Understanding how local structure and chemistry govern electrochemical performance is central to advancing functional materials for catalysis, sensing, and energy storage. Scanning electrochemical cell microscopy (SECCM) provides a uniquely powerful route to probe these relationships at the micro‑ and nanoscale, yet measurements on porous materials are often complicated by dynamic droplet–surface interactions and electrolyte ingress that mask intrinsic behaviour.
In the first part of this work, electrodeposited PEDOT:ClO₄ films are used as a model porous conducting polymer system to explore how controlling droplet–cell interactions can enhance SECCM fidelity. By tuning electrolyte viscosity and refining probe approach conditions, droplet ingress into the polymer matrix can be minimised, enabling stable and reproducible mapping. Under these conditions, SECCM measurements with 1,1‑ferrocenedimethanol reveal clear, spatially localised variations in the electrochemical behaviour across the PEDOT:ClO₄ surface, reflecting its underlying heterogeneity.
In the second part, we demonstrate the emerging potential of SECCM as a microscale fabrication tool. Controlled droplet delivery enables the deposition of PEDOT‑based features with spatial precision, while in situ electrochemical monitoring provides insight into early‑stage polymer growth. Experiments using refined probe‑retraction strategies and functionalised pipette tips demonstrate that reproducible, well‑defined PEDOT deposits can be produced, opening a pathway toward studying and ultimately directing conducting‑polymer formation at the microscale.
Together, these studies position SECCM as a versatile platform that unifies high‑resolution electrochemical imaging with emerging capabilities in microscale additive manufacturing. This dual functionality opens new opportunities to link local electrochemical activity with structural and chemical features across porous, heterogeneous, and printed conducting‑polymer systems.