Nanotwinned (nt)-metals exhibit superior mechanical and electrical properties compared to their coarse-grained and nanograined counterparts. nt-metals in film and bulk forms are obtained using physical and chemical processes including pulsed electrodeposition (PED), plastic deformation, recrystallization, phase transformation, and sputter deposition. However, currently, there is no process for 3D printing (additive manufacturing) of nt-metals. Microscale 3D printing of nt-Cu is demonstrated with high density of coherent twin boundaries using a new room temperature process based on localized PED (L-PED). The 3D printed nt-Cu is fully dense, with low to none impurities, and low microstructural defects, and without obvious interface between printed layers, which overall result in good mechanical and electrical properties, without any postprocessing steps. The L-PED process enables direct 3D printing of layer-by-layer and complex 3D microscale nt-Cu structures, which may find applications for fabrication of metamaterials, sensors, plasmonics, and micro/nanoelectromechanical systems.

Nanotwinned-metals (nt-metals) offer superior mechanical (high ductility and strength) and electrical (low electromigration) properties compared to their nanocrystalline (nc) counterparts. These properties are advantageous in particular for applications in nanoscale devices. However, fabrication of nt-metals has been limited to films (two-dimensional) or template-based (one-dimensional) geometries, using various chemical and physical processes. In this Letter, we demonstrate the ambient environment localized pulsed electrodeposition process for direct printing of three-dimensional (3D) freestanding nanotwinned-Copper (nt-Cu) nanostructures. 3D nt-Cu structures were additively manufactured using pulsed electrodeposition at the tip of an electrolyte-containing nozzle. Focused ion beam (FIB) and transmission electron microscopy (TEM) analysis revealed that the printed metal was fully dense, and was mostly devoid of impurities and microstructural defects. FIB and TEM images also revealed nanocrystalline-nanotwinned-microstructure (nc-nt-microstructure), and confirmed the formation of coherent twin boundaries in the 3D-printed Cu. Mechanical properties of the 3D-printed nc-nt-Cu were characterized by direct printing (FIB-less) of micropillars for in situ SEM microcompression experiments. The 3D-printed nc-nt-Cu exhibited a flow stress of over 960 MPa, among the highest ever reported, which is remarkable for a 3D-printed material. The microstructure and mechanical properties of the nc-nt-Cu were compared to those of nc-Cu printed using the same process under direct current (DC) voltage.

The progress in microscale additive manufacturing (μ-AM) of metals requires engineering of the microstructure for various functional applications. In particular, achieving in situ control over the microstructure during 3D printing is critical to eliminate the need for post-processing and annealing. Recent reports have demonstrated the possibility of electrochemical μ-AM of nanotwinned metals, in which the presence of parallel arrays of twin boundaries (TBs) are known to enhance mechanical and electrical properties. For the first time, the authors report that the microstructure of metals printed using the microscale localized pulsed electrodeposition (L-PED) process can be controlled in situ during 3D-printing. In particular, the authors show that through electrochemical process parameters the density and the orientation of the TBs, as well as the grain size can be controlled. The results of the in situ SEM microcompression experiments on directly 3D-printed micro-pillars show that such control over microstructure directly correlates with the mechanical properties of the printed metal.

Capability to print metals at micro/nanoscale in arbitrary 3D patterns at local points of interest will have applications in nano-electronics and sensors. Meniscus-confined electrodeposition (MCED) is a manufacturing process that enables depositing metals from an electrolyte containing nozzle (pipette) in arbitrary 3D patterns. In this process, a meniscus (liquid bridge or capillary) between the pipette tip and the substrate governs the localized electrodeposition process. Fabrication of metallic microstructures using this process is a multi-physics process in which electrodeposition, fluid dynamics, and mass and heat transfer physics are simultaneously involved. We utilized multi-physics finite element simulation, guided by experimental data, to understand the effect of water evaporation from the liquid meniscus at the tip of the nozzle for deposition of free-standing copper microwires in MCED process.

Meniscus-confined electrodeposition (MCED) is a solution-based, room temperature process for 3D printing of metals at micro/nanoscale. In this process, a meniscus (liquid bridge or capillary) between a nozzle and a substrate governs the localized electrodeposition process, which involves multiple physics of electrodeposition, fluid dynamics, mass, and heat transfer. We have developed a multiphysics finite element (FE) model to investigate the effects of nozzle speed (vN) and nozzle diameter (D0) in the MCED process. The simulation results are validated with experimental data. Based on theoretical approach and experimental observation, the diameter of the deposited wire is in the range of 0.5–0.9 times of the nozzle diameter. The applicable range for vN for various nozzle diameters is computed. The results showed that the contribution of migration flux to total flux remains nearly constant (∼50%) for all values of pipette diameter in the range examined (100 nm–5 μm), whereas the contribution of diffusion and evaporation fluxes to total flux increase and decrease with the increasing pipette diameter, respectively. Results of this multiphysics study can be used to guide the experiment for optimal process conditions.