Cu(I)-I-2,4-diaminopyrimidine Coordination Polymers with Optoelectronic Properties as a Proof of Concept for Solar Cells.

Two coordination polymers with formulas [CuI(dapym)]n and [Cu2I2(dapym)]n (dapym = 2,4-diaminopyrimidine) have been synthesized in water at room temperature. According to the stoichiometry used, mono (1D) and the two-dimensional (2D) structures can be obtained. Both are made up of Cu2I2 double chains. Their high insolubility in the reaction medium also makes it possible to obtain them on a nanometric scale. Their structural flexibility and short Cu-Cu distances provoke interesting optoelectronic properties and respond to physical stimuli such as pressure and temperature, making them interesting for sensor applications. The experimental and theoretical studies allow us to propose different emission mechanisms with different behaviors despite containing the same organic ligand. These behaviors are attributed to their structural differences. The emission spectra versus pressure and temperature suggest competencies between different transitions, founding critical Cu2I2 environments, i.e., symmetric in the 1D compound and asymmetric for the 2D one. The intensity in the 2D compound's emission increases with decreasing temperature, and this behavior can be rationalized with a structural constriction that decreases the Cu-Cu and Cu-I distances. However, compound 1D exhibits a contrary behavior that may be related to a change of the organic ligand's molecular configuration. These changes imply that a more significant Π-Π interaction counteracts the contraction in distances and angles when the temperature decreased. Also, the experimental conductivity measurements and theoretical calculations show a semiconductor behavior. The absorption of the 1D compound in UV, its intense emission at room temperature, and the reduction to nanometric size have allowed us to combine it homogeneously with ethyl vinyl acetate (EVA), creating a new composite material. The external quantum efficiency of this material in a Si photovoltaic mini-module has shown that this compound is an active species with application in solar cells since it can move the photons of the incident radiation (UV region) to longer wavelengths.

Cu(i)-I coordination polymers as the possible substitutes of lanthanides as downshifters for increasing the conversion efficiency of solar cells.

This study tries to provide new solutions to increase the efficiency of conversion of photons in solar cells, using photoluminescent Cu(i) coordination polymers (CPs) as possible alternative materials of lower cost, than those used today, based on lanthanides. The selected CP of chemical formula [Cu(NH2MeIN)I]n (NH2MeIN = methyl, 2-amino isonicotinate) absorbs in the utraviolet and emits in the visible region, being also easily nanoprocessable, by a simple and one-pot bottom-up approach. Nanofibers of this CP can be embedded in organic matrices such as ethyl vinyl acetate (EVA), forming transparent and homogenous films, with a thermal stability of up to approximately 150 °C. These new materials maintain the optical properties of the CP used as a dopant, ([Cu(NH2MeIN)I]n), with emission in yellow (570 nm) at 300 K, which is intensified when the working temperature is lowered. In addition, these materials can be prepared with varying thicknesses, from a few microns to a few hundred nanometers, depending on the deposition method used (drop casting or spin coating respectively). The study of their external quantum efficiency (EQE) found an increase in the UV range, which translates into an increase in the conversion efficiency. The optimal CP concentration is 5% by weight in order to not diminish the transparency of the composite material. The calculated cost on the possible incorporation of this material into solar cells shows a 50% decrease over the cost reported in similar studies based on the use of lanthanides.

Bimodal Nd-Doped LuVO4 Nanoprobes Functionalized with Polyacrilic Acid for X-Ray Computed Tomography and NIR Luminescent Imaging.

Uniform Nd3+-doped LuVO4 nanophosphors have been synthesized for the first time in literature by using a poliol-based method at 120 °C from Nd3+ and vanadate precursors. After optimizing the Nd doping level, these phosphors present intense luminescence in the near-infrared biological windows. The X-ray attenuation capacity of the optimum nanophosphor has been found to be higher than that of a commercial X-ray computed tomography contrast agent. After surface coating with polyacrylic acid, such nanoparticles present high colloidal stability in physiological pH medium and high cell viability. Because of these properties, the developed Nd3+-doped LuVO4 nanoparticles have potential applications as a bimodal probe for NIR luminescent bioimaging and X-ray computed tomography.

Room temperature synthesis of water-dispersible Ln3+:CeF3 (Ln = Nd, Tb) nanoparticles with different morphology as bimodal probes for fluorescence and CT imaging.

The singular properties of lanthanide-based inorganic nanoparticles (NPs) has raised the attention of the scientific community in biotechnological applications. In particular, those systems with two or more functionalities are especially interesting. In this work, an effective and commercially attractive procedure has been developed that renders uniform, water-dispersible Ln3+:CeF3 (Ln = Tb, Nd) NPs with different shapes and size. The method consists of the homogeneous precipitation, in a mixture of polyol and water, of cations and anions using precursors that allow the controlled release of the latter. The advantages of the reported method are related to the absence of surfactants, dispersing agents or corrosive precursors as well as to the room temperature of the process. The obtained Tb:CeF3 NPs produce an intense emission after excitation through the Ce-Tb energy transfer band located in the UV spectral region, thus being potentially useful as phosphors for in-vitro imaging purposes. On the other hand, the synthesized Nd:CeF3 NPs are good candidates for in-vivo imaging because their excitation and emission wavelengths lie in the biological windows. Finally, the excellent X-ray attenuation efficacy of the Nd:CeF3 NPs is shown, which confers double functionality to this material as both luminescence bioprobe and contrast agent for X-ray computed-tomography.

Crystal structure, NIR luminescence and X-ray computed tomography of Nd3+:Ba0.3Lu0.7F2.7 nanospheres.

Uniform, hydrophilic 50 nm diameter Nd3+-doped Ba0.3Lu0.7F2.7 nanospheres are synthesized at 120 °C using a singular one-pot method based on the use of ethylene glycol as solvent, in the absence of any additive. The composition and crystal structure of the undoped material are analyzed in detail using ICP and XRD, which reveals a BaF2 cubic crystal structure that is able to incorporate 70 mol% of Lu ions. This finding contrasts with the reported phase diagram of the system, where the maximum solubility is around 30 mol% Lu. XRD proves as well that the Ba0.3Lu0.7F2.7 structure is able to incorporate Nd3+ ions up to, at least 10 mol%, without altering the uniform particles morphology. The Nd-doped particles exhibit near-infrared luminescence when excited at 810 nm. The maximum emission intensity with the minimum concentration quenching effect is obtained at 1.5% Nd doping level. X-ray computed tomography experiments are carried out on powder samples of the latter composition. The sample significantly absorbs X-ray photons, thus demonstrating that the Nd3+-doped Ba0.3Lu0.7F2.7 nanospheres are good candidates as contrast agents in computed tomography.

Multifunctional Eu-doped NaGd(MoO4)2 nanoparticles functionalized with poly(l-lysine) for optical and MRI imaging.

A method for the synthesis of non-aggregated and highly uniform Eu3+ doped NaGd(MoO4)2 nanoparticles is reported for the first time. The obtained particles present tetragonal structure, ellipsoidal shape and their size can be varied by adjusting the experimental synthesis parameters. These nanoparticles, which were coated with citrate anions and functionalised with PLL, have also been developed in order to improve their colloidal stability in physiological medium (2-(N-morpholino)ethanesulfonic acid, MES). A study of the luminescent dynamics of the samples as a function of the Eu doping level has been conducted in order to find the optimum nanophosphors, whose magnetic relaxivity and cell viability have also been evaluated for the first time for this system, in order to assess their suitability as multifunctional probes for optical (in vitro) and magnetic bioimaging applications.

Ligand-Free Synthesis of Tunable Size Ln:BaGdF5 (Ln = Eu³âº and Nd³âº) Nanoparticles: Luminescence, Magnetic Properties, and Biocompatibility.

Bifunctional and highly uniform Ln:BaGdF5 (Ln = Eu(3+) and Nd(3+)) nanoparticles have been successfully synthesized using a solvothermal method consisting of the aging at 120 °C of a glycerol solution containing the corresponding Lanthanide acetylacetonates and butylmethylimidazolium tetrafluoroborate. The absence of any surfactant in the synthesis process rendered hydrophilic nanospheres (with tunable diameter from 45 nm 85 nm, depending on the cations concentration of the starting solution) which are suitable for bioapplications. The particles are bifunctional because they showed both optical and magnetic properties due to the presence of the optically active lanthanides (Eu(3+) in the visible and Nd(3+) in the NIR regions of the electromagnetic spectrum) and the paramagnetic gadolinium ion, respectively. The luminescence decay curves of the nanospheres doped with different amounts of Eu(3+) and Nd(3+) have been recorded in order to determine the optimum dopant concentration in each case, which turned out to be 5% Eu(3+) and 0.5% Nd(3+). Likewise, proton relaxation times were measured at 1.5 T in water suspensions of the optimum particles found in the luminescence study. The values obtained suggested that both kinds of particles could be used as positive contrast agents for MRI. Finally, it was demonstrated that both the 5% Eu(3+) and 0.5% Nd(3+)-doped BaGdF5 nanospheres showed negligible cytotoxicity for VERO cells for concentrations up to 0.25 mg mL(-1).

Parallel multifunctionalization of nanoparticles: a one-step modular approach for in vivo imaging.

Multifunctional nanoparticles are usually produced by sequential synthesis, with long multistep protocols. Our study reports a generic modular strategy for the parallel one-step multifunctionalization of different hydrophobic nanoparticles. The method was designed and developed by taking advantage of the natural noncovalent interactions between the fatty acid binding sites of the bovine serum albumin (BSA) and the aliphatic surfactants on different inorganic nanomaterials. As a general example of the approach, three different nanoparticles-iron oxide, upconverting nanophosphors, and gold nanospheres-were nanoemulsified in water with BSA. To support specific applications, multifunctional capability was incorporated with a variety of previously modified BSA modules. These modules include different conjugated groups, such as chelating agents for (68)Ga or (89)Zr and ligand molecules for enhanced in vivo targeting. A large library of 13 multimodal contrast agents was developed with this convergent strategy. This platform allows a highly versatile and easy tailoring option for efficient incorporation of functional groups. Finally, as demonstration of this versatility, a bimodal (PET/MRI) probe including a maleimide-conjugated BSA was selectively synthesized with an RGD peptide for in vivo imaging detection of tumor angiogenesis.

Quantification of energy transfer processes in LiLa9(SiO4)6O2:Er³âº/Yb³âº under selective Er³âº excitation.

The energy transfer mechanisms between Er3+ and Yb3+ ions have been investigated in LiLa9(SiO4)6O2 under selective Er3+ excitation. IR emission spectra, measured in the CW excitation regime, were used to establish a relationship between the macroscopic transfer and back transfer parameters. These measurements were combined with the results obtained under pulsed excitation to quantify the absolute values of transfer (Yb3+ → Er3+) and back transfer coefficients (Er3+ → Yb3+), C25 = 9.5 × 10−17 cm3s−1 and C52 = 1.4 × 10−17 cm3s−1, respectively. Additionally, it has been observed an energy transfer that reduces the quantum efficiency of the green emitting Er3+ levels. The corresponding macroscopic coefficient has been also determined (CGQ = 6.1 × 10−17 cm3s−1).

Continuous-wave and Q-switched Tm-doped KY(WO4)2 planar waveguide laser at 1.84 µm.

High-quality monoclinic planar waveguide crystals of Tm-doped KY(WO4)2 codoped with Gd3+ and Lu3+ were grown by liquid-phase epitaxy. For the first time, planar waveguide lasing was demonstrated in a monolithic cavity in the 2 µm spectral range. The laser was operated in the Q-switched mode using a Cr2+:ZnSe crystal as saturable absorber and in the continuous-wave regimes. The Q-switched planar waveguide laser delivered pulse energies up to 120 nJ at a repetition rate of 7 kHz.

Tuning from blue to magenta the up-converted emissions of YF3:Tm3+/Yb3+ nanocrystals.

Monodisperse YF3:Tm3+/Yb3+ nanocrystals have been synthesized to explore the visible up-converting properties under near infrared (975 nm) excitation. It has been found that the nanoparticles exhibit intense red up-converted emissions, in addition to the characteristic UV and blue Tm3+-bands. It is demonstrated that, by carefully selecting Tm3+ and Yb3+ contents, the relative intensity of the different emissions can be changed producing an overall emission colour that can be tuned from blue to magenta.

Micro-Raman characterization of Zn-diffused channel waveguides in Tm(3+):LiNbO(3).

In this work micro-Raman scattering experiments have been performed in LiNbO(3):Tm(3+) samples with waveguides fabricated by Zn(2+) in-diffusion. The results shown that Zn(2+) ions enter the lattice in Li(+) sites, but also in interstitial positions. This produces a compaction of the lattice close to the surface of the sample, generating the waveguide. It is shown that this region is surrounded by a different area in which the lattice is relaxed to recover the characteristic lattice parameters of LiNbO(3):Tm(3+).

Mirrorless buried waveguide laser in monoclinic double tungstates fabricated by a novel combination of ion milling and liquid phase epitaxy.

Buried channel waveguides were fabricated by liquid phase epitaxial growth of a lattice-matched KY(0.58)Gd(0.22)Lu(0.17)Tm(0.03)(WO4)2 film on a microstructured KY(WO4)2 substrate. Channels were transferred to the substrates by standard photolithography and Ar-ion milling. The bottom and sidewalls of the milled channels were smooth enough (rms roughness = 70 nm and 20 nm, respectively) to favour the epitaxial growth of the active layer without defects at the boundary of substrate/epitaxial layer. The refractive index contrast was sufficient to enable light confinement and guided modes with low scattering losses were observed at wavelengths between 1440 nm and 1640 nm. CW laser operation at 1840 nm at room temperature was observed with feedback provided only by Fresnel reflection at the end faces, with slope efficiencies of 4% and 9% for TE and TM polarizations, respectively.