Jossana Damasco

Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal

Lanthanide-doped upconversion nanoparticles hold promises for bioimaging, solar cells, and volumetric displays. However, their emission brightness and excitation wavelength range are limited by the weak and narrowband absorption of lanthanide ions. Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an epitaxially designed core/shell inorganic nanostructure, with a sequential nonradiative energy transfer to upconverting ion pairs in the core. We show that this concept, when implemented in a core-shell architecture with suppressed surface-related luminescence quenching, yields multiphoton (three-, four-, and five-photon) upconversion quantum efficiency as high as 19% (upconversion energy conversion efficiency of 9.3%, upconversion quantum yield of 4.8%), which is about ~100 times higher than typically reported efficiency of upconversion at 800 nm in lanthanide-based nanostructures, along with a broad spectral range (over 150 nm) of infrared excitation and a large absorption cross-section of 1.47 × 10(-14) cm(2) per single nanoparticle. These features enable unprecedented three-photon upconversion (visible by naked eye as blue light) of an incoherent infrared light excitation with a power density comparable to that of solar irradiation at the Earth surface, having implications for broad applications of these organic-inorganic core/shell nanostructures with energy-cascaded upconversion.

Size-Tunable and Monodisperse Tm3+/Gd3+-Doped Hexagonal NaYbF4 Nanoparticles with Engineered Efficient Near Infrared-to-Near Infrared Upconversion for In Vivo Imaging

Hexagonal NaYbF4:Tm3+ upconversion nanoparticles hold promise for use in high contrast near-infrared-to-near-infrared (NIR-to-NIR) in vitro and in vivo bioimaging. However, significant hurdles remain in their preparation and control of their morphology and size, as well as in enhancement of their upconversion efficiency. Here, we describe a systematic approach to produce highly controlled hexagonal NaYbF4:Tm3+ nanoparticles with superior upconversion. We found that doping appropriate concentrations of trivalent gadolinium (Gd3+) can convert NaYbF4:Tm3+ 0.5% nanoparticles with cubic phase and irregular shape into highly monodisperse NaYbF4:Tm3+ 0.5% nanoplates or nanospheres in a pure hexagonal-phase and of tunable size. The intensity and the lifetime of the upconverted NIR luminescence at 800 nm exhibit a direct dependence on the size distribution of the resulting nanoparticles, being ascribed to the varied surface-to-volume ratios determined by the different nanoparticle size. Epitaxial growth of a thin NaYF4 shell layer of ∼2 nm on the ∼22 nm core of hexagonal NaYbF4:Gd3+ 30%/Tm3+ 0.5% nanoparticles resulted in a dramatic 350 fold NIR upconversion efficiency enhancement, because of effective suppression of surface-related quenching mechanisms. In vivo NIR-to-NIR upconversion imaging was demonstrated using a dispersion of phospholipid-polyethylene glycol (DSPE-PEG)-coated core/shell nanoparticles in phosphate buffered saline.

Enhanced Upconversion Luminescence in Yb3+/Tm3+-Codoped Fluoride Active Core/Active Shell/Inert Shell Nanoparticles through Directed Energy Migration

The luminescence efficiency of lanthanide-doped upconversion nanoparticles is of particular importance for their embodiment in biophotonic and photonic applications. Here, we show that the upconversion luminescence of typically used NaYF4:Yb3+30%/Tm3+0.5% nanoparticles can be enhanced by ~240 times through a hierarchical active core/active shell/inert shell (NaYF4:Yb3+30%/Tm3+0.5%)/NaYbF4/NaYF4 design, which involves the use of directed energy migration in the second active shell layer. The resulting active core/active shell/inert shell nanoparticles are determined to be about 11 times brighter than that of well-investigated (NaYF4:Yb3+30%/Tm3+0.5%)/NaYF4 active core/inert shell nanoparticles when excited at ~980 nm. The strategy for enhanced upconversion in Yb3+/Tm3+-codoped NaYF4 nanoparticles through directed energy migration might have implications for other types of lanthanide-doped upconversion nanoparticles.

Simultaneous Multiple Wavelength Upconversion in a Core–Shell Nanoparticle for Enhanced Near Infrared Light Harvesting in a Dye-Sensitized Solar Cell

The efficiency of most photovoltaic devices is severely limited by near-infrared (NIR) transmission losses. To alleviate this limitation, a new type of colloidal upconversion nanoparticles (UCNPs), hexagonal core-shell-structured β-NaYbF4:Er(3+)(2%)/NaYF4:Nd(3+)(30%), is developed and explored in this work as an NIR energy relay material for dye-sensitized solar cells (DSSCs). These UCNPs are able to harvest light energy in multiple NIR regions, and subsequently convert the absorbed energy into visible light where the DSSCs strongly absorb. The NIR-insensitive DSSCs show compelling photocurrent increases through binary upconversion under NIR light illumination either at 785 or 980 nm, substantiating efficient energy relay by these UCNPs. The overall conversion efficiency of the DSSCs was improved with the introduction of UCNPs under simulated AM 1.5 solar irradiation.

TiO2-coated fluoride nanoparticles for dental multimodal optical imaging

Core-shell nanostructures associated with photonics techniques have found innumerous applications in diagnostics and therapy. In this work, we introduce a novel core-shell nanostructure design that serves as a multimodal optical imaging contrast agent for dental adhesion evaluation. This nanostructure consists of a rare-earth-doped (NaYF4 :Yb 60%, Tm 0.5%)/NaYF4 particle as the core (hexagonal prism, ~51 nm base side length) and the highly refractive TiO2 material as the shell (~thickness of 15 nm). We show that the TiO2 shell provides enhanced contrast for optical coherence tomography (OCT), while the rare-earth-doped core upconverts excitation light from 975 nm to an emission peaked at 800 nm for photoluminescence imaging. The OCT and the photoluminescence wide-field images of human tooth were demonstrated with this nanoparticle core-shell contrast agent. In addition, the described core-shell nanoparticles (CSNps) were dispersed in the primer of a commercially available dental bonding system, allowing clear identification of dental adhesive layers with OCT. We evaluated that the presence of the CSNp in the adhesive induced an enhancement of 67% scattering coefficient to significantly increase the OCT contrast. Moreover, our results highlight that the upconversion photoluminescence in the near-infrared spectrum region is suitable for image of deep dental tissue.