Heterostructures have attracted enormous interest due
to the properties
arising from the coupling and synergizing between multiscale structures
and the promising applications in electronics, mechanics, and optics.
However, it is challenging for current technologies to precisely integrate
cross-scale micro/nanomaterials in three dimensions (3D). Herein,
we realize the precise spatial allocation of nanoblocks on micromatrices
and programmable 3D optical heterostructure patterning via printing-assisted
self-assembly. This bottom-up approach fully exploits the advantages
of printing in on-demand patterning, low cost, and mass production,
as well as the merits of solution-based colloidal assembly for simple
structuring and high-precision regulating, which facilitates the patterned
integration of multiscale materials. Importantly, the luminescent
nanoparticle assembly can be accurately coupled to the dye-doped polymer
matrix by regulating the interface wettability, enabling facile multicolor
tuning in a single heterostructure. Thus, the heterostructure can
be specially encoded for anticounterfeiting and encryption applications
due to the morphology-dependent and interface-coupling-induced luminescence.
Moreover, with the capability to achieve single-nanoparticle resolution,
these findings have great potential for designing photonic superstructures
and advanced optical devices.