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.

Towards Establishing Best Practice in the Analysis of Hydrogen and Deuterium by Atom Probe Tomography.

As hydrogen is touted as a key player in the decarbonization of modern society, it is critical to enable quantitative hydrogen (H) analysis at high spatial resolution and, if possible, at the atomic scale. H has a known deleterious impact on the mechanical properties (strength, ductility, toughness) of most materials that can hinder their use as part of the infrastructure of a hydrogen-based economy. Enabling H mapping including local hydrogen concentration analyses at specific microstructural features is essential for understanding the multiple ways that H affect the properties of materials including embrittlement mechanisms and their synergies. In addition, spatial mapping and quantification of hydrogen isotopes is essential to accurately predict tritium inventory of future fusion power plants thus ensuring their safe and efficient operation. Atom probe tomography (APT) has the intrinsic capability to detect H and deuterium (D), and in principle the capacity for performing quantitative mapping of H within a material's microstructure. Yet, the accuracy and precision of H analysis by APT remain affected by complex field evaporation behavior and the influence of residual hydrogen from the ultrahigh vacuum chamber that can obscure the signal of H from within the material. The present article reports a summary of discussions at a focused workshop held at the Max-Planck Institute for Sustainable Materials in April 2024. The workshop was organized to pave the way to establishing best practices in reporting APT data for the analysis of H. We first summarize the key aspects of the intricacies of H analysis by APT and then propose a path for better reporting of the relevant data to support interpretation of APT-based H analysis in materials.

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.

Local electrode atom probe analysis of silicon nanowires grown with an aluminum catalyst.

Local electrode atom probe (LEAP) tomography of Al-catalyzed silicon nanowires synthesized by the vapor­liquid­solid method is presented. The concentration of Al within the Al-catalyzed nanowire was found to be 2 × 10(20) cm(-3), which is higher than the expected solubility limit for Al in Si at the nanowire growth temperature of 550°C. Reconstructions of the Al contained within the nanowire indicate a denuded region adjacent to the Al catalyst/Si nanowire interface, while Al clusters are distributed throughout the rest of the silicon nanowire.

Unconventional magnetization textures and domain-wall pinning in Sm-Co magnets.

Some of the best-performing high-temperature magnets are Sm-Co-based alloys with a microstructure that comprises an [Formula: see text] matrix and magnetically hard [Formula: see text] cell walls. This generates a dense domain-wall-pinning network that endows the material with remarkable magnetic hardness. A precise understanding of the coupling between magnetism and microstructure is essential for enhancing the performance of Sm-Co magnets, but experiments and theory have not yet converged to a unified model. Here, transmission electron microscopy, atom probe tomography, and nanometer-resolution off-axis electron holography have been combined with micromagnetic simulations to reveal that the magnetization state in Sm-Co magnets results from curling instabilities and domain-wall pinning effects at the intersections of phases with different magnetic hardness. Additionally, this study has found that topologically non-trivial magnetic domains separated by a complex network of domain walls play a key role in the magnetic state by acting as nucleation sites for magnetization reversal. These findings reveal previously hidden aspects of magnetism in Sm-Co magnets and, by identifying weak points in the microstructure, provide guidelines for improving these high-performance magnetic materials.

Size-dependent diffusion controls natural aging in aluminium alloys.

A key question in materials science is how fast properties evolve, which relates to the kinetics of phase transformations. In metals, kinetics is primarily connected to diffusion, which for substitutional elements is enabled via mobile atomic-lattice vacancies. In fact, non-equilibrium vacancies are often required for structural changes. Rapid quenching of various important alloys, such as Al- or Mg-alloys, results for example in natural aging, i.e. slight movements of solute atoms in the material, which significantly alter the material properties. In this study we demonstrate a size effect of natural aging in an AlMgSi alloy via atom probe tomography with near-atomic image resolution. We show that non-equilibrium vacancy diffusional processes are generally stopped when the sample size reaches the nanometer scale. This precludes clustering and natural aging in samples below a certain size and has implications towards the study of non-equilibrium diffusion and microstructural changes via microscopy techniques.

Observations of Si field evaporation.

Field evaporation studies of crystalline <100> Si were performed in a three-dimensional atom-probe, which utilized a local electrode geometry. Several distinct phenomena were observed. Si field evaporation rates showed: (1) no measurable dependence on temperature below 110K, (2) an exponential dependence on evaporation rate as a function of temperature above 110K, and (3) no dependence on substrate doping (i.e., electrical conductivity) as high as 10 Omega cm in the temperature range of 40-150K. Two distinct evaporation modes were observed. The first was associated with approximately 1at% H+ in the mass spectrum. Negligible amounts of H were detected in the mass spectra of the second mode. When the pulse fraction (pf) was increased from 5% to 30%, the presence of H+ in the mass spectra, i.e. operation in the first mode, was associated with a degradation in mass resolution by as much as 80% for the 10 Omega cm Si samples. Conversely, no loss in mass resolution was detected for the approximately 0.001 Omega cm samples over the pf range studied.

An environmental transfer hub for multimodal atom probe tomography.

Environmental control during transfer between instruments is required for samples sensitive to air or thermal exposure to prevent morphological or chemical changes prior to analysis. Atom probe tomography is a rapidly expanding technique for three-dimensional structural and chemical analysis, but commercial instruments remain limited to loading specimens under ambient conditions. In this study, we describe a multifunctional environmental transfer hub allowing controlled cryogenic or room-temperature transfer of specimens under atmospheric or vacuum pressure conditions between an atom probe and other instruments or reaction chambers. The utility of the environmental transfer hub is demonstrated through the acquisition of previously unavailable mass spectral analysis of an intact organic molecule made possible via controlled cryogenic transfer into the atom probe using the hub. The ability to prepare and transfer specimens in precise environments promises a means to access new science across many disciplines from untainted samples and allow downstream time-resolved in situ atom probe studies.