Mechanism-based design of precursors for focused electron beam-induced deposition

Carden, Will G.; Lü, Hang; Spencer, Julie A.; Fairbrother, D. Howard; McElwee‐White, Lisa

doi:10.1557/mrc.2018.77

Cited by 32 publications

(40 citation statements)

References 109 publications

(177 reference statements)

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“…Under these conditions, it needs to be easily deliverable in the gas phase, adsorb on a substrate, be sensitive to the electron beam, and decompose in a clean manner to the desired products. Furthermore, it should be inexpensive and easy to prepare, non-toxic, and easy to store and handle [ 17 ]. The choice of such molecules requires a compromise to be made between volatility, stability, and reactivity induced by electron irradiation of the molecule.…”

Section: Resultsmentioning

confidence: 99%

“…Normally, the metal content is quite limited, and the deposits are often heavily contaminated with carbon. Therefore, it makes sense to use as little carbon as possible in the design of the molecule [ 17 ]. Furthermore, it has been observed that large ligands, such as the methylcyclopentadienyl group in MeCpPtMe 3 and acetylacetonate in Au(acac)Me 2 , do not decompose favourably under electron irradiation.…”

Section: Resultsmentioning

confidence: 99%

“…However, when using organometallic precursors, usually, undesired dissociation fragments also end up in the deposit. A major challenge is therefore to achieve control over the composition of the deposited material through a proper design of the precursor molecule [ 17 – 18 ].…”

Section: Introductionmentioning

confidence: 99%

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Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition

Glessi¹,

Mahgoub²,

Hagen³

et al. 2021

Beilstein J. Nanotechnol.

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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−.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition

Glessi¹,

Mahgoub²,

Hagen³

et al. 2021

Beilstein J. Nanotechnol.

View full text Add to dashboard Cite

show abstract

“…The design of suitable FEBID precursors requires insight into the mechanisms that govern their electron-induced decomposition [ 13 ]. As demonstrated herein for the case of Ag(I) complexes, the efficient decomposition of the precursors depends decisively on the structure of the organic ligands that are coordinated to the metal.…”

Section: Introductionmentioning

confidence: 99%

Electron-Induced Decomposition of Different Silver(I) Complexes: Implications for the Design of Precursors for Focused Electron Beam Induced Deposition

et al. 2022

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Focused electron beam induced deposition (FEBID) is a versatile tool to produce nanostructures through electron-induced decomposition of metal-containing precursor molecules. However, the metal content of the resulting materials is often low. Using different Ag(I) complexes, this study shows that the precursor performance depends critically on the molecular structure. This includes Ag(I) 2,2-dimethylbutanoate, which yields high Ag contents in FEBID, as well as similar aliphatic Ag(I) carboxylates, aromatic Ag(I) benzoate, and the acetylide Ag(I) 3,3-dimethylbutynyl. The compounds were sublimated on inert surfaces and their electron-induced decomposition was monitored by electron-stimulated desorption (ESD) experiments in ultrahigh vacuum and by reflection−absorption infrared spectroscopy (RAIRS). The results reveal that Ag(I) carboxylates with aliphatic side chains are particularly favourable for FEBID. Following electron impact ionization, they fragment by loss of volatile CO2. The remaining alkyl radical converts to a stable and equally volatile alkene. The lower decomposition efficiency of Ag(I) benzoate and Ag(I) 3,3-dimethylbutynyl is explained by calculated average local ionization energies (ALIE) which reveal that ionization from the unsaturated carbon units competes with ionization from the coordinate bond to Ag. This can stabilise the ionized complex with respect to fragmentation. This insight provides guidance with respect to the design of novel FEBID precursors.

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“…FEBID depends on the electron-stimulated decomposition of volatile precursors. In this context, the most extensive body of data for precursor derivatives is focused on homometallic metal carbonyls M y (CO) x [ 10 , 11 ]. The plethora of data related to the electron-induced decomposition of this class of compounds is a result of their commercial availability and typically convenient handling as well as the simplicity of the CO ligand.…”

Section: Introductionmentioning

confidence: 99%

Vanadium and Manganese Carbonyls as Precursors in Electron-Induced and Thermal Deposition Processes

et al. 2022

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The material composition and electrical properties of nanostructures obtained from focused electron beam-induced deposition (FEBID) using manganese and vanadium carbonyl precursors have been investigated. The composition of the FEBID deposits has been compared with thin films derived by the thermal decomposition of the same precursors in chemical vapor deposition (CVD). FEBID of V(CO)6 gives access to a material with a V/C ratio of 0.63–0.86, while in CVD a lower carbon content with V/C ratios of 1.1–1.3 is obtained. Microstructural characterization reveals for V-based materials derived from both deposition techniques crystallites of a cubic phase that can be associated with VC1−xOx. In addition, the electrical transport measurements of direct-write VC1−xOx show moderate resistivity values of 0.8–1.2 × 103 µΩ·cm, a negligible influence of contact resistances and signatures of a granular metal in the temperature-dependent conductivity. Mn-based deposits obtained from Mn2(CO)10 contain ~40 at% Mn for FEBID and a slightly higher metal percentage for CVD. Exclusively insulating material has been observed in FEBID deposits as deduced from electrical conductivity measurements. In addition, strong tendencies for postgrowth oxidation have to be considered.

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Mechanism-based design of precursors for focused electron beam-induced deposition

Abstract: Abstract

Cited by 32 publications

References 109 publications

Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition

Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition

Electron-Induced Decomposition of Different Silver(I) Complexes: Implications for the Design of Precursors for Focused Electron Beam Induced Deposition

Vanadium and Manganese Carbonyls as Precursors in Electron-Induced and Thermal Deposition Processes

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