An electrochemical
cell designed to allow in situ observation of
crystal growth of organic conductors was fabricated, and the initial
growth process of a partially oxidized salt of bis(ethylenedithio)tetrathiafulvalene
(ET) was investigated for different current values. The shape, number,
and size of the single crystals grown on the electrode depended on
the current. However, our results suggested that the presence of trap
sites on the electrode surfaces, which promote crystal nucleation,
is more important for crystal growth, since flawless surfaces prepared
by melting the electrode gave no crystals. The flawless electrode
modified with an alkanethiol self-assembled monolayer (SAM) did not
give crystals, while with a terminal carboxylate SAM, it yielded quality
crystals over the entire surface, indicating that, when modified by
anionic species, the electrode surfaces promote clustering of the
oxidized ET radical cations and succeed in nucleating crystal growth
of the partially oxidized salt.