Qi Zhang

Minimizing contact resistance between metal electrodes and perovskites remains a critical challenge in developing perovskite‐based electronic and optoelectronic devices. Despite extensive experimental and theoretical efforts to minimize the contact resistance, atomic‐level insights into metal‐perovskite interfaces remain insufficiently understood. In this paper, we investigate the electronic and transport properties of 2D hybrid organic–inorganic perovskites, specifically (BA) ₂ PbBr ₄ and (PEA) ₂ PbBr ₄ , which consist of monolayer bromide perovskite layers with different organic spacer molecules: n‐butylammonium (BA) and phenylethylammonium (PEA) cations. We provide a comprehensive analysis of the Au/perovskites interface, considering two contact configurations, i.e., top‐contact and edge‐contact. We perform first‐principles calculations and use the nonequilibrium Green's function formalism to calculate the transport characteristics. We find that a Schottky barrier forms in the top‐contact configuration, but the edge‐contact configuration shows ohmic behavior for both Au/(BA) ₂ PbBr ₄ and Au/(PEA) ₂ PbBr ₄ . The edge‐contact configuration also enables highly efficient charge injection with a negligible interfacial tunneling barrier due to Au‐induced midgap states. For the top contact configuration, Au/(PEA) ₂ PbBr ₄ shows better transport behavior compared to (BA) ₂ PbBr ₄ , which is attributed to its lower tunneling barrier and higher density of metal‐induced midgap states. This work provides theoretical guidelines for designing low‐resistance metal‐2D hybrid perovskite contacts.