Hierarchical Self‐Assembly of Phosphorene Into Multilayered Superlattices for Air‐Stable Polarimetric Optoelectronics

Precise solution‐based control over the morphology and crystallographic orientation of two‐dimensional (2D) black phosphorus (BP) is essential for scalable optoelectronics, yet its instability and high surface energy hinder ordering assembly. Here, we report a meniscus‐guided, gas‐flow‐assisted evaporation‐induced hierarchical self‐assembly strategy to construct van der Waals bulk heterojunctions (BHJs). This approach defines a dimensionality‐transition pathway from bulk BP to isotropic zero‐dimensional (0D) quantum dots and further to ordered 2D superlattices, enabling the reconstruction of macroscopic in‐plane optical anisotropy. The resulting continuous architecture maximizes interfacial area and percolation pathways, enabling ultrafast charge transfer (∼9.8 ps) that kinetically stabilizes phosphorene for over six months. The BHJ photodetectors further exhibit wavelength‐dependent polarity switching: positive photoconductivity for wavelengths below 635 nm, and negative photoconductivity for wavelengths exceeding 685 nm. This phenomenon is rooted in competitive trap‐mediated carrier dynamics at the heterojunction interface, where the activation energy for de‐trapping (negative thermal quenching energy) serves as the energetic barrier. Supported by finite element analysis and high‐resolution characterization, our work provides a scalable route for integrating air‐sensitive 2D semiconductors into robust, bendable polarimetric optoelectronic systems.