An extensive range of metals can be dissolved and re-deposited in liquid solvents using electrochemistry. We harness this concept for additive manufacturing, demonstrating the focused electrohydrodynamic ejection of metal ions dissolved from sacrificial anodes and their subsequent reduction to elemental metals on the substrate. This technique, termed electrohydrodynamic redox printing (EHD-RP), enables the direct, ink-free fabrication of polycrystalline multi-metal 3D structures without the need for post-print processing. On-the-fly switching and mixing of two metals printed from a single multichannel nozzle facilitates a chemical feature size of <400 nm with a spatial resolution of 250 nm at printing speeds of up to 10 voxels per second. As shown, the additive control of the chemical architecture of materials provided by EHD-RP unlocks the synthesis of 3D bi-metal structures with programmed local properties and opens new avenues for the direct fabrication of chemically architected materials and devices.

The agglomeration of metal thin films on dielectric materials is a topic of high technological importance. In this contribution, a coupled morphology-agglomeration approach has been chosen to reveal the basic mechanism of rupture, mass transport, and the substrate dependence of agglomeration. The morphological evolution of Pt thin films has been investigated by means of scanning electron microscopy, atomic force microscopy, and focused ion-beam (FIB) etching techniques. Pt thin films were deposited on amorphous ${\text{Si}}_3{\text{N}}_4$ and polycrystalline yttria stabilized ${\text{ZrO}}_2$ substrates and subjected to heat treatments up to 1193 K for 2 h. Three main observations have been made: (i) the early stage of rupture can be described via basic thermodynamics as an order-disorder transition. The dominating mechanism of initial film rupture is a defect associated barrierless nucleation of holes in the spinodal regime of the Pt thin film as shown by means of Minkowski measures. (ii) Up to 1073 K the hole growth is found to be a surface-diffusion limited process, and in first approximation it is in agreement with Brandon and Bradshaw’s theory for the morphological evolution of thin metal films at elevated temperatures. Values for mass transport have been derived. (iii) It is shown that two in general independent physical processes control the morphological evolution and kinetics of thin-film agglomeration: one attributes to the film-ambient interface and the other to the film-substrate interface. Void formation at the film-substrate interface is enhanced by a factor of 9 in the case of the amorphous-crystalline interface due to a lower adhesion energy of the film. The corresponding adhesion energies have been determined experimentally using FIB techniques and the Wulff-Kaishew theorem for equilibrium crystal shapes.

Structural color is frequently exploited by living organisms for biological functions and has also been translated into synthetic materials as a more durable and less hazardous alternative to conventional pigments. Additive manufacturing approaches were recently exploited for the fabrication of exquisite photonic objects, but the angle-dependence observed limits a broader application of structural color in synthetic systems. Here, we propose a manufacturing platform for the 3D printing of complex-shaped objects that display isotropic structural color generated from photonic colloidal glasses. Structurally colored objects are printed from aqueous colloidal inks containing monodisperse silica particles, carbon black, and a gel-forming copolymer. Rheology and Small-Angle-X-Ray-Scattering measurements are performed to identify the processing conditions leading to printed objects with tunable structural colors. Multimaterial printing is eventually used to create complex-shaped objects with multiple structural colors using silica and carbon as abundant and sustainable building blocks.

Structural colors have drawn wide attention for their potential as a future printing technology for various applications, ranging from biomimetic tissues to adaptive camouflage materials. However, an efficient approach to realize robust colors with a scalable fabrication technique is still lacking, hampering the realization of practical applications with this platform. Here, we develop a new approach based on large-scale network metamaterials that combine dealloyed subwavelength structures at the nanoscale with lossless, ultra-thin dielectric coatings. By using theory and experiments, we show how subwavelength dielectric coatings control a mechanism of resonant light coupling with epsilon-near-zero regions generated in the metallic network, generating the formation of saturated structural colors that cover a wide portion of the spectrum. Ellipsometry measurements support the efficient observation of these colors, even at angles of 70°. The network-like architecture of these nanomaterials allows for high mechanical resistance, which is quantified in a series of nano-scratch tests. With such remarkable properties, these metastructures represent a robust design technology for real-world, large-scale commercial applications.