Improved Anisotropic Thermoelectric Behavior of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) via Magnetophoresis

[Image: see text] There is strong demand for achieving morphological control of conducting polymers in its many potential applications, from energy harvesting to spintronics. Here, the static magnetic-field-induced alignment of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) particles is demonstrated. PEDOT:PSS thin films cast under modest mT-level magnetic fields exhibit a fourfold increase in the Seebeck coefficient and doubled electrical conductivity. Atomic force microscopy measurements confirm the presence of conducting islands that exhibit a 10-fold increase in the local charge carrier mobility and threshold behavior that is associated with phase separation. High-resolution scanning electron microscopy identifies a consistent structural coil-to-rod transition, and three-dimensional time-of-flight secondary-ion mass spectrometry imaging shows that the rodlike structures coincide with PEDOT domains that generally align with the magnetic field and cluster on the outer surface. Grazing-incidence small-angle X-ray scattering, Raman spectra, electron paramagnetic resonance, and circular dichroism spectroscopy point to the physical nature of the magnetophoretic alignment, which is expected to occur via magnetic coupling of PEDOT domains with polaron modes. Because casting under mT-level magnetic fields increases the electrical conductivity and Seebeck coefficient of PEDOT:PSS thin films without additional dopants that commonly limit the thermoelectric performance, our research reveals that low-field magnetophoresis significantly influences the structure and corresponding physical properties of PEDOT:PSS. Our results also point to concerns that the presence of small external magnetic fields in laboratory settings may appreciably and inadvertently influence the PEDOT:PSS morphology during settling, drying, or annealing processes.