Improved Thermal Stability and Film Uniformity of Halide Perovskite by Confinement Effect brought by Polymer Chains of Polyvinyl Pyrrolidone

Abstract Polyvinyl pyrrolidone (PVP) is doped to PbI₂ and organic salt during two‐step growth of halideperovskite. It is observed that PVP molecules can interact with both PbI₂ and organic salt, reduce the aggregation and crystallization of the two, and then slow down the coarsening rate of perovskite. As doping concentration increases from 0 to 1 mM in organic salt, average crystallite size of perovskite decreases monotonously from 90 to 34 nm; Surface fluctuation reduces from 259.9 to 179.8 nm at first, and then increases; Similarly, surface roughness decreases from 45.55 to 26.64 nm at first, and then rises. Accordingly, a kind of “confinement effect” is resolved to crystallite growth and surface fluctuation/roughness, which helps to build compact and uniform perovskite film. Density of trap states (t‐DOS) is cut down by ≈60% at moderate doping (0.2 mM). Due to the “confinement effect”, power conversion efficiency of perovskite solar cells is improved from 19.46 (±2.80) % to 21.50 (±0.99) %, and further improved to 24.11% after surface modification. Meanwhile, “confinement effect” strengthens crystallite/grain boundaries and improves thermal stability of both film and device. T₈₀ of device increases to 120 h, compared to 50 h for reference ones.