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

Utke, Ivo; Swiderek, Petra; Höflich, Katja; Madajska, Katarzyna; Jurczyk, Jakub; Martinović, Petra; Szymańska, Iwona

doi:10.1016/j.ccr.2021.213851

Cited by 48 publications

(47 citation statements)

References 390 publications

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“…The molecules of complexes are composed of organic ligands to render the metal volatile for delivery to the substrate inside the SEM vacuum chamber. A large variety of precursor families have been involved in FEBID studies, including metal carbonyls, β-diketonates, carboxylates, cyclopentadienyls, phosphines, halides, and alkyls [ 38 , 65 ]. However, FEBID and metal-organic resist approaches still suffer from relatively low metal contents in the deposited material [ 20 ].…”

Section: Introductionmentioning

confidence: 99%

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum

et al. 2022

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Recent developments in nanoprinting using focused electron beams have created a need to develop analysis methods for the products of electron-induced fragmentation of different metalorganic compounds. The original approach used here is termed focused-electron-beam-induced mass spectrometry (FEBiMS). FEBiMS enables the investigation of the fragmentation of electron-sensitive materials during irradiation within the typical primary electron beam energy range of a scanning electron microscope (0.5 to 30 keV) and high vacuum range. The method combines a typical scanning electron microscope with an ion-extractor-coupled mass spectrometer setup collecting the charged fragments generated by the focused electron beam when impinging on the substrate material. The FEBiMS of fragments obtained during 10 keV electron irradiation of grains of silver and copper carboxylates and shows that the carboxylate ligand dissociates into many smaller volatile fragments. Furthermore, in situ FEBiMS was performed on carbonyls of ruthenium (solid) and during electron-beam-induced deposition, using tungsten carbonyl (inserted via a gas injection system). Loss of carbonyl ligands was identified as the main channel of dissociation for electron irradiation of these carbonyl compounds. The presented results clearly indicate that FEBiMS analysis can be expanded to organic, inorganic, and metal organic materials used in resist lithography, ice (cryo-)lithography, and focused-electron-beam-induced deposition and becomes, thus, a valuable versatile analysis tool to study both fundamental and process parameters in these nanotechnology fields.

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Section: Introductionmentioning

confidence: 99%

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum

et al. 2022

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“…Unfortunately, the organic ligands often become incorporated in the deposits leading to unwanted contaminations. Without applying post-deposition purification methods, the metal content of typical FEBID deposits fabricated from metal-containing precursors typically lies in the range 5–40 atom% [ 3 , 5 , 6 ]. This impedes possible applications requiring, e.g., high electrical conductivity.…”

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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“…This limits the range of applications for nanostructures created via FEBID [ 1 , 15 , 16 ]. The purity of the deposition depends strongly on the utilized precursor and the writing parameters such as primary beam energy/current, beam diameter, and replenishment time [ 17 ]. It has been shown that it is possible to obtain almost pure iron [ 18 ] structures from Fe(CO) 5 (>95 at.%) or tungsten [ 19 ] from WF 6 (>97 at.%).…”

Section: Introductionmentioning

confidence: 99%

“…The electron-induced decomposition mechanisms of FEBID-relevant precursor molecules have been investigated in combined gas-phase and surface science studies [ 17 , 34 , 35 , 36 ]. The corresponding results suggest that deposition is mainly initiated by reactions between precursor molecules and low-energy electrons [ 35 , 36 ].…”

Section: Introductionmentioning

confidence: 99%

On the Electron-Induced Reactions of (CH3)AuP(CH3)3: A Combined UHV Surface Science and Gas-Phase Study

et al. 2022

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Focused-electron-beam-induced deposition (FEBID) is a powerful nanopatterning technique where electrons trigger the local dissociation of precursor molecules, leaving a deposit of non-volatile dissociation products. The fabrication of high-purity gold deposits via FEBID has significant potential to expand the scope of this method. For this, gold precursors that are stable under ambient conditions but fragment selectively under electron exposure are essential. Here, we investigated the potential gold precursor (CH3)AuP(CH3)3 using FEBID under ultra-high vacuum (UHV) and spectroscopic characterization of the corresponding metal-containing deposits. For a detailed insight into electron-induced fragmentation, the deposit’s composition was compared with the fragmentation pathways of this compound through dissociative ionization (DI) under single-collision conditions using quantum chemical calculations to aid the interpretation of these data. Further comparison was made with a previous high-vacuum (HV) FEBID study of this precursor. The average loss of about 2 carbon and 0.8 phosphor per incident was found in DI, which agreed well with the carbon content of the UHV FEBID deposits. However, the UHV deposits were found to be as good as free of phosphor, indicating that the trimethyl phosphate is a good leaving group. Differently, the HV FEBID experiments showed significant phosphor content in the deposits.

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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

Cited by 48 publications

References 390 publications

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum

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

On the Electron-Induced Reactions of (CH3)AuP(CH3)3: A Combined UHV Surface Science and Gas-Phase Study

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