Abstract
The electrodeposition mechanisms of poly(3,4-ethylenedithiathiophene) (PEDTT), which is the sulfur analogue of the well-known poly(3,4-ethylenedioxythiophene) (PEDOT), is investigated in acetonitrile solution by means of potentiostatic methods. By analyzing the current transients within electrocrystallization theory, we observe that the electrodeposition process is a combination of two mechanisms: progressive nucleation, followed by a diffusion-controlled three-dimensional growth (PN3DD); and an instantaneous nucleation, followed by a three-dimensional growth mechanism with charge transfer as the rate-limiting factor (IN3DC). This trend is contrary to PEDOT electrodeposition mechanisms. Cyclic voltametric measurements show important differences between PEDOT and PEDTT. The most unexpected result is that, although 3,4-ethylenedithiathiophene (EDTT) has a lower oxidation potential than 3,4-ethylenedioxythiophene (EDOT), the polymer PEDTT presents a higher oxidation potential and larger band gap than PEDOT....
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