Managing Growth and Dimensionality of Quasi 2D Perovskite Single‐Crystalline Flakes for Tunable Excitons Orientation

Abstract Hybrid perovskites are among the most promising materials for optoelectronic applications. Their 2D crystalline form is even more interesting since the alternating inorganic and organic layers naturally forge a multiple quantum‐well structure, leading to the formation of stable excitonic resonances. Nevertheless, a controlled modulation of the quantum well width, which is defined by the number of inorganic layers (n) between two organic ones, is not trivial and represents the main synthetic challenge in the field. Here, a conceptually innovative approach to easily tune n in lead iodide perovskite single‐crystalline flakes is presented. The judicious use of potassium iodide is found to modulate the supersaturation levels of the precursors solution without being part of the final products. This allows to obtain a fine tuning of the n value. The excellent optical quality of the as synthesized flakes guarantees an in‐depth analysis by Fourier‐space microscopy, revealing that the excitons orientation can be manipulated by modifying the number of inorganic layers. Excitonic out‐of‐plane component, indeed, is enhanced when “n” is increased. The combined advances in the synthesis and optical characterization fill in the picture of the exciton behavior in low‐dimensional perovskite, paving the way to the design of materials with improved optoelectronic characteristics.