Interface Molecular Engineering for Laminated Monolithic Perovskite/Silicon Tandem Solar Cells with 80.4% Fill Factor

A multipurpose interconnection layer based on poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS), and d‐sorbitol for monolithic perovskite/silicon tandem solar cells is introduced. The interconnection of independently processed silicon and perovskite subcells is a simple add‐on lamination step, alleviating common fabrication complexities of tandem devices. It is demonstrated experimentally and theoretically that PEDOT:PSS is an ideal building block for manipulating the mechanical and electrical functionality of the charge recombination layer by controlling the microstructure on the nano‐ and mesoscale. It is elucidated that the optimal functionality of the recombination layer relies on a gradient in the d‐sorbitol dopant distribution that modulates the orientation of PEDOT across the PEDOT:PSS film. Using this modified PEDOT:PSS composite, a monolithic two‐terminal perovskite/silicon tandem solar cell with a steady‐state efficiency of 21.0%, a fill factor of 80.4%, and negligible open circuit voltage losses compared to single‐junction devices is shown. The versatility of this approach is further validated by presenting a laminated two‐terminal monolithic perovskite/organic tandem solar cell with 11.7% power conversion efficiency. It is envisioned that this lamination concept can be applied for the pairing of multiple photovoltaic and other thin film technologies, creating a universal platform that facilitates mass production of tandem devices with high efficiency. A multipurpose interconnection layer for the fabrication of monolithic perovskite/silicon tandem solar cells with high power conversion efficiency is explored. The interconnection of independently processed silicon and perovskite subcells could be a simple add‐on lamination step, alleviating the common fabrication complexity of perovskite/silicon tandem devices.