Thierry Pauporté

The incorporation of large organic ammonium ions renders the crystallization dynamics and layer formation process of halide perovskites complex, difficult to control, and leads to problems of suppressed charge transport with the formation of tiny‐sized grains. In this paper, the use of methylammonium chloride (MACl) and an excess of PbI 2 is introduced as a co‐additives in the precursor solution for the control of phenylmethylammonium or benzylammonium (PMA + spacer) and formamidinium (FA + )‐based quasi‐2D PMA 2 FA n−1 Pb n I 3n+1 ( n = 5) perovskite layers formation. By this method, the morphology of the layer, the inner phase distribution, and the charge transport properties are improved. By employing glow discharge‐optical emission spectroscopy (GD‐OES) and other techniques, it is revealed that the quasi‐2D perovskites prepared in the presence of co‐additives exhibit uniform removal dynamics of the solvent across the film. Furthermore, the grain growth mode, upon thermal annealing, is lateral. It results in large, monolithic grains with low‐trap state density and excellent substrate coverage. Particularly, co‐additives improve the cations dispersion upon the crystallization process, thus suppressing the low‐n phase formed through the aggregation of spacer cations and accelerating the formation of the high‐n phase.