  The fabrication of hybrid materials consisting of nanoporous hosts with
conductive polymers is a challenging task, since the extreme spatial
confinement often conflicts with the stringent physico-chemical requirements
for polymerization of organic constituents. Here, several low-threshold and
scalable synthesis routes for such hybrids are presented. First, the
electrochemical synthesis of composites based on mesoporous silicon (pore size
of 7 nm) and the polymers PANI, PPy and PEDOT is discussed and validated by
scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy
(EDX). Polymer filling degrees of 74% are achieved. Second, the production of
PEDOT/pSi hybrids, based on the solid-state polymerization (SSP) of DBEDOT to
PEDOT is shown. The resulting amorphous structure of the nanopore-embedded
PEDOT is investigated via in-situ synchrotron-based X-ray scattering. In
addition, a twofold increase in the electrical conductivity of the hybrid
compared to the porous silicon host is shown, making this system particularly
promising for thermoelectric applications.
