Detailed knowledge of electron-induced chemical reactions of FEBID precursors

The fundamental electron-induced chemistry of a range of different potential FEBID precursors has been investigated by participants of CELINA. A complete understanding of the chemistry involved in FEBID is based on a combination of (i) gas phase measurements of the electron-induced fragmentation of the individual precursor molecules, (ii) studies of the electron-induced decomposition of the same molecules adsorbed on a surface, and (iii) theory that helps to make predictions for processes that cannot be monitored experimentally. Before CELINA, comprehensive information was available only for few precursors (MeCpPtMe₃, Pt(PF₃)₄, Co(CO)₃NO, W(CO)₆) as reviewed in

• Rachel M. Thorman, Ragesh Kumar T.P., D. Howard Fairbrother, Oddur Ingolfsson:
  The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors,
  Beilstein J. Nanotechnol. 6 (2015) 1904–1926.

Even for these four precursors, however, the picture was not complete. During the duration of the Action, more details of the electron-induced chemistry of these precursors and others, among them several newly synthesized ones, were unraveled:

Pt(PF₃)₄ - the role of neutral excitation to precursor fragmentation

• M. Zlatar, M. Allan, J. Fedor:
  Excited States of Pt(PF₃)₄ and Their Role in Focused Electron-Beam Nanofabrication,
  J. Phys. Chem. C 120 (2016) 10667–10674.

Co(CO)₃NO - the role of the molecular environment on precursor decomposition

• Johannes Postler, Michael Renzler, Alexander Kaiser, Stefan E. Huber, Michael Probst, Paul Scheier, Andrew M. Ellis:
  Electron-Induced Chemistry of Cobalt Tricarbonyl Nitrosyl (Co(CO)₃NO) in Liquid Helium Nanodroplets,
  J. Phys. Chem. C 119 (2015) 20917–20922.

• F. Vollnhals, M. Drost, F. Tu, E. Carrasco, A. Späth, R. H. Fink, H.-P. Steinrück, H. Marbach:
  Electron Beam-Induced Deposition and Autocatalytic Decomposition of Co(CO)₃NO,
  Beilstein J. Nanotechnol. 5 (2014) 1175–1185.

W(CO)₆ - a surprisingly complete fragmentation

• Michael Neustetter, Andreas Mauracher, Paulo Lima˜o-Vieira, Stephan Denifl:
  Complete ligand loss in electron ionization of the weakly bound organometallic tungsten hexacarbonyl dimer,
  Phys.Chem.Chem.Phys. 18 (2016) 9893.

• M. Neustetter, E. Jabbour Al Maalouf, P. Limão-Vieira, S. Denifl:
  Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization,
  J. Chem. Phys. 145 (2016) 054301/1-6.

• M. Mendes, K. Regeta, F. Ferreira da Silva, N. C. Jones, S. V. Hofmann, G. García, C. Daniel, P. Limão-Vieira:
  Comprehensive investigation of W(CO)6 electronic excitation by photoabsorption and ab initio calculations in the energy region from 3.9 to 10.8 eV,
  Beilstein J. Nanotechnol. 8 (2017) 2208–2218.

Fe(CO)₅ - comprehensive insight in its fragmentation channels

• Anita Ribar, Marián Danko, Juraj Országh, Filipe Ferreira da Silva, Ivo Utke, Štefan Matejčík:
  Dissociative excitation study of iron pentacarbonyl molecule
  Eur. Phys. J. D 69 (2015) 117.

• Michal Lacko, Peter Papp, Karol Wnorowski, Štefan Matejčík:
  Electron-induced ionization and dissociative ionization of iron pentacarbonyl molecules,
  Eur. Phys. J. D 69 (2015) 84.

• J. Lengyel, J. Fedor, and M. Fárník:
  Ligand Stabilization and Charge Transfer in Dissociative Ionization of Fe(CO)₅ Aggregates,
  J. Phys. Chem. C 120 (2016) 17810−17816.

• Jozef Lengyel, Peter Papp, Štefan Matejčík, Jaroslav Kočišek, Michal Fárník, Juraj Fedor:
  Suppression of low-energy dissociative electron attachment in Fe(CO)₅ upon clustering,
  Beilstein J. Nanotechnol. 8 (2017) 2200–2207.

WCl₆ - problem of oxidation and electron-induced fragmentation

• Michael Neustetter, Filipe Ferreira da Silva, Stephan Denifl:
  Electron interactions with the focused electron beam induced processing (FEBID) precursor tungsten hexachloride,
  Rapid Commun. Mass Spectrom. 30 (2016) 1139–1144.

Cr(0)(C₆H₆)(CO)₃ - surprisingly facile removal of the benzene ligand

• Janina Kopyra, Paulina Maciejewska, Jelena Maljković:
  Dissociative electron attachment to coordination complexes of chromium: chromium(0) hexacarbonyl and benzene-chromium(0) tricarbonyl,
  Beilstein J. Nanotechnol. 8 (2017) 2257–2263.

Novel silanes - the role of fragmentation mechanisms on deposit broadening

• Elías H. Bjarnason, Benedikt Ómarsson, Nanna Rut Jónsdóttir, Ingvar Árnason,
  Oddur Ingólfsson:
  Dissociative electron attachment and dissociative ionization of 1,1-dichloro-1-silacyclohexane and silacyclohexane,
  International Journal of Mass Spectrometry 370 (2014) 39–43.

• Ragesh Kumar T P, Sangeetha Hari, Krishna K Damodaran, Oddur Ingólfsson, Cornelis W. Hagen:
  Electron beam induced deposition of silacyclohexane and dichlorosilacyclohexane: the role of dissociative ionization and dissociative electron attachment in the deposition process,
  Beilstein J. Nanotechnol. 8 (2017) 2376–2388.

A novel Ru containing precursor - influence of ligand architecture on precursor fragmentation processes

• Rachel M. Thorman, Ragnar Bjornsson, Oddur Ingólfsson:
  Computational study of dissociative electron attachment to π-allyl ruthenium (II) tricarbonyl bromide,
  Eur. Phys. J. D 70 (2016) 164.

• Rachel M. Thorman, Joseph A. Brannaka, Lisa McElwee-White, Oddur Ingolfsson:
  Low energy electron-induced decomposition of (η³-C₃H₅)Ru(CO)₃Br, a potential focused electron beam induced deposition precursor with a heteroleptic ligand set,
  Phys.Chem.Chem.Phys. 19 (2017) 13264-13271.

A novel bimetallic precursor HFeCo₃(CO)₁₂ - detailed understanding of its electron-induced fragmentation

• Ragesh Kumar T.P., Ragnar Bjornsson, Sven Barth, Oddur Ingólfsson:
  Formation and decay of negative ion states up to 11 eV above the ionization energy of the nanofabrication precursor HFeCo₃(CO)₁₂,
  Chem. Sci. 8 (2017) 5949-5952.

• Ragesh Kumar T.P., Sven Barth, Ragnar Bjornsson, Oddur Ingólfsson:
  Structure and energetics in dissociative electron attachment to HFeCo₃(CO)₁₂
  Eur. Phys. J. D 70 (2016) 163.

Further studies

Several other compounds were also studied (Cu(II)carboxylates, Tetraethyl orthosilicate, H₂FeRu₃(CO)₁₃, η⁵-CpFe(CO)₂Mn(CO)₅) as described in STSM reports and the book of abstracts from CELINA 2016 and Cat CELINA 2017. The publications will be listed here as they appear.