Sacrificial layer concept interface engineering for robust, lossless monolithic integration of perovskite/Si tandem solar cells yielding high fill factor of 0.813.

Efficient monolithic perovskite/Si tandem solar cells require a robust recombination junction (RJ) with excellent electrical and optical properties. This study introduces an interface engineering method using an organic sacrificial layer to enable effective monolithic integration. An ultrathin layer of poly(3,4-ethylene-dioxythiophene):polystyrene sulfonate (PEDOT:PSS) is inserted between the transparent conductive oxide recombination layer and the hole transport layer (HTL) of a methylammonium lead iodide (MAPbI)-based perovskite top cell. This layer restores junction functionality and enables charge transfer between sub-cells via efficient carrier recombination at the RJ, which electrically connects the two cells. Acting as a sacrificial layer, PEDOT:PSS temporarily prevents resistive SiO formation and improves interface quality. High-resolution transmission electron microscopy and X-ray photoelectron spectroscopy confirm suppression of SiO growth during HTL annealing. Moreover, the Cu-doped NiO HTL fabrication method proves critical, where process optimization improves electrical contact. Combined with PEDOT:PSS interface engineering, these enhancements promote efficient recombination by tuning interfacial energy levels and increasing band bending at the RJ. As a result, tandem devices comprising an aluminum back-surface field p-type homojunction Si bottom cell and a p-i-n perovskite top cell achieve 21.95% power conversion efficiency and an 81.3% fill factor -among the highest reported for monolithic perovskite/Si tandem solar cells.