Tuning the sensitivity of lanthanide-activated NIR nanothermometers in the biological windows.

Lanthanide-activated SrF2 nanoparticles with a multishell architecture were investigated as optical thermometers in the biological windows. A ratiometric approach based on the relative changes in the intensities of different lanthanide (Nd3+ and Yb3+) NIR emissions was applied to investigate the thermometric properties of the nanoparticles. It was found that an appropriate doping with Er3+ ions can increase the thermometric properties of the Nd3+-Yb3+ coupled systems. In addition, a core containing Yb3+ and Tm3+ can generate light in the visible and UV regions upon near-infrared (NIR) laser excitation at 980 nm. The multishell structure combined with the rational choice of dopants proves to be particularly important to control and enhance the performance of nanoparticles as NIR nanothermometers.

Covering the optical spectrum through collective rare-earth doping of NaGdF4 nanoparticles: 806 and 980 nm excitation routes.

Today, at the frontier of biomedical research, the need has been clearly established for integrating disease detection and therapeutic function in one single theranostic system. Light-emitting nanoparticles are being intensively investigated to fulfil this demand, by continuously developing nanoparticle systems simultaneously emitting in both the UV/visible (light-triggered release and activation of drugs) and the near-infrared (imaging and tracking) spectral regions. In this work, rare-earth (RE) doped nanoparticles (RENPs) were synthesized via a thermal decomposition process and spectroscopically investigated as potential candidates as all-in-one optical imaging, diagnostic and therapeutic agents. These core/shell/shell nanoparticles (NaGdF4:Er3+,Ho3+,Yb3+/NaGdF4:Nd3+,Yb3+/NaGdF4) are optically excited by heating-free 806 nm light that, aside from minimizing the local thermal load, also allows to obtain a deeper sub-tissue penetration with respect to the still widely used 980 nm light. Moreover, these water-dispersed nanoplatforms offer interesting assets as triggers/probes for biomedical applications, by virtue of a plethora of emission bands (spanning the 380-1600 nm range). Our results pave the way to use these RENPs for UV/visible-triggered photodynamic therapy/drug release, while simultaneously tracking the nanoparticle biodistribution and monitoring their therapeutic action through the near-infrared signal that overlaps with biological transparency windows.

Double rare-earth nanothermometer in aqueous media: opening the third optical transparency window to temperature sensing.

Owing to the alluring possibility of contactless temperature probing with microscopic spatial resolution, photoluminescence nanothermometry at the nanoscale is rapidly advancing towards its successful application in biomedical sciences. The emergence of near-infrared nanothermometers has paved the way for temperature sensing at the deep tissue level. However, water dispersibility, adequate size at the nanoscale, and the capability to efficiently operate in the second and third biological optical transparency windows are the requirements that still have to be fulfilled in a single nanoprobe. In this work, these requirements are addressed by rare-earth doped nanoparticles with core/shell-architecture, dispersed in water, whose excitation and emission wavelengths conveniently fall within the biological optical transparency windows. Under heating-free 800 nm excitation, double nanothermometry is realized either with Ho3+-Nd3+ (1.18-1.34 µm) or Er3+-Nd3+ (1.55-1.34 µm) NIR emission band ratios, both displaying equal thermal sensitivities around 1.1% °C-1. It is further demonstrated that, along with the interionic energy transfer processes, the thermometric properties of these nanoparticles are also governed by the temperature dependent energy transfer to the surrounding solvent (water) molecules. Overall, this work presents a novel water dispersible double ratiometric nanothermometer operating in the second and third biological optical transparency windows. The temperature dependent particle-solvent interaction is also presented, which is critical for e.g. future in vivo applications.

Nanoparticles for photothermal therapies.

The current status of the use of nanoparticles for photothermal treatments is reviewed in detail. The different families of heating nanoparticles are described paying special attention to the physical mechanisms at the root of the light-to-heat conversion processes. The heating efficiencies and spectral working ranges are listed and compared. The most important results obtained in both in vivo and in vitro nanoparticle assisted photothermal treatments are summarized. The advantages and disadvantages of the different heating nanoparticles are discussed.

Direct laser writing of near-IR step-index buried channel waveguides in rare earth doped YAG.

A new (to our knowledge) ultrashort laser pulse irradiation regime that allows us to directly modify and increase the refractive index of rare earth doped YAG polycrystalline ceramics has been identified. Single-mode buried channel waveguides in both Ho:YAG and Er:YAG ceramics at the near-IR wavelengths of 1.55 µm and 1.95 µm are demonstrated by fabricating positive square step-index cores. Minimum propagation losses of 1.5 dB cm(-1) at a 1.51 µm wavelength have been preliminarily obtained. Confocal microluminescence mapping reveals that the increased refractive index regions retain the near-IR spectral properties of Er3+ ions in the YAG crystalline matrix.

Microstructuring of Nd:YAG crystals by proton-beam writing.

We report on the microstructuring of Nd:YAG crystals by direct proton-beam writing. Buried channel waveguides have been fabricated with full spatial control by the combined variation of crystal position and proton energy. The fluorescence images of the obtained structures have been used to evaluate the potential application of the fabricated structures for laser gain as well as to elucidate the mechanism at the basis of the refractive index increment induced at the end of the proton path. We have concluded that this increment is very likely a local enhancement in the electronic polarizability caused by nuclear collisions.

Swift heavy-ion irradiated active waveguides in Nd:YAG crystals: fabrication and laser generation.

An Nd:YAG planar waveguide laser has been fabricated by ultra-low-fluence (2×10(12) cm(-2)) swift heavy-ion irradiation (60 MeV Ar(4+) ions). The appearance of the buried waveguiding has been associated with an increased refractive index layer as a consequence of the ion-induced electronic damage. Continuous-wave laser oscillations at 1064.2 nm have been observed from the waveguide under 808 nm optical excitation, with the absorbed pump power at threshold and laser slope efficiency close to 26 mW and 5.9%, respectively.

Femtosecond-laser-written, stress-induced Nd:YVO4 waveguides preserving fluorescence and Raman gain.

We report the formation of optical waveguides in the self-Raman Nd:YVO(4) laser crystal by femtosecond laser inscription. The confocal fluorescence and Raman images have revealed that the waveguide is constituted by a locally compressed area in which the original fluorescence and Raman gains of the Nd:YVO(4) system are preserved. Thus the obtained structures emerge as promising candidates for highly efficient self-Raman integrated laser sources.

Thermally resistant waveguides fabricated in Nd:YAG ceramics by crossing femtosecond damage filaments.

We report on femtosecond laser writing of channel waveguides in Nd(3+) ion doped YAG ceramics by multiple inscriptions of damage filaments. Waveguiding between filaments was found to resist annealing temperatures as high as 1500 degrees C. Microluminescence imaging experiments have been carried out to elucidate the potential application of the obtained waveguides as integrated laser sources as well as to elucidate the waveguiding mechanisms.

Microstructuration induced differences in the thermo-optical and luminescence properties of Nd:YAG fine grain ceramics and crystals.

The temperature and compositional dependences of thermo-optical properties of neodymium doped yttrium aluminum garnet (YAG) crystals and fine grain ceramics have been systematically investigated by means of time-resolved thermal lens spectrometry. We have found that Nd:YAG ceramics show a reduced thermal diffusivity compared to Nd:YAG single crystals in the complete temperature range investigated (80-300 K). The analysis of the time-resolved luminescent properties of Nd(3+) has revealed that the reduction in the phonon mean free path taking place in Nd:YAG ceramics cannot be associated with an increment in the density of lattice defects, indicating that phonon scattering at grain boundaries is the origin of the observed reduction in the thermal diffusivity of Nd:YAG ceramics. Finally, our results showed the ability of the time-resolved thermal lens to determine and optimize the thermo-optical properties of Nd:YAG ceramic based lasers.

Effects of neodymium incorporation on the structural and luminescence properties of the YAl(3)(BO(3))(4)-NdAl(3)(BO(3))(4) system.

The luminescence of Nd(3+) ions in Nd(x)Y(1-x)Al(3)(BO(3))(4) (Nd:YAB) single crystals has been investigated as a function of the neodymium concentration in order to evidence the relation between the structural and spectroscopic properties in this nonlinear laser system. The analysis of the experimental data allowed us to individuate four different composition ranges. For moderate concentrations (x<0.2) the lattice parameters are nearly constant, and the emission spectra arise from Nd(3+) ions in unperturbed crystal sites. For concentrations in the 0.20.9 the final formation of the NdAl(3)(BO(3))(4) (NAB) monoclinic phase is complete, and a new local ordering around Nd(3+) is very evident in the spectral features.