Structural engineering is crucial for tuning the properties of artificial materials. As one of the most important two-dimensional (2D) materials, black phosphorus (BP) has been rediscovered in 2014 and attracted tremendous attentions all over the world. It shows great potentials in optoelectronic and integrated photonic applications due to the direct and tunable bandgap, high carrier mobility, and intrinsic anisotropy. However, some deficiencies are yet to be settled before its large-scale applications, such as the massive synthesis methods and structure–property relationship. To investigate the influence of structural engineering on the performance of 2D BP-based devices thoroughly, recent studies on deformation, atomic defects, superlattice, alloying, thickness and phase transition are maximality summarized in this review covering from the intrinsic properties to optoelectronic applications. Benefiting from the broad research in this field, challenges and opportunities of 2D BP for advanced integrated photonic applications are also provided, which supplies a useful reference to realize large-scale 2D BP-based all-optical communications in future.
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