On the Resolution Limit of Electrohydrodynamic Redox 3D Printing.

Additive manufacturing (AM) will empower the next breakthroughs in nanotechnology by combining unmatched geometrical freedom with nanometric resolution. Despite recent advances, no micro-AM technique has been able to synthesize functional nanostructures with excellent metal quality and sub-100 nm resolution. Here, significant breakthroughs in electrohydrodynamic redox 3D printing (EHD-RP) are reported by directly fabricating high-purity Cu (>98 at.%) with adjustable voxel size from >6µm down to 50 nm. This unique tunability of the feature size is achieved by managing in-flight solvent evaporation of the ion-loaded droplet to either trigger or prevent the Coulomb explosion. In the first case, the landing of confined droplets on the substrate allows the fabrication of high-aspect-ratio 50 nm-wide nanopillars, while in the second, droplet disintegration leads to large-area spray deposition. It is discussed that the reported pillar width corresponds to the ultimate resolution achievable by EHD printing. The unrivaled feature size and growth rate (>100 voxel s -1 ) enable the direct manufacturing of 30 µm-tall atom probe tomography (APT) tips that unveil the pristine microstructure and chemistry of the deposit. This method opens up prospects for the development of novel materials for 3D nano-printing.