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.

Targeted Additive Micromodulation of Grain Size in Nanocrystalline Copper Nanostructures by Electrohydrodynamic Redox 3D Printing.

The control of materials' microstructure is both a necessity and an opportunity for micro/nanometer-scale additive manufacturing technologies. On the one hand, optimization of purity and defect density of printed metals is a prerequisite for their application in microfabrication. On the other hand, the additive approach to materials deposition with highest spatial resolution offers unique opportunities for the fabrication of materials with complex, 3D graded composition or microstructure. As a first step toward both-optimization of properties and site-specific tuning of microstructure-an overview of the wide range of microstructure accessed in pure copper (up to >99.9 at.%) by electrohydrodynamic redox 3D printing is presented, and on-the-fly modulation of grain size in copper with smallest segments ≈400 nm in length is shown. Control of microstructure and materials properties by in situ adjustment of the printing voltage is demonstrated by variation of grain size by one order of magnitude and corresponding compression strength by a factor of two. Based on transmission electron microscopy and atom probe tomography, it is suggested that the small grain size is a direct consequence of intermittent solvent drying at the growth interface at low printing voltages, while larger grains are enabled by the permanent presence of solvent at higher potentials.

Nanodroplet Flight Control in Electrohydrodynamic Redox 3D Printing.

Electrohydrodynamic 3D printing is an additive manufacturing technique with enormous potential in plasmonics, microelectronics, and sensing applications thanks to its broad material palette, high voxel deposition rate, and compatibility with various substrates. However, the electric field used to deposit material is concentrated at the depositing structure, resulting in the focusing of the charged droplets and geometry-dependent landing positions, which complicates the fabrication of complex 3D shapes. The low level of concordance between the design and printout seriously impedes the development of electrohydrodynamic 3D printing and rationalizes the simplicity of the designs reported so far. In this work, we break the electric field centrosymmetry to study the resulting deviation in the flight trajectory of the droplets. Comparison of experimental outcomes with predictions of an FEM model provides new insights into the droplet characteristics and unveils how the product of droplet size and charge uniquely governs its kinematics. From these insights, we develop reliable predictions of the jet trajectory and allow the computation of optimized printing paths counterbalancing the electric field distortion, thereby enabling the fabrication of geometries with unprecedented complexity.

Microstructure-driven electrical conductivity optimization in additively manufactured microscale copper interconnects.

As the microelectronics field pushes to increase device density through downscaling component dimensions, various novel micro- and nano-scale additive manufacturing technologies have emerged to expand the small scale design space. These techniques offer unprecedented freedom in designing 3D circuitry but have not yet delivered device-grade materials. To highlight the complex role of processing on the quality and microstructure of AM metals, we report the electrical properties of micrometer-scale copper interconnects fabricated by Fluid Force Microscopy (FluidFM) and Electrohydrodynamic-Redox Printing (EHD-RP). Using a thin film-based 4-terminal testing chip developed for the scope of this study, the electrical resistance of as-printed metals is directly related to print strategies and the specific morphological and microstructural features. Notably, the chip requires direct synthesis of conductive structures on an insulating substrate, which is shown for the first time in the case of FluidFM. Finally, we demonstrate the unique ability of EHD-RP to tune the materials resistivity by one order of magnitude solely through printing voltage. Through its novel electrical characterization approach, this study offers unique insight into the electrical properties of micro- and submicrometer-sized copper interconnects and steps towards a deeper understanding of micro AM metal properties for advanced electronics applications.

Thermal Management in Ni/Al Reactive Multilayers: Understanding and Preventing Reaction Quenching on Thin Film Heat Sinks.

Thermal management is conventionally the design of microelectronics circuitry to maximize heat extraction and minimize local heating. In this work, we investigate a reverse thermal management problem related to understanding and preventing heat dissipation during the propagation of a self-sustained reaction in Ni/Al reactive multilayers, metastable nanostructures that can release heat through a self-sustained propagating exothermic reaction. While it was recently demonstrated that reactive multilayers can serve as on-chip heat sources for on-demand healing of metal films, they still face challenges of device integration due to conductive heat losses to the substrate or adjacent on-chip components, which act as heat sinks and consequently quench the reaction. Here, we study the impact of different heat sink materials, such as gold, copper, and silicon, on the propagation velocity and temperature of the self-sustained heat wave and show that the propagation can be controlled and even stopped by varying the heat sink thickness. Further, we demonstrate that the introduction of a multilayered Al2O3/Zr/Al2O3 thermal barrier enables stable propagation on substrates that would otherwise quench the reaction. The results of this study will facilitate the integration of Ni/Al multilayers as intrinsic heat sources on different substrates for applications in micro/nanodevices.