Organic multicolor heterostructures with spatially resolved luminescent colors and identifiable patterns have exhibited considerable potential for achieving micro-/nanoscale photonic barcodes. Nevertheless, such types of barcodes reported thus far are exclusively based on a single heterostructure with limited coding elements. Here, a directional self-assembly strategy is proposed to achieve high-coding-capacity spatially resolved photonic barcodes through rationally constructing organic hierarchical super-heterostructures, where numerous subheterostructure blocks with flat hexagonal facets are precisely oriented with their specific facets via a reconfigurable capillary force. The building blocks were prepared through a one-pot sequential heteroepitaxial growth, which enables the effective modulation of the structural and color characteristics in coding structures. Significantly, a directional facet-tofacet attraction between particles via facet registration leads to the formation of well-defined 1D super-heterostructures, which contain multiple coding elements, thus providing a good platform for constructing the high-coding-capacity photonic barcodes. The results may be useful in fabricating organic hierarchical hybrid super-heterostructures for security labels and optical data recording.

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