Artificial p–n‐like Junction Based on Pure 2D Organic–Inorganic Halide Perovskite Structure Having Naphthalene Diimide Acceptor Moieties

2D organic–inorganic perovskites are an emerging class of materials with great potential for optoelectronics since a wide variety of large functional chromophores can be regularly incorporated. Among this new type of materials, hybrid perovskite systems incorporating strong electron acceptor molecules are considered as a promising approach to designing a new type of functional 2D perovskites for optoelectronics. In this work, a rare example of organic–inorganic 2D perovskite incorporating strong acceptors such as naphthalene diimide (NDI) building blocks between inorganic sheets is presented. This hybrid architecture forms highly air‐stable thin films with a structure consisting of inorganic perovskite monolayers of metal‐halide octahedra separated by bilayers of NDI‐based organic cations. The presence of strong electron‐accepting moieties in this multifunctional donor–acceptor hybrid heterostructure leads to a rare type II heterojunction in which the excitons can be efficiently dissociated via the electron‐transfer process and in which holes and electrons can be easily confined in the inorganic and organic sublayers, respectively. Such an ultimate p–n heterojunction shows improved photoconduction properties with a photocurrent multiplied by ≈40 under white‐light illumination in comparison to a similar 2D perovskite structure containing optically and electrically inert alkyl chains as organic components. A 2D perovskite incorporating strong acceptor naphthalene diimide (NDI) moities between inorganic sheets is prepared, leading to a multifunctional donor–acceptor hybrid type II heterostructure. In such an ultimate p–n heterojunction, excitons can be efficiently dissociated via the electron‐transfer process, and holes and electrons can be easily confined in the inorganic and organic sublayers, respectively, producing improved photoconduction properties.