title: In Situ Measurement of Voltage-Induced Stress in Conducting Polymers with Redox-Active Dopants.
abstract: Minimization of stress-induced mechanical rupture and delamination of conducting polymer (CP) films is desirable to prevent failure of devices based on these materials. Thus, precise in situ measurement of voltage-induced stress within these films should provide insight into the cause of these failure mechanisms. The evolution of stress in films of polypyrrole (pPy), doped with indigo carmine (IC), was measured in different electrochemical environments using the multibeam optical stress sensor (MOSS) technique. The stress in these films gradually increases to a constant value during voltage cycling, revealing an initial break-in period for CP films. The nature of the ions involved in charge compensation of pPy[IC] during voltage cycling was determined from electrochemical quartz crystal microbalance (EQCM) data. The magnitude of the voltage-induced stress within pPy[IC] at neutral pH correlated with the radius of the hydrated mobile ion in the order Li(+) > Na(+) > K(+). At acidic pH, the IC dopant in pPy[IC] undergoes reversible oxidation and reduction within the range of potentials investigated, providing a secondary contribution to the observed voltage-induced stress. We report on the novel stress response of these polymers due to the presence of pH-dependent redox-active dopants and how it can affect material performance.
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Sujat
authors: S
authors: Sen
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Sung Yeol
authors: SY
authors: Kim
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Lia R
authors: LR
authors: Palmore
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Shenghua
authors: S
authors: Jin
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Nitin
authors: N
authors: Jadhav
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: Eric
authors: E
authors: Chason
authors: Department of Chemistry and ‡School of Engineering, Brown University , Providence, Rhode Island 02912, United States.
authors: G Tayhas R
authors: GT
authors: Palmore
keywords: EQCM; MOSS; conducting polymers; film stress; indigo carmine; ion transport; polypyrrole