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Lanthanides in Luminescent Thermometry Chapter 281 401 FIG. 27 (A) Optical image of a mouse with two tumors. LaF3:Nd3+ NPs were injected only in the left-side tumor whereas the right-side one was used as a control. (B) and (C) Infrared fluores- cence and thermal images of the mouse under 808 nm (4 W cm2) laser irradiation, respectively. Adapted with permission from Carrasco, E., del Rosal, B., Sanz-Rodrı ́guez, F., de la Fuente, A ́.J., Gonzalez, P.H., Rocha, U., Kumar, K.U., Jacinto, C., Sole, J.G., Jaque, D. 2015. Intratumoral thermal reading during photo-thermal therapy by multifunctional fluorescent nanoparticles. Adv. Funct. Mater. 25, 615–626. © 2015 Wiley-VCH Verlag GmbH. proposed by Wang and Liu in 2011, (Wang et al., 2011b) is an important breakthrough on the historical development of photon upconversion in Ln3+- doped materials (Bettinelli et al., 2015). Based on this idea, a core–shell–shell NP design displaying tunable upconversion emissions spanning from UV to the visible spectral region by single wavelength excitation at 808 nm was sug- gested two years later (Wen et al., 2013). The design involved the growth of NaYbF4:Nd3+ (50 mol%) core NPs followed by successive deposition of two epitaxial shells of Na(Yb,Gd)F4:Er3+ (or Na(Yb,Gd)F4:Ho3+/Tm3+) and NaGdF4. The Nd3+ ions were used to harvest the NIR excitation, whereas the Yb3+ ions are designed to extract the excitation energy from Nd3+ and to subsequently transport the energy to the inner shell layer where upconverter ions (Er3+, Ho3+, or Tm3+) were confined. The NaGdF4 outermost shell layer passivates the active inner shell layer, protecting the upconverting process from surface quenchers (Han et al., 2014) and tuning the optical emission by encoding additional emitter ions (eg, Tb3+, Eu3+, Dy3+) that are able to capture the upconverted energy through the Gd network of the sublattice (Wen et al., 2013). The main advantage of a two-photon excitation process, relatively to one- photon absorption, is the substantial improvement that could be achieved in spatial resolution, due to the high order nature of the excitation process and the use of shorter emission wavelengths (Bettinelli et al., 2015; Pereira et al., 2015). Further spatial resolution improvement of temperature measure- ments would, therefore, be obtained if the thermosensitive luminescence would be excited under a three-, four-, or even five-photon excitation mecha- nism (Caillat et al., 2013). Three-photon excited Ln3+ emissions werePDF Image | HANDBOOK ON THE PHYSICS AND CHEMISTRY OF RARE EARTHS
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