Vibrational spectroscopy reveals electrostatic and electrochemical doping in organic thin film transistors gated with a polymer electrolyte dielectric

We apply attenuated total internal reflection Fourier transform infrared (ATR-FTIR) spectroscopy to directly probe active layers in organic thin film transistors (OTFTs). The OTFT studied uses the n-type organic semiconductor N-N′-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C8) and a polymer electrolyte gate dielectric made from poly(ethylene oxide) and LiClO₄. FTIR spectroscopy of the device shows signatures of anionic PTCDI-C8 species and broad polaron bands when the organic semiconductor layer is doped under positive gate bias (V_G). There are two distinctive doping regions: a reversible and electrostatic doping region for V_G ≤ 2 V and an irreversible and electrochemical doping regime for V_G > 2 V. On the basis of intensity loss of vibrational peaks attributed to neutral PTCDI-C8, we obtain a charge carrier density of 2.9 × 10 ¹⁴/cm² at V_G = 2 V; this charge injection density corresponds to the conversion of slightly more than one monolayer of PTCDI-C8 molecules into anions. At higher gate bias voltage, electrochemical doping involving the intercalation of Li⁺ into the organic semiconductor film can convert all PTCDI-C8 molecules in a 30-nm film into anionic species. For comparison, when a conventional gate dielectric (polystyrene) is used, the maximum charge carrier density achievable at V _G = 200 V is ∼4.5 × 10¹³/cm², which corresponds to the conversion of 18% of a monolayer of PTCDI-C8 molecules into anions.