Molecular assembly and electro polymerization of 3,4-ethylenedioxy thiophene on Au(100) single crystal electrode using in-situ electrochemical scanning tunneling microscopy

Electrochemical scanning tunneling microscopy (Ec-STM) is a powerful technique that can provide molecular-level information regarding electrode surface processes in-situ in electrolyte solvent under ambient conditions. In this study, the adsorption and electro polymerization of an industrially important conducting polymer precursor, 3,4-ethylenedioxy thiophene (EDOT), on Au (100) single crystal was probed using Ec-STM. The Au (100) single crystal electrode substrate used for this study was fabricated using the well-known Clavilier's flame melting procedure. Cyclic voltammetry (CV) was used along with Ec-STM to characterize the bare, EDOT-modified, and poly(EDOT)-modified Au (100) single crystal electrode. Time-dependent Ec-STM imaging at 0.550 V showed the formation of an EDOT self-assembled monolayer through 2-D surface dillusion. The resulting EDOT molecular assembly on Au (100) single crystal electrode was found to fit in a 4√2χ3√2 unit cell. Difference in apparent corrugation between molecular rows was attributed to different angular orientation with respect to the substrate. The electro polymerization of EDOT on Au (100) single crystal electrode was done by potentiostatic and potentiodynamic methods. Both methods suggested a solution-process mechanism for EDOT electro polymerization. (author)