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Abstract The fabrication of Ru nanostructures by focused electron beam induced deposition (FEBID) requires suitable precursor molecules and processes to obtain the pure metal. So far this is problematic because established organometallic Ru precursors contain large organic ligands, such as cyclopentadienyl anions, that tend to become embedded in the deposit during the FEBID process. Recently, (η³-C₃H₅)Ru(CO)₃X (X = Cl, Br) has been proposed as an alternative precursor because CO can easily desorb under electron exposure. However, allyl and Cl ligands remain behind after electron irradiation and the removal of the halide requires extensive electron exposures. Auger electron spectroscopy is applied to demonstrate a postdeposition purification process in which NH₃is used as a reactant that enhances the removal of Cl from deposits formed by electron irradiation of thin condensed layers of (η³-C₃H₅)Ru(CO)₃Cl. The loss of CO from the precursor during electron-induced decomposition enables a reaction between NH₃and the Cl ligands that produces HCl. The combined use of electron-stimulated desorption experiments and thermal desorption spectrometry further reveals that thermal reactions contribute to the loss of CO in the FEBID process but remove only minor amounts of the allyl and Cl ligands. 

Ion beam-induced deposition (IBID) using Pt(CO)₂Cl₂and Pt(CO)₂Br₂as precursors has been studied with ultrahigh-vacuum (UHV) surface science techniques to provide insights into the elementary reaction steps involved in deposition, complemented by analysis of deposits formed under steady-state conditions. X-ray photoelectron spectroscopy (XPS) and mass spectrometry data from monolayer thick films of Pt(CO)₂Cl₂and Pt(CO)₂Br₂exposed to 3 keV Ar⁺, He⁺, and H₂⁺ions indicate that deposition is initiated by the desorption of both CO ligands, a process ascribed to momentum transfer from the incident ion to adsorbed precursor molecules. This precursor decomposition step is accompanied by a decrease in the oxidation state of the Pt(II) atoms and, in IBID, represents the elementary reaction step that converts the molecular precursor into an involatile PtX₂species. Upon further ion irradiation these PtCl₂or PtBr₂species experience ion-induced sputtering. The difference between halogen and Pt sputter rates leads to a critical ion dose at which only Pt remains in the film. A comparison of the different ion/precursor combinations studied revealed that this sequence of elementary reaction steps is invariant, although the rates of CO desorption and subsequent physical sputtering were greatest for the heaviest (Ar⁺) ions. The ability of IBID to produce pure Pt films was confirmed by AES and XPS analysis of thin film deposits created by Ar⁺/Pt(CO)₂Cl₂, demonstrating the ability of data acquired from fundamental UHV surface science studies to provide insights that can be used to better understand the interactions between ions and precursors during IBID from inorganic precursors. 

The electron-induced decomposition of Fe(CO)₄MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)₄MA and Fe(CO)₅revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)₄MA and Fe(CO)₅were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)₄MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)₄MA and Fe(CO)₅on an Fe seed layer prepared by EBID was compared. While Fe(CO)₅sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)₄MA. The heteroleptic precursor Fe(CO)₄MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes. 

We probe the separation of ligands from iron tetracarbonyl methyl acrylate (Fe(CO)₄(C₄H₆O₂) or Fe(CO)₄MA) induced by the interaction with free electrons. The motivation comes from the possible use of this molecule as a nanofabrication precursor and from the corresponding need to understand its elementary reactions fundamental to the electron-induced deposition. We utilize two complementary electron collision setups and support the interpretation of data by quantum chemical calculations. This way, both the dissociative ionization and dissociative electron attachment fragmentation channels are characterized. Considerable differences in the degree of precursor fragmentation in these two channels are observed. Interesting differences also appear when this precursor is compared to structurally similar iron pentacarbonyl. The present findings shed light on the recent electron-induced chemistry of Fe(CO)₄MA on a surface under ultrahigh vacuum. 

The focused ion beam (FIB) is a powerful tool for fabrication, modification, and characterization of materials down to the nanoscale. Starting with the gallium FIB, which was originally intended for photomask repair in the semiconductor industry, there are now many different types of FIB that are commercially available. These instruments use a range of ion species and are applied broadly in materials science, physics, chemistry, biology, medicine, and even archaeology. The goal of this roadmap is to provide an overview of FIB instrumentation, theory, techniques, and applications. By viewing FIB developments through the lens of various research communities, we aim to identify future pathways for ion source and instrumentation development, as well as emerging applications and opportunities for improved understanding of the complex interplay of ion–solid interactions. We intend to provide a guide for all scientists in the field that identifies common research interest and will support future fruitful interactions connecting tool development, experiment, and theory. While a comprehensive overview of the field is sought, it is not possible to cover all research related to FIB technologies in detail. We give examples of specific projects within the broader context, referencing original works and previous review articles throughout.