ablation system in a large animal tumor model. J. Vascul. Interv. Radiol. 2010, 21, 555-561.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 03 April 2018
Revised: 23 July 2018
Accepted: 28 July 2018
Published: 16 August 2018
Issue date: June 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

U. R. G. acknowledges financial support by research grants RE 1203/18-1 (German research council; DFG) and RE 1203/20-1 (project NANOHYPE; DFG and M-Eranet) and M. K. from the Ph.D. program of BAM. Moreover, COST Action CM1403, the European upconversion network from the design of photon-upconverting nanomaterials to (biomedical) applications, is gratefully acknowledged.

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