Three-dimensional (3D) functional solids with programmable hierarchical micro/nanoarchitectures are critical for several fundamental applications, including structural composites, microfluidics, photonics, and tissue engineering. Due to the broad range of application possibilities, a large amount of effort has been devoted to the in-depth exploration of various top-down and bottom-up strategies to construct these complex multi-dimensional structures. In this review, we introduce and discuss selected examples of fabrication techniques which have successfully developed large area, novel 3D functional architectures with exquisite control over their morphology at the nano/subnanolevel. Emphasis is placed on the nanofabrication techniques, their salient features as well as advantages. A summary of the emerging application possibilities of such structures, especially in biomedicine, energy, and device construction, is also discussed.

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ZnO-nanofilm/Si-micropillar p-n nanoheterostructure arrays were prepared by growing n-type ZnO onto a p-type nanoporous Si pillar array. Its current-voltage characteristics of nanoheterostructure showed good rectifying behavior with onset voltage of ~1.5 V, forward current density of ~28.7 mA/cm(2) at 2.5 V, leakage current density of ~0.15 mA/cm(2) and rectifying ratio of ~121 at ± 2.5 V. The electron transport across nanohetreostructure obeys the trap-charge-limit current model. Moreover, strong white light electroluminescence from ZnO-nanofilm/Si-micropillar light-emitting diode (LED) has been achieved, which could open up possibilities to build new ZnO/Si-based highly efficient solid-state lighting devices.

Large scale and highly ordered flowerlike ZnO/Si nanostructures are successfully prepared by combining two common techniques, viz. hydrothermally etch fabrication of nanoporous Si pillar array (NSPA) and self-catalytic chemical vapor transport growth of ZnO nanowires. Au nanoparticles are decorated onto the ZnO/Si nanoflowers by the hydrothermal method. The formed Au/ZnO/NSPA array is evaluated as a surface-enhanced Raman scattering SERS-active substrate, which exhibits very high sensitivity and good stability and reproducibility. The excellent SERS enhancement is mainly attributed to the strong local electromagnetic effect which is associated with the unique flowerlike nanostructures of Au/ZnO/NSPA and the formed metal-induced gap states at the Au/ZnO interfaces. The results indicated that Au/ZnO/NSPA might be employed as a promising SERS substrate for the fast detection of low-concentration biomolecules.