Dye-sensitized Er³⁺-doped CaF₂ nanoparticles for enhanced near-infrared emission at 1.5  μm

Abstract

Lanthanide (Ln)-doped nanoparticles have shown potential for applications in various fields. However, the weak and narrow absorption bands of the Ln ions (Ln 3 ), hamper efficient optical pumping and severely limit the emission intensity. Dye sensitization is a promising way to boost the near-infrared (NIR) emission of Er 3 , hence promoting possible application in optical amplification at 1.5 μm, a region that is much sought after for telecommunication technology. Herein, we introduce the fluorescein isothiocyanate (FITC) organic dye with large absorption cross section as energy donor of small-sized (∼3.6 nm) Er 3 -doped CaF 2 nanoparticles. FITC molecules on the surface of CaF 2 work as antennas to efficiently absorb light, and provide the indirect sensitization of Er 3 boosting its emission. In this paper, we employ photoluminescence and transient absorption spectroscopy, as well as density functional theory calculations, to provide an in-depth investigation of the FITC → Er 3 energy transfer process. We show that an energy transfer efficiency of over 89% is achieved in CaF 2 :Er 3 @FITC nanoparticles resulting in a 28 times enhancement of the Er 3 NIR emission with respect to bare CaF 2 :Er 3 . Through the multidisciplinary approach used in our work, we are able to show that the reason for such high sensitization efficiency stems from the suitable size and geometry of the FITC dye with a localized transition dipole moment at a short distance from the surface of the nanoparticle.

Activatable Lanthanide Nanoprobes with Dye-Sensitized Second Near-Infrared Luminescence for in Vivo Inflammation Imaging

“…To circumvent this, organic dyes with a large absorption cross-section have been employed to enhance the light harvesting capability of lanthanide nanoparticles . Since the first report in 2007, strategies including incorporating different dyes, − precise particle size and geometry control, adjustment of the species, or ratios in the nanoregion have been reported to enhance the luminescence of lanthanide nanoparticles, − etc. In most cases, the dye acts as both the recognition moiety of the biomarkers and antenna for lanthanide nanoparticles.…”