Understanding the mass uptake, morphological changes,
and charge
transport in organic mixed ionic–electronic conductors (OMIECs)
during device operation is crucial for applications in energy, actuators,
and bioelectronics. In this work, we quantify the chemical composition
and rheological properties of a model OMIEC material, acid-treated
poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT/PSS),
during electrochemical cycling using electrochemical quartz crystal
microbalance (EQCM) and elemental analysis techniques. We find an
asymmetry in the de- and redoping mass transport kinetics and attribute
this process to subsecond ion migration and slower ion reorganization.
Furthermore, the kinetic constants from the EQCM measurements are
compared to those from organic electrochemical transistors and from
changes in structural packing by normalizing the corresponding RC
time constants across experiments. This multimodal investigation allows
us to deduce a sequence of mass, charge, and structure kinetics in
OMIEC materials during the de- and redoping processes. The kinetics
of processes in acid-treated PEDOT/PSS in response to step voltages
can be clustered into three main subprocesses, namely, fast polarization,
charge carrier population kinetics and macroscale transport, and slow
relaxation. These findings provide a basis for future OMIEC design
by determining the factors that affect response time and short-term
stability of OMIEC devices.