Mapping the electronic structure of polypyrrole with image‐based electrochemical scanning tunneling spectroscopy

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