In Situ Measurement of Breathing Strain and Mechanical Degradation in Organic Electrochromic Polymers

Organic mixed ionic–electronic conductors (OMIECs) are an emerging family of materials crucial in the development of flexible, bio-, and optoelectronics. In electrochromic polymers, the cyclic redox reaction is associated with a mechanical breathing strain, which deforms the OMIECs and degrades the device reliability. We set forth an in situ nanoindentation approach to measure the breathing strain of a poly­(3,4-propylenedioxythiophene) (PProDOT) thin film in a customized liquid cell during electrochromic cycles. A breathing volumetric strain of 12–25% is persistent in different sets of electrolytes of various solvents, salts, and salt molarities. The electrochemical conditioning, intermittence time, and cyclic protocol have minor effects on the mechanical response of PProDOT. The mechanical behavior and anion diffusivity measurement further infer the redox kinetics. Heavily cycled PProDOT films show reduced volumetric strain and accumulated mechanical damage of channel cracks and dysfunctional regions of slow and inhomogeneous electrochromic switching. This work is a systematic characterization of mechanical deformation and damage in a model OMIEC and informs the mechanical reliability of organic electrochromic devices.