It is known that the molecular architecture plays a fundamental role in the electrical and optical properties of materials processed in the form of thin films. Here, zinc phthalocyanine (ZnPc) thin films were fabricated through the vacuum thermal evaporation technique (PVD, physical vapor deposition) up to 50 nm thickness with the objective of determining their molecular architecture and some electrical and optical properties. Structurally, the results showed a uniform growth of the films depending on how the evaporation is performed (step-by-step or straightforward). The uniform films present a molecular organization dominated by the ZnPc macrocycle ring forming almost 90°in relation to the substrate surface. These films are crystalline (R-form) and possess molecular aggregates in the form of dimers (or higher order of aggregates) and monomers. Such aggregates are seen at the nanometer scale; however, at the micrometer scale, the films are morphologically homogeneous. In relation to the optical properties, it was observed that these films, besides absorbing in the ultraviolet-visible region, present a photoluminescence when irradiated with the 785 nm laser line. In terms of electrical properties, it was determined an electrical conductivity of ca. 10 -10 S/m and a significant photoconducting activity. Finally, a dependence of the molecular organization, crystallinity, and optical properties on the film annealing (and thickness) was investigated, and the sensitivity of the ZnPc PVD films against gasoline vapor was tested as proof-of-principle.
Langmuir films have been fabricated from poly[(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene] (OC1OC6-PPV). The stability and the area per monomer for condensed films indicate the formation of true monolayers with a very small extent of aggregation, which is unusual for polymer films. This is attributed to the linearity of the alkyl side chain. The Y-type Langmuir-Blodgett (LB) films produced from Langmuir films of OC 1OC6-PPV have distinctive features compared to those of cast films, probably due to the organization in the LB films whereas the molecules are randomly oriented in cast films. Infrared absorption spectra recorded for both transmission and reflection modes indicate that OC 1OC6-PPV molecules are anchored to the substrate by the lateral groups. This is confirmed by the Raman spectrum, in which a distortion of the vinylene group was observed, and by surface enhanced fluorescence (SEF) on an LB monolayer deposited onto Ag nanoparticles. The more homogeneous nature of the LB films in comparison with the case of cast films was demonstrated by optical microscopy and fluorescence measurements where the emission spectra were essentially the same for different regions of an LB film but showed dispersion in cast films. The LB films also displayed reversible photoconductivity.
Langmuir-Blodgett (LB) and layer-by-layer films (LbL) of a PPV (p-phenylenevinylene) derivative, an azo compound and tetrasulfonated phthalocyanines were successfully employed as transducers in an "electronic tongue" system for detecting trace levels of phenolic compounds in water. The choice of the materials was based on their distinct electrical natures, which enabled the array to establish a fingerprint of very similar liquids. Impedance spectroscopy measurements were taken in the frequency range from 10 Hz to 1 MHz, with the data analysed with principal component analysis (PCA). The sensing units were obtained from five-layer LB films of (poly[(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene]), OC(1)OC(18)-PPV (poly(2-methoxy,5-(n-octadecyl)-p-phenylenevinylene)), DR (HEMA-co-DR13MA (poly-(hydroxyethylmethacrylate-co-[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene]))) and five-bilayer LbL films of tetrasulfonated metallic phthalocyanines deposited onto gold interdigitated electrodes. The sensors were immersed into phenol, 2-chloro-4-methoxyphenol, 2-chlorophenol and 3-chlorophenol (isomers) solutions at 1 x 10(-9) mol L(-1), with control experiments carried out in ultra pure water. Samples could be distinguished if the principal component analysis (PCA) plots were made with capacitance values taken at 10(3) Hz, which is promising for detection of trace amounts of phenolic pollutants in natural water.
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