Influence of Polyfluorinated Side Chains and Soft-Template Method on the Surface Morphologies and Hydrophobic Properties of Electrodeposited Films from Fluorene Bridged Dicarbazole Monomers.

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.

Improving the Electropolymerization Properties of Fluorene-Bridged Dicarbazole Monomers through Polyfluoroalkyl Side Chains.

The facile functionalization of the fluorene scaffold at the 2,7-positions was utilized to provide access to two soluble carbazole-π-carbazole derivatives CFC-H1 and CFC-F1 featuring fully hydrogenated and polyfluorinated alkyl chains at the 9-position of the fluorene π-bridging unit, respectively. The optical and electrochemical properties of the new dicarbazoles were investigated. Their electrochemical polymerization over Pt and indium tin oxide electrodes allowed the generation of electroactive polymeric films, whose physicochemical characteristics were strongly dependent on the kind of alkyl chain present on the fluorene bridge. In particular, the electropolymerization of the polyfluorinated monomer allowed the fabrication of thin films with good electrical conductivity, reversible electrochemical processes, good electrochromic properties, and enhanced water repellency with respect to its nonfluorinated analogue.

High performance PbS Quantum Dot Sensitized Solar Cells exceeding 4% efficiency: the role of metal precursors in the electron injection and charge separation.

Here we report the preparation of high performance Quantum Dot Sensitized Solar Cells (QDSCs) based on PbS-CdS co-sensitized nanoporous TiO2 electrodes. QDs were directly grown on the TiO2 mesostructure by the Successive Ionic Layer Absorption and Reaction (SILAR) technique. This method is characterized by a fast deposition rate which involves random crystal growth and poor control of the defect states and lattice mismatch in the QDs limiting the quality of the electrodes for photovoltaic applications. In this work we demonstrate that the nature of the metallic precursor selected for SILAR has an active role in both the QD's deposition rate and the defect's distribution in the material, with important consequences for the final photovoltaic performance of the device. For this purpose, acetate and nitrate salts were selected as metallic precursors for the SILAR deposition and films with similar absorption properties and consequently with similar density of photogenerated carriers were studied. Under these conditions, ultrafast carrier dynamics and surface photovoltage spectroscopy reveal that the use of acetate precursors leads to higher injection efficiency and lower internal recombination due to contribution from defect states. This was corroborated in a complete cell configuration with films sensitized with acetate precursors, achieving unprecedented photocurrents of ~22 mA cm(-2) and high power conversion efficiency exceeding 4%, under full 1 sun illumination.

Electrochemical bubble generation via hydrazine oxidation for the in situ control of an electrodeposited conducting polymer micro/-nanostructure.

Herein, a simple, in situ, on step and highly repeatable electrochemical method that allows controlling the nanostructure of electrodeposited polymer films is reported. As an example, the tuning of the electrodeposited polypyrrole nanostructures using inert gas bubbles as the template at the electrode surface generated by the electrochemical oxidation of hydrazine is shown. The hydrazine discharge occurs at a lower potential regarding the beginning of pyrrole electropolymerization process, which allows the modulation of the density and size of the bubbles on the surface electrode controlling electrochemical parameters (applied potential, concentration, time, etc.). Subsequently, the applied potential is moved to where the pyrrole polymerization begins, which induces the material discharges around the bubble template producing polypyrrole hollow structures with definite patterns on the electrode surface. This methodology is proposed as a simple model for the electrodeposition with the morphological control of a wide range of conductive polymers.

The optoelectronic behaviour of carbon nanoparticles: evidence of the importance of the outer carbon shell.

The particular properties of carbon nanoparticles (CNPs) have generated great interest in biomedicine, bioanalysis and optoelectronics. However, an association between the CNPs' physicochemical properties with their molecular and morphological characteristics is, even today, a topic of discussion. In this work, we use a simple method of synthesis with the ultimate aim of elucidating the structural nature of the obtained CNPs and its relationship with their well-known fluorescent properties. The sample is studied by high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy (EELS), nuclear magnetic resonance (NMR), UV-visible and IR spectroscopy, electrochemistry and electrogenerated chemiluminescence (ECL). The results showed that the nanoparticles are constituted by a graphitic core surrounded by an amorphous layer, which seems to be significant in the determination of the optical and electronic properties observed in the system under study.