Sub-nanometer expansions of redox responsive polymer films monitored by imaging ellipsometry

We describe a novel approach to quantitatively visualize sub nm height changes occurring in thin films of redox active polymers upon reversible electrochemicaL oxidation/reduction in situ and in real-time with electrochemical imaging ellipsometry (EC-IE). Our approach is based on the utilization of a micro-patterned substrate containing circular patterns of passive (non-redox active) 11-mercapto-1-undecanol (MCU) within a redox-responsive oligoethylene sulfide end-functionalized poly(ferrocenyldimethylsilane) (ES-PFS) film on a gold substrate. The non-redox responsive MCU layer was used as a molecular reference layer for the direct visualization of the minute thickness variations of the ES-PFS film. The ellipsometric microscopy images were recorded in aqueous electrolyte solutions at potentials of -0.1 V and 0.6 V vs. Ag/AgCl corresponding to the reduced and oxidized redox states of ES-PFS, respectively. The ellipsometric contrast images showed a 37 (+/- 2)% intensity increase in the ES-PFS layer upon oxidation. The thickness of the ES-PFS layer reversibly changed between 4.0 (+/- 0.1) nm and 3.4 (+/- 0.1) nm upon oxidation and reduction, respectively, as determined by IE. Additionally, electrochemical atomic force microscopy (EC-AFM) was used to verify the redox controlled thickness variations. The proposed method opens novel avenues to optical visualize minute and rapid height changes occurring e.g. in redox active (and other stimulus responsive) polymer films in a fast and non-invasive manner.