Stacking‐Controlled Growth of rBN Crystalline Films with High Nonlinear Optical Conversion Efficiency up to 1%

Abstract Nonlinear optical crystals lie at the core of ultrafast laser science and quantum communication technology. The emergence of 2D materials provides a revolutionary potential for nonlinear optical crystals due to their exceptionally high nonlinear coefficients. However, uncontrolled stacking orders generally induce the destructive nonlinear response due to the optical phase deviation in different 2D layers. Therefore, conversion efficiency of 2D nonlinear crystals is typically limited to less than 0.01% (far below the practical criterion of >1%). Here, crystalline films of rhombohedral boron nitride (rBN) with parallel stacked layers are controllably synthesized. This success is realized by the utilization of vicinal FeNi (111) single crystal, where both the unidirectional arrangement of BN grains into a single‐crystal monolayer and the continuous precipitation of (B,N) source for thick layers are guaranteed. The preserved in‐plane inversion asymmetry in rBN films keeps the in‐phase second‐harmonic generation field in every layer and leads to a record‐high conversion efficiency of 1% in the whole family of 2D materials within the coherence thickness of only 1.6 µm. The work provides a route for designing ultrathin nonlinear optical crystals from 2D materials, and will promote the on‐demand fabrication of integrated photonic and compact quantum optical devices.