Temperature Hypersensitive Organic Electroluminescence in a Reverse Biased, Frozen Polymer P–I–N Junction

Abstract Semiconductor junctions are among the most important material interfaces in modern technology. The solid polymer light‐emitting electrochemical cell (PLEC) possesses a semiconducting polymer homojunction that is reminiscent of a conventional p–n junction but also exhibits distinct features that are profoundly intriguing. The PLEC junction is formed under bias when the propagating p‐ and n‐doping fronts make contact. The PLEC junction can be immobilized by cooling after the initial junction formation. Further, the resulting frozen junction can be relaxed, or partially de‐doped into a p–i–n junction by controlled heating/cooling cycles. It is on such a frozen polymer p–i–n junction that the authors observed one of the most puzzling phenomena in organic electroluminescence (EL). The frozen p–i–n junction displays the brightest reverse bias (RB) EL ever imaged in a polymer junction and a large photovoltage. Moreover, the RB EL exhibits hypersensitivity to temperature, increasing in intensity by 22.6% K⁻¹ when the de‐doped cell is cooled from 250 to 200 K. A model based on the tunnel injection of charge carriers with fast transit time across the intrinsic region explains the RB EL's hypersensitivity to temperature and super‐linear dependence on cell current.