Jose Manuel Caicedo

Low-temperature, solution-processed, layered V2O5 hydrate as the hole-transport layer for stable organic solar cells

Layered V2O5 hydrate has been applied as the hole transport layer (HTL) in organic solar cells (OSCs). V2O5 is obtained from a sodium metavanadate solution in water under ambient conditions, resulting in a final thin film of formula V2O5·0.5H2O. The 0.5 water molecules are not removed from the V2O5 layered structure unless the sample is heated above 250 °C, which makes the thin film highly stable under real working conditions. The HTL was used in OSCs in the normal and the inverted configurations, applying metallic Ag as the back-metal electrode in both cases. Fabrication of both OSC configurations completely by solution-processing printing methods in air is possible, since the Al electrode needed for the normal-configuration OSC is not required. The work function (WF) and band gap energy (BG) of the V2O5 thin films were assessed by XPS, UPS and optical analyses. Different WF values were observed for V2O5 prepared from a fresh V2O5–isopropanol (IPA) solution (5.15 eV) and that prepared from a 24 h-old solution (5.5 eV). This difference is due to the gradual reduction of vanadium (from V5+ to V4+) in IPA. The OSCs made with the V2O5 thin film obtained from the 24 h-old V2O5–IPA solution required photo-activation, whereas those made with the freshly obtained V2O5 did not. Outdoor stability analyses of sealed OSCs containing a V2O5 HTL in either configuration revealed high stability for both devices: the photovoltaic response at T80 was retained for more than 1000 h.

Magnetophotonic Response of Three- Dimensional Opals

Three-dimensional magnetophotonic crystals (3D-MPCs) are being postulated as appropriate platforms to tailor the magneto-optical spectral response of magnetic materials and to incorporate this functionality in a new generation of optical devices. By infiltrating self-assembled inverse opal structures with monodisperse nickel nanoparticles we have fabricated 3D-MPCs that show a sizable enhancement of the magneto-optical signal at frequencies around the stop-band edges of the photonic crystals. We have established a proper methodology to disentangle the intrinsic magneto-optical spectra from the nonmagnetic optical activity of the 3D-MPCs. The results of the optical and magneto-optical characterization are consistent with a homogeneous magnetic infiltration of the opal structure that gives rise to both a red-shift of the optical bandgap and a modification of the magneto-optical spectral response due to photonic bandgap effects. The results of our investigation demonstrate the potential of 3D-MPCs fabricated following the approach outlined here and offer opportunities to adapt the magneto-optical spectral response at optical frequencies by appropriate design of the opal structure or magnetic field strength.

Magneto-optical enhancement by plasmon excitations in nanoparticle/metal structures.

Coupling magnetic materials to plasmonic structures provides a pathway to dramatically increase the magneto-optical response of the resulting composite architecture. Although such optical enhancement has been demonstrated in a variety of systems, some basic aspects are scarcely known. In particular, reflectance/transmission modulations and electromagnetic field intensification, both triggered by plasmon excitations, can contribute to the magneto-optical enhancement. However, a quantitative evaluation of the impact of both factors on the magneto-optical response is lacking. To address this issue, we have measured magneto-optical Kerr spectra on corrugated gold/dielectric interfaces with magnetic (nickel and iron oxide) nanoparticles. We find that the magneto-optical activity is enhanced by up to an order of magnitude for wavelengths that are correlated to the excitation of propagating or localized surface plasmons. Our work sheds light on the fundamental principles for the observed optical response and demonstrates that the outstanding magneto-optical performance is originated by the increase of the polarization conversion efficiency, whereas the contribution of reflectance modulations is negligible.

Magneto-optical characterization of colloidal dispersions. Application to nickel nanoparticles.

We report here on a fast magneto-optical characterization method for colloidal liquid dispersions of magnetic nanoparticles. We have applied our methodology to Ni nanoparticles with size equal or below 15 nm synthesized by a ligand stabilized solution-phase synthesis. We have measured the magnetic circular dichroism (MCD) of colloidal dispersions and found that we can probe the intrinsic magnetic properties within a wide concentration range, from 10(-5) up to 10(-2) M, with sensitivity to concentrations below 1 microg/mL of magnetic Ni particles. We found that the measured MCD signal scales up with the concentration thus providing a means of determining the concentration values of highly diluted dispersions. The methodology presented here exhibits large flexibility and versatility and might be suitable to study either fundamental problems related to properties of nanosize particles including surface related effects which are highly relevant for magnetic colloids in biomedical applications or to be applied to in situ testing and integration in production lines.

Ultrathin conformal coating for complex magneto-photonic structures

We report on an extremely fast and versatile synthetic approach, based on microwave assisted sol-gel chemistry, that allows a conformal nanometric coating of intricate three-dimensional structures. Using this methodology, we have achieved a conformal coverage of large areas of three-dimensional opals with a superparamagnetic manganese ferrite layer, yielding magneto-photonic crystals with excellent quality. The use of a ternary oxide for the ultrathin coating demonstrates the potential of this methodology to realize three-dimensional structures with complex materials that may find applications beyond photonics, such as energy, sensing or catalysis.

Magneto-optic material selectivity in self-assembled BiFeO3–CoFe2O4 biferroic nanostructures

Material selective sensitivity of a magneto-optical polar Kerr effect to magnetic contributions from different inclusions in self-organized magnetic nanostructures is presented. The method is supported by modeling of the magneto-optic response based on the effective medium approximation and by hysteresis loop measurement of the multiferroic BiFeO3–CoFe2O4 self-assembled nanostructure. Magneto-optic selective sensitivity is demonstrated and explained as an effect of different complex diagonal and off-diagonal permittivity tensor elements of two materials.

An in operando study of chemical expansion and oxygen surface exchange rates in epitaxial GdBaCo2O5.5 electrodes in a solid-state electrochemical cell by time-resolved X-ray diffraction

This report explores the fundamental characteristics of epitaxial thin films of a mixed ionic electronic conducting GdBaCo2O5.5±δ (GBCO) material with a layered perovskite structure, relevant for use as an active electrode for the oxygen reduction and evolution reactions in electrochemical devices. Time-resolved X-ray diffraction in combination with voltage step chrono-amperometric measurements in a solid state electrochemical cell provides a deeper insight into the chemical expansion mechanism in the GBCO electrode. The chemical expansion coefficient along the c-axis, αc, shows a negative value upon the compound oxidation contrary to standard perovskite materials with disordered oxygen vacancies. Chemical expansion also shows a remarkable asymmetry from αc = −0.037 to −0.014 at δ 0, respectively. This change in chemical expansion is an indication of a different mechanism of the structural changes associated with the variable Co cation oxidation state from Co2+ → Co3+ → Co4+. Since redox reactions are dominated by oxygen surface exchange between the GBCO electrode and gas atmosphere, monitoring the time response of the structural changes allows for direct determination of oxygen reduction and evolution reaction kinetics. The reaction kinetics are progressively slowed down upon reduction in the δ 0 region, in agreement with the structural changes and the electronic carrier delocalization when crossing δ = 0. This work validates the time-resolved XRD technique for fast and reversible measurements of electrode activity in a wide range of oxygen non-stoichiometry in a solid-state electrochemical cell operating under realistic working conditions.