Effective Phase‐Alignment for 2D Halide Perovskites Incorporating Symmetric Diammonium Ion for Photovoltaics

New structural type of 2D AA'n-1 Mn X3n+1 type halide perovskites stabilized by symmetric diammonium cations has attracted research attention recently due to the short interlayer distance and better charge-transport for high-performance solar cells (PSCs). However, the distribution control of quantum wells (QWs) and its influence on optoelectronic properties are largely underexplored. Here effective phase-alignment is reported through dynamical control of film formation to improve charge transfer between quantum wells (QWs) for 2D perovskite (BDA)(MA)n-1 Pbn I3n+1 (BDA = 1,4-butanediamine, 〈n〉 = 4) film. The in situ optical spectra reveal a significantly prolonged crystallization window during the perovskite deposition via additive strategy. It is found that finer thickness gradient by n values in the direction orthogonal to the substrate leads to more efficient charge transport between QWs and suppressed charge recombination in the additive-treated film. As a result, a power conversion efficiency of 14.4% is achieved, which is not only 21% higher than the control one without additive treatment, but also one of the high efficiencies of the low-n (n ≤ 4) AA'n-1 Mn X3n+1 PSCs. Furthermore, the bare device retains 92% of its initial PCE without any encapsulation after ambient exposure for 1200 h.