Sputtering Mechanism of an Unsintered Organic–Inorganic Sputtering Target for Perovskite Solar Cells

ABSTRACT Vacuum‐based deposition of hybrid organic–inorganic perovskites (HOIPs) remains a critical yet unresolved challenge for enabling scalable, solvent‐free manufacturing of perovskite optoelectronics. Here, tetragonal methylammonium lead iodide ( β ‐MAPbI ₃ ) single‐phase crystals with high structural uniformity are synthesized via an antisolvent vapor‐assisted crystallization process and utilized as feedstock for a 3‐inch unsintered MAPbI ₃ sputtering target fabricated through mechanochemical processing and low‐temperature consolidation. The resulting target exhibits sufficient compactness and mechanical integrity to sustain RF magnetron sputtering without macroscopic fracture while retaining its β ‐phase crystallographic signature under plasma exposure. However, sputtered films derived from this target consistently exhibit PbI ₂ ‐dominant characteristics. Correlative analysis of target surface evolution and film composition indicates a progressive loss of organic and iodine species during sputtering, leading to a compositionally altered sputtered flux. Such behavior can be reasonably attributed to the combined effects of energetic ion bombardment and photon irradiation intrinsic to RF plasma environments. Consequently, direct sputter deposition does not readily preserve MAPbI ₃ stoichiometry, even when high‐quality single‐phase crystal‐derived targets are employed, suggesting that post‐deposition reconstruction strategies may be required to restore the perovskite phase. This work provides fundamental insights into plasma–perovskite interactions and establishes a foundation for sputtering‐based routes toward scalable perovskite photoabsorber fabrication.