Refined structural studies on the fluorite-related polymorphs of sol-gel undoped and Eu3+-doped yttrium tantalates.

Compounds with the general formula RE3MO7 (RE = rare earth ions; M = Ta, Nb, Sb, Ru, Ir, Os, Re, etc.), crystallize as a fluorite-related structure, forming polymorphs with different space groups. The space group strongly depends on the RE3+ and M5+ ionic radii and processing conditions. Structural characterization is well-established for the lanthanide series, but literature studies have divergent views about how to attribute yttrium tantalate (Y3TaO7) space groups-some authors have described the Y3TaO7 structure as orthorhombic and belonging to space group C2221 or Ccmm, whereas others have assigned a cubic Fm3̄m structure to it. Here, we have characterized the structure of undoped and Eu3+-doped Y3TaO7 (0.1 to 50 mol% of Eu3+) samples synthesized by the sol-gel method that crystallized as a cubic disordered fluorite-type structure, space group Fm3̄m. Their powder X-ray diffraction measurements, Rietveld analyzes and Raman spectra were used as a conclusive technique of the structural properties. We have also investigated whether a secondary phase (M'-YTaO4) emerged in the samples and compared the phase composition of each sample to their Raman spectra. Low-temperature photoluminescence measurements (∼15 K) using Eu3+ as a structural probe helped us analyze the inhomogeneous broadening observed in the emission spectra. These measurements can be used as an important tool to attribute the crystalline phases of rare earth tantalates and niobates.

Super Broadband at Telecom Wavelengths From RE3+-Doped SiO2-Ta2O5 Glass Ceramics Planar Waveguides.

This paper reports on the preparation of Er3+/Yb3+/Tm3+, Er3+/Yb3+/Nd3+, and Er3+/Tm3+/Nd3+ triply doped and Er3+-doped SiO2-Ta2O5 glass ceramic nanocomposites and active planar waveguides by the sol-gel process using the dip-coating technique as deposition method. The investigation of their structural, morphological, and luminescent properties using XRD, AFM, and photoluminescence analysis, are reported here. The XRD results showed the presence of L-Ta2O5 nanocrystals dispersed in the SiO2-based amorphous host for all the nanocomposites and films. The rare earth ion (RE3+) doping concentration affected both the crystallinity, and the crystallite sizes of the Ta2O5 dispersed into SiO2-Ta2O5 nanocomposites and waveguides. AFM characterization revealed crack free and smooth surface roughness and differences in viscoelasticity on the Er3+-doped SiO2-Ta2O5 films surface, which allows the identification of Ta2O5 nanocrystals on the SiO2 amorphous host. The Er3+ doped and triply doped SiO2-Ta2O5 nanocomposites displayed broad- and super broadband NIR emissions with a FWHM up to 173 nm achieved in the telecom wavelengths. The lifetime of the 4I13/2 emitting level of the Er3+-doped SiO2-Ta2O5 waveguides is strongly dependent on Er3+ concentration and an emission quenching was negligible up to 0.81 mol%. The structural and luminescent investigations indicated that RE3+-doped SiO2-Ta2O5 glass ceramics are promising candidates for photonic applications in optical devices operating in wide wavelengths at the telecom bands.

Single Er3+, Yb3+: KGd3F10 Nanoparticles for Nanothermometry.

Among several optical non-contact thermometry methods, luminescence thermometry is the most versatile approach. Lanthanide-based luminescence nanothermometers may exploit not only downshifting, but also upconversion (UC) mechanisms. UC-based nanothermometers are interesting for biological applications: they efficiently convert near-infrared radiation to visible light, allowing local temperatures to be determined through spectroscopic investigation. Here, we have synthesized highly crystalline Er3+, Yb3+ co-doped upconverting KGd3F10 nanoparticles (NPs) by the EDTA-assisted hydrothermal method. We characterized the structure and morphology of the obtained NPs by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and dynamic light scattering. Nonlinear spectroscopic studies with the Er3+, Yb3+: KGd3F10 powder showed intense green and red emissions under excitation at 980 and 1,550 nm. Two- and three-photon processes were attributed to the UC mechanisms under excitation at 980 and 1,550 nm. Strong NIR emission centered at 1,530 nm occurred under low 980-nm power densities. Single NPs presented strong green and red emissions under continuous wave excitation at 975.5 nm, so we evaluated their use as primary nanothermometers by employing the Luminescence Intensity Ratio technique. We determined the temperature felt by the dried NPs by integrating the intensity ratio between the thermally coupled 2H11/2→4I15/2 and 4S3/2→4I15/2 levels of Er3+ ions in the colloidal phase and at the single NP level. The best thermal sensitivity of a single Er3+, Yb3+: KGd3F10 NP was 1.17% at the single NP level for the dry state at 300 K, indicating potential application of this material as accurate nanothermometer in the thermal range of biological interest. To the best of our knowledge, this is the first promising thermometry based on single KGd3F10 particles, with potential use as biomarkers in the NIR-II region.

Magnetic and Highly Luminescent Heterostructures of Gd3+/ZnO Conjugated to GCIS/ZnS Quantum Dots for Multimodal Imaging.

In recent years, the use of quantum dots (Qdots) to obtain biological images has attracted attention due to their excellent luminescent properties and the possibility of their association with contrast agents for magnetic resonance imaging (MRI). In this study, Gd3+/ZnO (ZnOGd) were conjugated with Qdots composed of a gadolinium-copper-indium-sulphur core covered with a ZnS shell (GCIS/ZnS Qdots). This conjugation is an innovation that has not yet been described in the literature, and which aims to improve Qdot photoluminescent properties. Structural and morphological Qdots features were obtained by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analyses (TGA). The photoluminescent properties were examined by emission (PL) and excitation (PLE) spectra. A new ZnOGd and GCIS/ZnS (ZnOGd-GCIS/ZnS) nanomaterial was synthesized with tunable optical properties depending on the ratio between the two native Qdots. A hydrophilic or lipophilic coating, using 3-glycidyloxypropyltrimethoxysilane (GPTMS) or hexadecyltrimethoxysilane (HTMS) on the surface of ZnOGd-GCIS/ZnS Qdots, was carried out before assessing their efficiency as magnetic resonance contrast agents. ZnOGd-GCIS/ZnS had excellent luminescence and MRI properties. The new Qdots developed ZnOGd-GCIS/ZnS, mostly constituted of ZnOGd (75%), which had less cytotoxicity when compared to ZnOGd, as well as greater cellular uptake.

Luminescence in colorless, transparent, thermally stable thin films of Eu3+ and Tb3+ beta-diketonates in hybrid inorganic-organic zinc-based sol-gel matrix.

Luminescent zinc-based hybrid inorganic-organic films with rare-earth (RE) complexes have been prepared using a non-alkoxide sol-gel process. The films were fabricated by the dip-coating method starting from zinc acetate dihydrate, rare earth chloride, lactic acid as hydrolytic catalyst, and anhydrous ethanol. The beta-diketones thenoylltrifluoroacetone (Httfa) and dibenzoylmethane (Hdbm) were used as ligands to Eu(3+) and Tb(3+), respectively. After deposition of the first layer, the films were fired at temperatures between 50 and 300 degrees C, in air. Photophysical properties such as excitation, emission and emission, lifetimes were determined for the films obtained in different conditions. Eu(3+)/ttfa and Tb(3+)/dbm films fired at 300 and 250 degrees C, respectively, are still transparent and gave rise to intense emission when excited through the ligand (antenna effect).

High Eu3+ concentration quenching in Y3TaO7 solid solution for orange-reddish emission in photonics.

We report the synthesis of a Y3TaO7 solid solution containing a high Eu3+ concentration (from 7 up to 50 mol%) and investigate how Eu3+ influences the Y3TaO7 crystallization process. To this end, we evaluate the Y3TaO7 structural features and photoluminescence properties after Eu3+ introduction into the Y3TaO7 lattice. The higher the Eu3+ ion concentration, the more stable the crystallization process of the Y3TaO7 phase seems to be. The Eu3+-containing Y3TaO7 displays intense orange-reddish, broad band emission because Eu3+ occupies different symmetry sites in the host and causes inhomogeneous broadening. Eu3+ emission quenching due to Eu3+ concentration is negligible up to 30 mol% and absolute quantum yield values of up to nearly 30% were obtained, making Eu3+-containing Y3TaO7 interesting materials for application as high-intensity emitters in photonics.

A technique to produce thin cucurbit[6]uril films.

We report a methodology to obtain thin films of cucurbit[6]uril, starting from ammoniacal solutions. This technique is very useful for the obtention of modified electrodes or other substrates for sensor purposes. Cucurbit[6]uril is insoluble in most media, and film formation was impossible until now.