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Ultraefficient cascade energy transfer in dye-sensitized core/shell fluoride nanoparticles

Jing Liu (UGent) , Anna Kaczmarek (UGent) , Flavia Artizzu (UGent) and Rik Van Deun (UGent)
(2019) ACS PHOTONICS. 6(3). p.659-666
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Abstract
The multistep sequential dye -> Nd3+ -> Yb3+ energy transfer leading to significantly enhanced emission at 1 pm has been investigated in core-shell CaF2 nanoparticles. We demonstrate that, by controlling the relative positions and the distance between energy donor (Nd3+) and acceptor (Yb3+) units through the confinement of the donor into a thin shell well below the Forster's radius, virtually fully efficient Yb3+ sensitization can be achieved. Optimized and facile synthetic protocols by employing a hot injection approach allowed the controlled deposition of a similar to 0.4 nm thick Nd3+-doped outer shell on Yb3+-doped core nanoparticles of less than 4 nm diameter. The fluorescein isothiocyanate (FITC) dye on the surface of the nanoparticles acts as efficient visible-light harvester, enabling the sensitization via nonradiative energy transfer of emitting lanthanide ions (Ln(3+)). The short distance between Nd3+ and Yb3+ allows for ultraefficient (similar to 90%) interlanthanide energy transfer resulting in an Yb3+ sensitization efficiency of over 90% thanks to the "bridging effect" of Nd3+ energy donors. As a result, the overall near-infrared quantum yield increases by similar to 40% with respect to dye-only sensitized Yb3+ and a total enhancement of about 2100x the 1 mu m luminescence intensity with respect to directly excited Yb-only nanoparticles, which is the highest figure of merit reported in literature so far for NIR-emitting analogous systems, is observed. The achievement of sensitization efficiencies so far only obtained in tightly bonded lanthanide molecular complexes, through a design strategy of general validity, opens new perspectives in regard to the potential application of this type of nanoparticle for optical amplification at 1 mu m.
Keywords
lanthanide energy transfer, donor-acceptor, Forster's radius, core-shell nanoparticles, NIR optical amplification, UP-CONVERSION, LANTHANIDE, COMPLEXES, LASER, YB3+

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MLA
Liu, Jing, et al. “Ultraefficient Cascade Energy Transfer in Dye-Sensitized Core/Shell Fluoride Nanoparticles.” ACS PHOTONICS, vol. 6, no. 3, 2019, pp. 659–66, doi:10.1021/acsphotonics.8b01465.
APA
Liu, J., Kaczmarek, A., Artizzu, F., & Van Deun, R. (2019). Ultraefficient cascade energy transfer in dye-sensitized core/shell fluoride nanoparticles. ACS PHOTONICS, 6(3), 659–666. https://doi.org/10.1021/acsphotonics.8b01465
Chicago author-date
Liu, Jing, Anna Kaczmarek, Flavia Artizzu, and Rik Van Deun. 2019. “Ultraefficient Cascade Energy Transfer in Dye-Sensitized Core/Shell Fluoride Nanoparticles.” ACS PHOTONICS 6 (3): 659–66. https://doi.org/10.1021/acsphotonics.8b01465.
Chicago author-date (all authors)
Liu, Jing, Anna Kaczmarek, Flavia Artizzu, and Rik Van Deun. 2019. “Ultraefficient Cascade Energy Transfer in Dye-Sensitized Core/Shell Fluoride Nanoparticles.” ACS PHOTONICS 6 (3): 659–666. doi:10.1021/acsphotonics.8b01465.
Vancouver
1.
Liu J, Kaczmarek A, Artizzu F, Van Deun R. Ultraefficient cascade energy transfer in dye-sensitized core/shell fluoride nanoparticles. ACS PHOTONICS. 2019;6(3):659–66.
IEEE
[1]
J. Liu, A. Kaczmarek, F. Artizzu, and R. Van Deun, “Ultraefficient cascade energy transfer in dye-sensitized core/shell fluoride nanoparticles,” ACS PHOTONICS, vol. 6, no. 3, pp. 659–666, 2019.
@article{8613996,
  abstract     = {The multistep sequential dye -> Nd3+ -> Yb3+ energy transfer leading to significantly enhanced emission at 1 pm has been investigated in core-shell CaF2 nanoparticles. We demonstrate that, by controlling the relative positions and the distance between energy donor (Nd3+) and acceptor (Yb3+) units through the confinement of the donor into a thin shell well below the Forster's radius, virtually fully efficient Yb3+ sensitization can be achieved. Optimized and facile synthetic protocols by employing a hot injection approach allowed the controlled deposition of a similar to 0.4 nm thick Nd3+-doped outer shell on Yb3+-doped core nanoparticles of less than 4 nm diameter. The fluorescein isothiocyanate (FITC) dye on the surface of the nanoparticles acts as efficient visible-light harvester, enabling the sensitization via nonradiative energy transfer of emitting lanthanide ions (Ln(3+)). The short distance between Nd3+ and Yb3+ allows for ultraefficient (similar to 90%) interlanthanide energy transfer resulting in an Yb3+ sensitization efficiency of over 90% thanks to the "bridging effect" of Nd3+ energy donors. As a result, the overall near-infrared quantum yield increases by similar to 40% with respect to dye-only sensitized Yb3+ and a total enhancement of about 2100x the 1 mu m luminescence intensity with respect to directly excited Yb-only nanoparticles, which is the highest figure of merit reported in literature so far for NIR-emitting analogous systems, is observed. The achievement of sensitization efficiencies so far only obtained in tightly bonded lanthanide molecular complexes, through a design strategy of general validity, opens new perspectives in regard to the potential application of this type of nanoparticle for optical amplification at 1 mu m.},
  author       = {Liu, Jing and Kaczmarek, Anna and Artizzu, Flavia and Van Deun, Rik},
  issn         = {2330-4022},
  journal      = {ACS PHOTONICS},
  keywords     = {lanthanide energy transfer,donor-acceptor,Forster's radius,core-shell nanoparticles,NIR optical amplification,UP-CONVERSION,LANTHANIDE,COMPLEXES,LASER,YB3+},
  language     = {eng},
  number       = {3},
  pages        = {659--666},
  title        = {Ultraefficient cascade energy transfer in dye-sensitized core/shell fluoride nanoparticles},
  url          = {http://dx.doi.org/10.1021/acsphotonics.8b01465},
  volume       = {6},
  year         = {2019},
}

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