Unlocking the Single‐Domain Epitaxy of Halide Perovskites

Abstract The growth of epitaxial semiconductors and oxides has long since revolutionized the electronics and optics fields, and continues to be exploited to uncover new physics stemming from quantum interactions. While the recent emergence of halide perovskites offers exciting new opportunities for a range of thin‐film electronics, the principles of epitaxy have yet to be applied to this new class of materials and the full potential of these materials is still not yet known. In this work, single‐domain inorganic halide perovskite epitaxy is demonstrated. This is enabled by reactive vapor phase deposition onto single crystal metal halide substrates with congruent ionic interactions. For the archetypical halide perovskite, cesium tin bromide, two epitaxial phases, a cubic phase and tetragonal phase, are uncovered which emerge via stoichiometry control that are both stabilized with vastly differing lattice constants and accommodated via epitaxial rotation. This epitaxial growth is exploited to demonstrate multilayer 2D quantum wells of a halide‐perovskite system. This work ultimately unlocks new routes to push halide perovskites to their full potential.