The fabrication of nanostructures with high resolution and precise control of the deposition site makes Focused Electron Beam Induced Deposition (FEBID) a unique nanolithography process. In the case of magnetic materials, apart from the FEBID potential in standard substrates for multiple applications in data storage and logic, the use of this technology for the growth of nanomagnets on different types of scanning probes opens new paths in magnetic sensing, becoming a benchmark for magnetic functionalization. This work reviews the recent advances in the integration of FEBID magnetic nanostructures onto cantilevers to produce advanced magnetic sensing devices with unprecedented performance.
Seven gold(I) N-heterocyclic carbene (NHC) complexes were synthesized, characterized, and identified as suitable precursors for focused electron beam-induced deposition (FEBID). Several variations on the core Au(NHC)X moiety were introduced, that is, variations of the NHC ring (imidazole or triazole), of the alkyl N-substituents (Me, Et, or iPr), and of the ancillary ligand X (Cl, Br, I, or CF3). The seven complexes were tested as FEBID precursors in an on-substrate custom setup. The effect of the substitutions on deposit composition and growth rate indicates that the most suitable organic ligand for the gold precursor is triazole-based, with the best deposit composition of 15 atom % gold, while the most suitable anionic ligand is the trifluoromethyl group, leading to a growth rate of 1 × 10−2 nm3/e−.
AbstractA comparative study of vacuum versus ambient pressure inert gas thermogravimetry was performed on silver carboxylates compounds. Some of the complexes from this group have been previously successfully applied as precursors for both chemical vapour deposition and electron beam-induced deposition. Considerable differences were found between the thermogravimetry methods, which we associate with changes in evaporation dynamics. Vacuum thermogravimetry sublimation onsets consistently occurred at lower temperatures than ambient pressure N2-flow thermogravimetry, where the differences reached up to 120 °C. Furthermore, compound sublimation during N2-TGA was suppressed to such an extent that significant thermal decomposition of the compounds into metal and volatile organic fragments was observed while at vacuum the same complexes sublimed as intact molecules. Moreover, thermal stability of silver complexes was investigated using isothermal thermogravimetry. These findings are interesting for the field of thin film synthesis and nanomanufacturing via chemical vapour deposition, atomic layer deposition and focused electron beam induced deposition. In all three methods, delivery of functional precursor over the substrate is crucial. The presented results prove that vacuum thermogravimetry can be used as fast method of pre-screening for novel, especially low-volatility precursors.
Graphic abstract
Focused electron beam induced deposition is a versatile tool for the direct fabrication of complex-shaped nanostructures with unprecedented shape fidelity and resolution. While the technique is well-established for various materials, the direct electron beam writing of silver is still in its infancy. Here, five different silver carboxylates, three fluorinated: [Ag2(µ-O2CCF3)2], [Ag2(µ-O2CC2F5)2], [Ag2(µ-O2CC3F7)2] and two containing hydrogen: [Ag2(µ-O2CCMe2Et)2] and [Ag2(µ-O2CtBu)2] were examined and compared as potential precursors for focused electron beam induced deposition. All of the compounds show high sensitivity to electron dissociation and efficient dissociation of Ag-O bonds. The as-deposited materials showed high silver content from 42 at.% to above 70at.% and silver nano-crystal formation with impurities of carbon and fluorine incorporated between metal grains. A correlation of the number of carbon atoms in the precursor ligands and silver content of the deposited structures was found. The highest silver contents were achieved for compounds with the shortest CF chains. The deposited silver content depends on the balance of electron induced ligand co-deposition and thermal ligand desorption. Low electron flux is advantageous for high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for focused electron beam nanoprinting of high silver content materials.
Coordination and organometallic precursors of group 10 and 11: Focused electron beam induced deposition of metals and insight gained from chemical vapour deposition, atomic layer deposition, and fundamental surface and gas phase studies
