Decoding the Polymer p–n Junction: Controlled Dedoping and Reverse Bias Electroluminescence

Abstract The polymer light‐emitting electrochemical cell (PLEC) is a unique solid‐state device possessing attractive attributes for low‐cost applications, but also a junction structure that is still poorly understood. In a PLEC, the applied voltage causes in situ electrochemical p‐ and n‐doping of the semiconducting polymer and the formation of a dynamic light‐emitting p–n junction. Once the junction is fixed by cooling or chemical manipulation, the “frozen‐junction” PLEC exhibits a unipolar electroluminescence (EL) and photovoltaic response. Repeated thermal cycling, however, can cause the frozen‐junction PLEC to experience drastically enhanced EL under forward bias and the emergence of reverse bias EL. In this study, a combination of transport measurements and direct imaging is used to elucidate the origin of the mysterious reverse bias EL. A model is developed that explains the reverse bias EL as caused by the tunnel injection of electrons and holes from bandgap states into a dedoped “intrinsic” region between the p‐ and n‐doped regions. The model explains the location, relative intensity, and evolution of EL under both forward and reverse bias. The results hint at a junction that is much narrower than previously resolved.