International audienceMolecular semiconductor–doped insulator (MSDI) heterojunctions were designed using a new family of sublayers, namely triphenodioxazines (TPDO). The device obtained by combining the tetracyano triphenodioxazine bearing two triisopropylsilylethynyl moieties as a sublayer with the lutetium bisphthalocyanine (LuPc2) as a top layer showed a nonlinear current–voltage characteristic independent of the sign of the polarization, which is the signature of MSDI heterojunctions. Thus, a TPDO was used in a chemical sensor for the first time. Despite LuPc2 being the only material exposed to the atmosphere, the positive response of the device under ammonia revealed the key role played by the n-type TPDO sublayer. The device exhibits ...