Pillar Growth by Focused Electron Beam-Induced Deposition Using a Bimetallic Precursor as Model System: High-Energy Fragmentation vs. Low-Energy Decomposition.

Electron-induced fragmentation of the HFeCo3(CO)12 precursor allows direct-write fabrication of 3D nanostructures with metallic contents of up to >95 at %. While microstructure and composition determine the physical and functional properties of focused electron beam-induced deposits, they also provide fundamental insights into the decomposition process of precursors, as elaborated in this study based on EDX and TEM. The results provide solid information suggesting that different dominant fragmentation channels are active in single-spot growth processes for pillar formation. The use of the single source precursor provides a unique insight into high- and low-energy fragmentation channels being active in the same deposit formation process.

Additive Manufacturing of Co3Fe Nano-Probes for Magnetic Force Microscopy.

Magnetic force microscopy (MFM) is a powerful extension of atomic force microscopy (AFM), which mostly uses nano-probes with functional coatings for studying magnetic surface features. Although well established, additional layers inherently increase apex radii, which reduce lateral resolution and also contain the risk of delamination, rendering such nano-probes doubtful or even useless. To overcome these limitations, we now introduce the additive direct-write fabrication of magnetic nano-cones via focused electron beam-induced deposition (FEBID) using an HCo3Fe(CO)12 precursor. The study first identifies a proper 3D design, confines the most relevant process parameters by means of primary electron energy and beam currents, and evaluates post-growth procedures as well. That way, highly crystalline nano-tips with minimal surface contamination and apex radii in the sub-15 nm regime are fabricated and benchmarked against commercial products. The results not only reveal a very high performance during MFM operation but in particular demonstrate virtually loss-free behavior after almost 8 h of continuous operation, thanks to the all-metal character. Even after more than 12 months of storage in ambient conditions, no performance loss is observed, which underlines the high overall performance of the here-introduced FEBID-based Co3Fe MFM nano-probes.

Controlled Morphological Bending of 3D-FEBID Structures via Electron Beam Curing.

Focused electron beam induced deposition (FEBID) is one of the few additive, direct-write manufacturing techniques capable of depositing complex 3D nanostructures. In this work, we explore post-growth electron beam curing (EBC) of such platinum-based FEBID deposits, where free-standing, sheet-like elements were deformed in a targeted manner by local irradiation without precursor gas present. This process diminishes the volumes of exposed regions and alters nano-grain sizes, which was comprehensively characterized by SEM, TEM and AFM and complemented by Monte Carlo simulations. For obtaining controlled and reproducible conditions for smooth, stable morphological bending, a wide range of parameters were varied, which will here be presented as a first step towards using local EBC as a tool to realize even more complex nano-architectures, beyond current 3D-FEBID capabilities, such as overhanging structures. We thereby open up a new prospect for future applications in research and development that could even be further developed towards functional imprinting.

Mesoscopic Structures and Coexisting Phases in Silica Films.

Silica films represent a unique two-dimensional film system, exhibiting both crystalline and vitreous forms. While much scientific work has focused on the atomic-scale features of this film system, mesoscale structures can play an important role for understanding confined space reactions and other applications of silica films. Here, we report on mesoscale structures in silica films grown under ultrahigh vacuum and examined with scanning tunneling microscopy (STM). Silica films can exhibit coexisting phases of monolayer, zigzag, and bilayer structures. Both holes in the film structure and atomic-scale substrate steps are observed to influence these coexisting phases. In particular, film regions bordering holes in silica bilayer films exhibit vitreous character, even in regions where the majority film structure is crystalline. At high coverages mixed zigzag and bilayer phases are observed at step edges, while at lower coverages silica phases with lower silicon densities are observed more prevalently near step edges. The STM images reveal that silica films exhibit rich structural diversity at the mesoscale.

FEBID 3D-Nanoprinting at Low Substrate Temperatures: Pushing the Speed While Keeping the Quality.

High-fidelity 3D printing of nanoscale objects is an increasing relevant but challenging task. Among the few fabrication techniques, focused electron beam induced deposition (FEBID) has demonstrated its high potential due to its direct-write character, nanoscale capabilities in 3D space and a very high design flexibility. A limitation, however, is the low fabrication speed, which often restricts 3D-FEBID for the fabrication of single objects. In this study, we approach that challenge by reducing the substrate temperatures with a homemade Peltier stage and investigate the effects on Pt based 3D deposits in a temperature range of 5-30 °C. The findings reveal a volume growth rate boost up to a factor of 5.6, while the shape fidelity in 3D space is maintained. From a materials point of view, the internal nanogranular composition is practically unaffected down to 10 °C, followed by a slight grain size increase for even lower temperatures. The study is complemented by a comprehensive discussion about the growth mechanism for a more general picture. The combined findings demonstrate that FEBID on low substrate temperatures is not only much faster, but practically free of drawbacks during high fidelity 3D nanofabrication.

High-Fidelity 3D Nanoprinting of Plasmonic Gold Nanoantennas.

The direct-write fabrication of freestanding nanoantennas for plasmonic applications is a challenging task, as demands for overall morphologies, nanoscale features, and material qualities are very high. Within the small pool of capable technologies, three-dimensional (3D) nanoprinting via focused electron beam-induced deposition (FEBID) is a promising candidate due to its design flexibility. As FEBID materials notoriously suffer from high carbon contents, the chemical postgrowth transfer into pure metals is indispensably needed, which can severely harm or even destroy FEBID-based 3D nanoarchitectures. Following this challenge, we first dissect FEBID growth characteristics and then combine individual advantages by an advanced patterning approach. This allows the direct-write fabrication of high-fidelity shapes with nanoscale features in the sub-10 nm range, which allow a shape-stable chemical transfer into plasmonically active Au nanoantennas. The here-introduced strategy is a generic approach toward more complex 3D architectures for future applications in the field of 3D plasmonics.

A Two-Dimensional 'Zigzag' Silica Polymorph on a Metal Support.

We present a new polymorph of the two-dimensional (2D) silica film with a characteristic 'zigzag' line structure and a rectangular unit cell which forms on a Ru(0001) metal substrate. This new silica polymorph may allow for important insights into growth modes and transformations of 2D silica films as a model system for the study of glass transitions. Based on scanning tunneling microscopy, low energy electron diffraction, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy measurements on the one hand, and density functional theory calculations on the other, a structural model for the 'zigzag' polymorph is proposed. In comparison to established monolayer and bilayer silica, this 'zigzag' structure system has intermediate characteristics in terms of coupling to the substrate and stoichiometry. The silica 'zigzag' phase is transformed upon reoxidation at higher annealing temperature into a SiO2 silica bilayer film which is chemically decoupled from the substrate.

Metal tungstates at the ultimate two-dimensional limit: fabrication of a CuWO4 nanophase.

Metal tungstates (with general formula MWO4) are functional materials with a high potential for a diverse set of applications ranging from low-dimensional magnetism to chemical sensing and photoelectrocatalytic water oxidation. For high level applications, nanoscale control of film growth is necessary, as well as a deeper understanding and characterization of materials properties at reduced dimensionality. We succeeded in fabricating and characterizing a two-dimensional (2-D) copper tungstate (CuWO4). For the first time, the atomic structure of an ultrathin ternary oxide is fully unveiled. It corresponds to a CuWO4 monolayer arranged in three sublayers with stacking O-W-O/Cu from the interface. The resulting bidimensional structure forms a robust framework with localized regions of anisotropic flexibility. Electronically it displays a reduced band gap and increased density of states close to the Fermi level with respect to the bulk compound. These unique features open a way for new applications in the field of photo- and electrocatalysis, while the proposed synthesis method represents a radically new and general approach toward the fabrication of 2-D ternary oxides.