Additive manufacturing of Zn with submicron resolution and its conversion into Zn/ZnO core–shell structures

Nydegger, Mirco; Pruška, Adam; Galinski, Henning; Zenobi, Renato; Reiser, Alain; Spolenak, Ralph

doi:10.1039/d2nr04549d

Cited by 9 publications

(11 citation statements)

References 59 publications

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“…Our results demonstrate the deposition of metallic structures with EHD-RP from aqueous metal salt solutions with similar characteristics to those previously printed from sacrificial anodes 35,38,39 . The general advantage in the use of metal salts over sacrificial anodes is the increased range of printable metals, because no anodic dissolution must be guaranteed (which can be a challenge, as shown for the case of Zn 38 ) and soluble salts exist for a large variety of metals.…”

Section: Introductionsupporting

confidence: 80%

“…Intriguingly though, the previously reported deposition of Cu-Ag alloys by EHD-RP indicated that this technology can directly deposit alloys without the need of elaborate tailoring of the plating bath -potentially significantly simplifying alloying by electrochemical deposition. EHD-RP is based on a solvent-filled quartz nozzle (both, organic and aqueous solvents have been demonstrated 35,38 ) in close proximity (approx. 10 µm) to a conductive substrate.…”

Section: Introductionmentioning

confidence: 99%

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Micron-scale additive manufacturing of binary and ternary alloys by electrohydrodynamic redox 3D printing

Porenta

Nydegger

Menétrey

et al. 2023

Preprint

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Across disciplines and length scales, alloying of metals is a common and necessary strategy to optimise materials performance. While the manufacturing of alloys in bulk and thin film form is well understood, the fabrication of alloyed 3D nanostructures with precise control over the composition remains a challenge. Herein, we demonstrate that electrohydrodynamic redox printing from mixed metal salt solutions is a versatile approach for the 3D nanofabrication of alloys. We propose that the droplet-by-droplet nature of the electrohydrodynamic redox printing process allows straightforward electroplating of alloys with composition solely controlled by the composition of the electrolyte solution, independent of the reduction potential of the involved cations. As a demonstration of the direct control of composition, we deposit binary and ternary alloys of Ag, Cu and Zn. TEM microstructure analysis indicates homogeneous alloying at the nanoscale and the formation of a metastable solid-solution phase for Ag-Cu and a two phase system for Ag-Cu-Zn alloys. The straightforward approach to alloying with an electrochemical technique promises novel opportunities for optimisation of properties of 3D nanofabricated metals.

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Section: Introductionsupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Micron-scale additive manufacturing of binary and ternary alloys by electrohydrodynamic redox 3D printing

Porenta

Nydegger

Menétrey

et al. 2023

Preprint

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“…To tackle this challenge of high geometric fidelity in EHD printing, we here develop a combined experimental and modeling approach to investigate the flight dynamics of charged droplets using electrohydrodynamic redox 3D printing (EHDRP) process as a model system. EHDRP has recently been introduced as an electrochemical alternative to EHD, 4,23 in which the nanoparticles suspension is replaced with metal ions in solution. This technique advantageously combines both the high deposition rate of EHD and the various benefits of EC-based nanoscale 3D printing, 24 including superior as-deposited materials quality, 25 tunable microstructures, [26][27][28] and no requirement for post-printing annealing steps.…”

Section: Introductionmentioning

confidence: 99%

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

Menétrey

Koch

Sologubenko

et al. 2022

Small

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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.

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“…To tackle this challenge of high geometric fidelity in EHD printing, we here develop a combined experimental and modeling approach to investigate the flight dynamics of charged droplets using the electrohydrodynamic redox 3D printing (EHD-RP) process as a model system. EHD-RP has recently been introduced as an electrochemical alternative to EHD, , in which the nanoparticle suspension is replaced with metal ions in solution. This technique advantageously combines both the high deposition rate of EHD and the various benefits of EC-based nanoscale 3D printing, including superior as-deposited material quality, tunable microstructures, − and no requirement for postprinting annealing steps.…”

Section: Introductionmentioning

confidence: 99%

Nanodroplet Flight Control in Electrohydrodynamic Redox 3D Printing

Menétrey,

Zezulka,

Fandré

et al. 2023

ACS Appl. Mater. Interfaces

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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.

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Additive manufacturing of Zn with submicron resolution and its conversion into Zn/ZnO core–shell structures

Abstract: Electrohydrodynamic redox 3D printing (EHD-RP) is an additive manufacturing (AM) technique with submicron resolution and multi-metal capabilities, offering the possibility to switch chemistry during deposition "on-the-fly". Despite the potential for...

Cited by 9 publications

References 59 publications

Micron-scale additive manufacturing of binary and ternary alloys by electrohydrodynamic redox 3D printing

Micron-scale additive manufacturing of binary and ternary alloys by electrohydrodynamic redox 3D printing

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

Nanodroplet Flight Control in Electrohydrodynamic Redox 3D Printing

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