Mapping the Electronic Structure of Polypyrrole with Image-Based Electrochemical Scanning Tunnelling Spectroscopy

Conducting polymers are versatile semiconductors whose applications cover a wide range of devices. Their versatility is due, in addition to other factors, to properties that can be easily modulated according to the intended application. It is therefore important to study and map the electronic structure of these materials to allow for a better correlation between structure and properties. Electrochemical scanning tunnelling spectroscopy (EC-STS) can be a powerful tool to characterize the electronic structure of the semiconductor electrolyte interface. In this work we have used image-based EC-STS (IB-EC-STS) to describe quantitatively the band structure of an electrochemically deposited polypyrrole (PPy) film. IB-EC-STS located the band edge of the polymer’s valence band (VB) at 0.95 V vs. RHE (-5.33 eV in the absolute potential scale) and the intragap polaron states formed when the polymer is oxidised (doped) at 0.46 V vs. RHE (-4.84 eV in the absolute potential scale). The IB-EC-STS data were cross checked with electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis of the interfacial capacitance. The DOS spectrum obtained from EIS data is consistent with the STS-deduced location of the VB and the polarons.