Bright Infrared-to-Ultraviolet/Visible Upconversion in Small Alkaline Earth-Based Nanoparticles with Biocompatible CaF2 Shells

Stefan Fischer; Chris Siefe; Dayne F. Swearer; Claire A. McLellan; A. Paul Alivisatos; Jennifer A. Dionne

doi:10.1002/anie.202007683

Bright Infrared-to-Ultraviolet/Visible Upconversion in Small Alkaline Earth-Based Nanoparticles with Biocompatible CaF₂ Shells

Stefan Fischer, Chris Siefe^*, Dayne F. Swearer, Claire A. McLellan, A. Paul Alivisatos, Jennifer A. Dionne^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

Upconverting nanoparticles (UCNPs) are promising candidates for photon-driven reactions, including light-triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR-to-UV/visible emission of sub-15 nm alkaline-earth rare-earth fluoride UCNPs (M_1−xLn_xF_2+x, MLnF) with a CaF₂ shell. We synthesize 8 alkaline-earth host materials doped with Yb³⁺ and Tm³⁺, with alkaline-earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping-dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm⁻² are achieved with 14.5 nm SrLuF@CaF₂ particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm³⁺@CaF₂ particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm³⁺@CaF₂, highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.

Original language	English (US)
Pages (from-to)	21603-21612
Number of pages	10
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	48
DOIs	https://doi.org/10.1002/anie.202007683
State	Published - Nov 23 2020

Funding

S.F., C.S., and J.A.D. acknowledge support from the Photonics at Thermodynamic limits Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE‐SC0019140. C.S. was supported by an Eastman Kodak fellowship, NIH Grant 5R21GM129879‐02, and NIH Grant 1DP2AI15207201. D.F.S acknowledges support from the Arnold and Mabel Beckman Foundation with a Postdoctoral Fellowship in the Chemical Sciences. C.A.M. and J.A.D. acknowledge financial support from the Stanford Bio‐X Interdisciplinary Initiatives Committee (IIP) and NIH Grant 5R21GM129879‐02. C.A.M. was supported by the Wu Tsai Neurosciences Institute and also received support from NIH Grant 1DP2AI15207201. TEM imaging was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS‐1542152. S.F., C.S., and J.A.D. acknowledge support from the Photonics at Thermodynamic limits Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0019140. C.S. was supported by an Eastman Kodak fellowship, NIH Grant 5R21GM129879-02, and NIH Grant 1DP2AI15207201. D.F.S acknowledges support from the Arnold and Mabel Beckman Foundation with a Postdoctoral Fellowship in the Chemical Sciences. C.A.M. and J.A.D. acknowledge financial support from the Stanford Bio-X Interdisciplinary Initiatives Committee (IIP) and NIH Grant 5R21GM129879-02. C.A.M. was supported by the Wu Tsai Neurosciences Institute and also received support from NIH Grant 1DP2AI15207201. TEM imaging was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS-1542152.

Keywords

alkaline earth metals
lanthanides
nanoparticles
photophysics
upconversion

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.202007683

Cite this

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title = "Bright Infrared-to-Ultraviolet/Visible Upconversion in Small Alkaline Earth-Based Nanoparticles with Biocompatible CaF2 Shells",

abstract = "Upconverting nanoparticles (UCNPs) are promising candidates for photon-driven reactions, including light-triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR-to-UV/visible emission of sub-15 nm alkaline-earth rare-earth fluoride UCNPs (M1−xLnxF2+x, MLnF) with a CaF2 shell. We synthesize 8 alkaline-earth host materials doped with Yb3+ and Tm3+, with alkaline-earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping-dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm−2 are achieved with 14.5 nm SrLuF@CaF2 particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm3+@CaF2 particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm3+@CaF2, highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.",

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author = "Stefan Fischer and Chris Siefe and Swearer, {Dayne F.} and McLellan, {Claire A.} and Alivisatos, {A. Paul} and Dionne, {Jennifer A.}",

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