Controlled Deposition of Nanostructured Hierarchical TiO2 Thin Films by Low Pressure Supersonic Plasma Jets.

Plasma-assisted supersonic jet deposition (PA-SJD) is a precise technique for the fabrication of thin films with a desired nanostructured morphology. In this work, we used quadrupole mass spectrometry of the neutral species in the jet and the extensive characterization of TiO2 films to improve our understanding of the relationship between jet chemistry and film properties. To do this, an organo-metallic precursor (titanium tetra-isopropoxide or TTIP) was first dissociated using a reactive argon-oxygen plasma in a vacuum chamber and then delivered into a second, lower pressure chamber through a nozzle. The pressure difference between the two chambers generated a supersonic jet carrying nanoparticles of TiO2 in the second chamber, and these were deposited onto the surface of a substrate located few centimeters away from the nozzle. The nucleation/aggregation of the jet nanoparticles could be accurately tuned by a suitable choice of control parameters in order to produce the required structures. We demonstrate that high-quality films of up to several µm in thickness and covering a surface area of few cm2 can be effectively produced using this PA-SJD technique.

Development of antibacterial quaternary ammonium silane coatings on polyurethane catheters.

Polyurethene (PU) catheters were coated with 3-(trimethoxysilyl)-propyldimethyloctadecylammonium chloride (QAS) by means of a multistep process which involved a vapor phase plasma-induced graft-polymerization of acrylic acid (AAc). The AAc coating, whose stability in aqueous media was assessed by immersion in Phospate Buffer Saline (PBS), was characterized by means of Attenuated Total Reflectance Fourier Transform Infrared (ATR/FTIR) spectroscopy. Moreover, the COOH surface density was evaluated by a colorimetric assay with Methylene Blue. Carrying a negative charge at neutral pH, AAc coatings were proficient in positively charged molecules (like QAS) adsorption. ATR/FTIR spectroscopy and a colorimetric assay with Bromophenol Blue allowed us to verify the presence and the uniformity of the QAS coating on the PU catheters and the positive effect of the AAc graft-polymerization on the QAS adsorption. Morphological characterization of the QAS-modified catheters was performed by means of Atomic Force Microscopy (AFM). QAS-coated catheters displayed in vitro antimicrobial activity against Gram-negative Escherichia coli bacterial cells.

The role of π bridges in high-efficiency DSCs based on unsymmetrical squaraines.

A series of squaraine-based sensitizers with various π bridges and anchors were prepared and examined in dye-sensitized solar cells. The carboxylic anchor group was attached onto a squaraine dye through π bridges with and without an ethynyl spacer. DFT studies indicate that the LUMO is delocalized throughout the dyes, whilst the HOMO resides on the squaraine core. The dye that incorporates a 4,4-di-n-hexyl-cyclopentadithiophene group that is directly attached onto the π bridge, JD10, exhibits the highest power conversion efficiency in a DSC; this result is attributed, in part, to the deaggregative properties that are associated with the gem-di-n-hexyl substituents, which extend above and below the π-conjugated dye plane. Dye JD10 demonstrates a power-conversion efficiency of 7.3% for liquid-electrolyte dye-sensitized solar cells and 7.9% for cells that are co-sensitized by another metal-free dye, D35, which substantially exceed the performance of any previously tested squaraine sensitizer. A panchromatic incident-photon-to-current-conversion efficiency curve is realized for this dye with an excellent short-circuit current of 18.0 mA cm(-2). This current is higher than that seen for other squaraine dyes, partially owing to a high molar absorptivity of >5,000 M(-1) cm(-1) from 400 nm to the long-wavelength onset of 724 nm for dye JD10.

Thiocyanate-free cyclometalated ruthenium sensitizers for solar cells based on heteroaromatic-substituted 2-arylpyridines.

The first examples of thiocyanate-free thiophene-substituted Ru(II) cyclometalated complexes, based on thiophene-derived 2-(2,4-difluorophenyl)pyridine ligands, are presented and investigated as photosensitizers in DSCs. Upon thiophene substitution the complexes presented enhanced optical properties compared to the reference dye with no thiophene substitution. DSCs based on the dithienyl-derived dye showed power conversion efficiencies up to 5.7%, more than twice that containing the complex without the thiophene substitution.

Towards flexibility: metal free plastic cathodes for dye sensitized solar cells.

We report herein lightweight, and economical dye-sensitized solar cells fabrication facilitated by an all plastic, metal free cathode consisting of poly(3,4-ethylenedioxythiophene).