Soluble polyacetylenes derived from the ring-opening metathesis polymerization of substituted cyclooctatetraenes: electrochemical characterization and Schottky barrier devices

Recent developments in ring-opening metathesis polymerization (ROMP) have enabled the synthesis of poly-cyclooctatetraene (poly-COT), a material which is isostructural to polyacetylene. This liquid-phase polymerization method allows facile construction of interfaces, films, and devices with polyacetylene-like materials. The ROMP method also allows the preparation of soluble, yet highly conjugated polyacetylene analogs from substituted cyclooctatetraenes (R-COT). The redox characteristics of R-COT polymers were investigated at electrodes modified with thin polymer films. Voltammetric methods were used to characterize the redox response, band gap, electrochemical doping, and cis-trans isomerization properties of these polyenes. We have applied poly-COT technology to the fabrication of Schottky diodes and photoelectrochemical cells, by forming poly-COT films on semiconductor surfaces. The resultant semiconductor/organic-metal interfaces behave more ideally than semiconductor contacts with conventional metals, in that changes in the work function of the conducting polymer exert a large and predictable effect on the electrical properties of the resulting Schottky diodes. Transparent films of the solution-processible polymer poly- trimethylsilyl-cyclooctatetraene (poly-TMS-COT) have been cast onto n-silicon substrates and doped with iodine to form surface barrier solar cells. These devices produce photovoltages that are much larger than can be obtained from n-silicon contacts with conventional metals.