Water-assisted purification during electron beam-induced deposition of platinum and gold

• Cristiano Glessi,
• Fabian A. Polman and
• Cornelis W. Hagen

Beilstein J. Nanotechnol. 2024, 15, 884–896, doi:10.3762/bjnano.15.73

• MeCpPtMe3 respectively. Purification of FEBID materials with a reactant gas agent Purification of FEBID products by the use of a reactant gas has been performed either through a one-step procedure, with the co-injection of the FEBID precursor and the reactant gas (purification during deposition), or through

Electron-induced ligand loss from iron tetracarbonyl methyl acrylate

• Hlib Lyshchuk,
• Atul Chaudhary,
• Thomas F. M. Luxford,
• Miloš Ranković,
• Jaroslav Kočišek,
• Juraj Fedor,
• Lisa McElwee-White and
• Pamir Nag

Beilstein J. Nanotechnol. 2024, 15, 797–807, doi:10.3762/bjnano.15.66

• (FEBID); FEBID precursor; iron tetracarbonyl methyl acrylate; Introduction In recent years, a wave of interest in the electron-induced loss of ligands from organometallic and coordination compounds appeared, which has been motivated by the need to understand focused electron beam-induced deposition

Electron-induced deposition using Fe(CO)₄MA and Fe(CO)₅ – effect of MA ligand and process conditions

• Hannah Boeckers,
• Atul Chaudhary,
• Petra Martinović,
• Amy V. Walker,
• Lisa McElwee-White and
• Petra Swiderek

Beilstein J. Nanotechnol. 2024, 15, 500–516, doi:10.3762/bjnano.15.45

• surface reactions; Introduction Focused electron beam-induced deposition (FEBID) is a state-of-the-art direct-write process for the fabrication of nanoscale materials and devices with arbitrary shape and size down to the sub-10 nm regime [1][2][3]. In FEBID, precursor molecules that contain the element

• -induced decomposition of the heteroleptic potential FEBID precursor Fe(CO)4MA was investigated by surface science experiments under UHV conditions. The comparison with Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation. ESD experiments showed that CO and H2 desorb

A combined gas-phase dissociative ionization, dissociative electron attachment and deposition study on the potential FEBID precursor [Au(CH₃)₂Cl]₂

• Elif Bilgilisoy,
• Ali Kamali,
• Thomas Xaver Gentner,
• Gerd Ballmann,
• Sjoerd Harder,
• Hans-Peter Steinrück,
• Hubertus Marbach and
• Oddur Ingólfsson

Beilstein J. Nanotechnol. 2023, 14, 1178–1199, doi:10.3762/bjnano.14.98

• using [Au(CH3)2Cl]2 as a potential FEBID precursor. The FEBID in an UHV setup was conducted, in conjunction with a gas-phase study on the electron energy dependence of the fragmentation of this compound through DI and DEA. Moreover, quantum chemical calculations were used to determine the dominating

• of magnitude for DI and DEA of the FEBID precursor Co(CO)3(NO) [49][50] and Pt(PF3)4 [51], the reactive area of this monolayer is 0.15 μm2. Statistically, this implies approx. 300 reactive incidents per molecule if the cross section is assumed to stay unchanged. This is clearly not a quantitative

Fragmentation of metal(II) bis(acetylacetonate) complexes induced by slow electrons

• Janina Kopyra and
• Hassan Abdoul-Carime

Beilstein J. Nanotechnol. 2023, 14, 980–987, doi:10.3762/bjnano.14.81

• electron beam with an organometallic target (e.g., focused electron beam-induced deposition, FEBID) is a promising technique for direct 3D deposition of high-purity materials with minimum residual carbon in the product on the surface [4][5]. The FEBID precursor molecules adsorb and diffuse on the surface

Low-energy electron interaction and focused electron beam-induced deposition of molybdenum hexacarbonyl (Mo(CO)₆)

• Po-Yuan Shih,
• Maicol Cipriani,
• Christian Felix Hermanns,
• Jens Oster,
• Klaus Edinger,
• Armin Gölzhäuser and
• Oddur Ingólfsson

Beilstein J. Nanotechnol. 2022, 13, 182–191, doi:10.3762/bjnano.13.13

• the metal–metal bond formation will be more easily surmounted. Conclusion Here we have reported on the interactions of low-energy electrons with the FEBID precursor Mo(CO)6 and on the composition of deposits made with this precursor. Dissociative electron attachment in the energy range from about 0 up

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

• Cristiano Glessi,
• Aya Mahgoub,
• Cornelis W. Hagen and
• Mats Tilset

Beilstein J. Nanotechnol. 2021, 12, 257–269, doi:10.3762/bjnano.12.21

• properties of a FEBID precursor molecule are crucial for the deposition process. The precursor molecule should be volatile in a suitable range of pressures and temperatures. Under these conditions, it needs to be easily deliverable in the gas phase, adsorb on a substrate, be sensitive to the electron beam

Electron beam-induced deposition of platinum from Pt(CO)₂Cl₂ and Pt(CO)₂Br₂

• Aya Mahgoub,
• Hang Lu,
• Rachel M. Thorman,
• Konstantin Preradovic,
• Titel Jurca,
• Lisa McElwee-White,
• Howard Fairbrother and
• Cornelis W. Hagen

Beilstein J. Nanotechnol. 2020, 11, 1789–1800, doi:10.3762/bjnano.11.161

• contained no carbon, but a large halogen content. Contrary to expectations based on volatility, Pt(CO)2Br2 turned out to perform worse than Pt(CO)2Cl2 as a FEBID precursor with the lowest growth rate and the lowest platinum content. Results from this investigation provide added motivation for studies

A novel copper precursor for electron beam induced deposition

• Caspar Haverkamp,
• George Sarau,
• Mikhail N. Polyakov,
• Ivo Utke,
• Marcos V. Puydinger dos Santos,
• Silke Christiansen and
• Katja Höflich

Beilstein J. Nanotechnol. 2018, 9, 1220–1227, doi:10.3762/bjnano.9.113

• ratios of copper to oxygen and copper to carbon (d) Height of FEBID pads for different deposition times, written with a dwell time of 10 μs and a point distance of 3 nm. (e) Atomic force microscope line scans of the FEBID pad in (a) and (b). (a) Raman spectra of a FEBID pad, FEBID precursor and the

Dynamics and fragmentation mechanism of (C₅H₄CH₃)Pt(CH₃)₃ on SiO₂ surfaces

• Kaliappan Muthukumar,
• Harald O. Jeschke and
• Roser Valentí

Beilstein J. Nanotechnol. 2018, 9, 711–720, doi:10.3762/bjnano.9.66

• ); focused electron beam induced deposition (FEBID); precursor; trimethyl(methylcyclopentadienyl)platinum(IV) ((CH3-C5H4)Pt(CH3)3); Introduction Nanoscale device applications require a growth of regular or specially patterned transition metal nanodeposits. Electron beam induced deposition (EBID), is a size

Electron interactions with the heteronuclear carbonyl precursor H₂FeRu₃(CO)₁₃ and comparison with HFeCo₃(CO)₁₂: from fundamental gas phase and surface science studies to focused electron beam induced deposition

• Ragesh Kumar T P,
• Paul Weirich,
• Lukas Hrachowina,
• Marc Hanefeld,
• Ragnar Bjornsson,
• Helgi Rafn Hrodmarsson,
• Sven Barth,
• D. Howard Fairbrother,
• Michael Huth and
• Oddur Ingólfsson

Beilstein J. Nanotechnol. 2018, 9, 555–579, doi:10.3762/bjnano.9.53

• as Co. However, alternative precursors for the direct deposition of high-purity compounds are desired especially for non-precious metals and more complex compositions. In FEBID precursor decomposition is primarily induced by secondary electrons produced as the high-energy primary beam impinges on the

Electron-driven and thermal chemistry during water-assisted purification of platinum nanomaterials generated by electron beam induced deposition

• Ziyan Warneke,
• Markus Rohdenburg,
• Jonas Warneke,
• Janina Kopyra and
• Petra Swiderek

Beilstein J. Nanotechnol. 2018, 9, 77–90, doi:10.3762/bjnano.9.10

• an electron-driven process but also proceeds via additional thermal chemistry. Such thermal chemistry that assists the removal of ligands from the precursor has been described before. In particular, previous surface science studies on the FEBID precursor Pt(PF3)4 have shown that the initial electron

• dimer by thermal cracking above 172 °C. It was kept below −20 °C in the sample reservoir throughout the experiments to prevent the reverse reaction to the dimer. Molecular structure of the FEBID precursor trimethyl(methyl-cyclopentadienyl)platinum(IV) (MeCpPtMe3) (a), schematic of the FEBID process and

Response under low-energy electron irradiation of a thin film of a potential copper precursor for focused electron beam induced deposition (FEBID)

• Leo Sala,
• Iwona B. Szymańska,
• Céline Dablemont,
• Anne Lafosse and
• Lionel Amiaud

Beilstein J. Nanotechnol. 2018, 9, 57–65, doi:10.3762/bjnano.9.8

• competitive with thermolysis of the ligands. The possibility to evaporate the compound allows one to envisage its use as a FEBID precursor. Moreover, the dissociation of the precursor to a pure heavy deposit and the release of volatile fragments is a crucial issue in FEBID. Considering the amine and

The rational design of a Au(I) precursor for focused electron beam induced deposition

• Ali Marashdeh,
• Thiadrik Tiesma,
• Niels J. C. van Velzen,
• Sjoerd Harder,
• Remco W. A. Havenith,
• Jeff T. M. De Hosson and
• Willem F. van Dorp

Beilstein J. Nanotechnol. 2017, 8, 2753–2765, doi:10.3762/bjnano.8.274

• , we propose a Au(I) compound for high-purity gold deposition. Results and Discussion Crystal structures of Au complexes The stability of FEBID precursor molecules in Figure 2 strongly depends on the stability of the metal–ligand bond. Apart from that, intermolecular Au–Au interactions (aurophilicity

Synthesis of [{AgO₂CCH₂OMe(PPh₃)}_n] and theoretical study of its use in focused electron beam induced deposition

• Jelena Tamuliene,
• Julian Noll,
• Peter Frenzel,
• Tobias Rüffer,
• Alexander Jakob,
• Bernhard Walfort and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 2615–2624, doi:10.3762/bjnano.8.262

• suitable as a FEBID precursor for silver deposition, its vapor pressure was determined (p170 °C = 5.318 mbar, ∆Hvap = 126.1 kJ mol−1), evincing little volatility. Also EI and ESI mass spectrometric studies were carried out. The dissociation of the silver(I) compound 2 under typical electron-driven FEBID

• fragmentation mechanisms are needed. Commonly, a FEBID precursor should display a high vapor pressure at reasonable temperatures and must have a satisfactorily long residence time on the surface typically lasting micro- to milliseconds, otherwise the corresponding layer thickness will be too small [4]. The

• [{AgO2CCH2OMe(PPh3)}n] is a suitable FEBID precursor for silver deposition. Thus, we discuss the synthesis and the chemical and physical properties of [{AgO2CCH2OMe}n] and [{AgO2CCH2OMe(PPh3)}n]. DFT (B3LYP) studies were applied to predict the most favorable fragmentation pathways according to the lowest energy

Interactions of low-energy electrons with the FEBID precursor chromium hexacarbonyl (Cr(CO)₆)

• Jusuf M. Khreis,
• João Ameixa,
• Filipe Ferreira da Silva and
• Stephan Denifl

Beilstein J. Nanotechnol. 2017, 8, 2583–2590, doi:10.3762/bjnano.8.258

• Ciências e Tecnologia, Universidade NOVA de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal 10.3762/bjnano.8.258 Abstract Interactions of low-energy electrons with the FEBID precursor Cr(CO)6 have been investigated in a crossed electron–molecular beam setup coupled with a double focusing mass

• + peak. Conclusion In this work, we have presented a detailed investigation of electron interactions with the FEBID precursor Cr(CO)6. Electron attachment leads to the dissociation of the compound and no molecular parent anion can be detected on mass spectrometric timescales in the present study. The

Dissociative electron attachment to coordination complexes of chromium: chromium(0) hexacarbonyl and benzene-chromium(0) tricarbonyl

• Janina Kopyra,
• Paulina Maciejewska and
• Jelena Maljković

Beilstein J. Nanotechnol. 2017, 8, 2257–2263, doi:10.3762/bjnano.8.225

• technological applications [22]. For instance, Cr is used in photomasks so that Cr-containing FEBID precursors are of interest for mask repair [23] and Cr(CO)6 has in fact been studied as a FEBID precursor earlier [24]. In the present work, we report the results from DEA to the gas-phase chromium(0

Comprehensive investigation of the electronic excitation of W(CO)₆ by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV

• Mónica Mendes,
• Khrystyna Regeta,
• Filipe Ferreira da Silva,
• Nykola C. Jones,
• Søren Vrønning Hoffmann,
• Gustavo García,
• Chantal Daniel and
• Paulo Limão-Vieira

Beilstein J. Nanotechnol. 2017, 8, 2208–2218, doi:10.3762/bjnano.8.220

• initio molecular dynamics simulations of focused electron beam induced deposition (FEBID) precursor molecules adsorbed on fully and partially hydroxylated SiO2 surfaces [24]. Electron-induced reactions in FEBID processes are initiated by low-energy secondary electrons rather than the high-energy primary

Suppression of low-energy dissociative electron attachment in Fe(CO)₅ upon clustering

• Jozef Lengyel,
• Peter Papp,
• Štefan Matejčík,
• Jaroslav Kočišek,
• Michal Fárník and
• Juraj Fedor

Beilstein J. Nanotechnol. 2017, 8, 2200–2207, doi:10.3762/bjnano.8.219

• typical FEBID precursor are extremely sensitive to its elementary environment. In the gas phase, the decomposition via anion production proceeds at very low electron energies. Even the presence of several neighboring molecules opens the possibility of a new anion synthesis channel at electron energies

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors

• Rachel M. Thorman,
• Ragesh Kumar T. P.,
• D. Howard Fairbrother and
• Oddur Ingólfsson

Beilstein J. Nanotechnol. 2015, 6, 1904–1926, doi:10.3762/bjnano.6.194

• general, the SE yield reaches a distinct maximum well below 1 keV PE energy, before decreasing rapidly again, as is discussed in more detail in context to the commonly used FEBID precursor MeCpPtMe3 in section 4.1. Figure 3 shows the experimentally determined SE energy distribution for 400 eV PEs

• cross sections at low incident energies. Good examples of such reactions are the extensive fragmentation of tetrafluorophenol and tetrafluoroaniline [35] as well as that of the commonly used FEBID precursor ligands tri- and hexafluoroacetylacetone [36]. In each of these cases, low energy electron

• studies To study low energy electron-induced processes in the gas phase, a low energy electron beam with a resolution of about 100 meV is crossed with an effusive beam of FEBID precursor molecules and the electron energy dependence for the formation of charged fragments is monitored by mass spectrometry

Continuum models of focused electron beam induced processing

• Milos Toth,
• Charlene Lobo,
• Vinzenz Friedli,
• Aleksandra Szkudlarek and
• Ivo Utke

Beilstein J. Nanotechnol. 2015, 6, 1518–1540, doi:10.3762/bjnano.6.157

• Figure 10, is often advantageous, such as in the deposition of high purity materials using a FEBID precursor and an oxygen-containing background gas [56][57][58][59][60][61][62][63], or a mixture of two FEBID precursors [4][8][64][65][66]. Unintentional deposition of carbonaceous films through electron

• the deposit contains an indent caused by preferential depletion of the FEBID precursor adsorbates “d”. At the highest electron flux (f0 = 5 × 103 Å−2s−1), FEBIE dominates in the central region of the deposit due to complete depletion of “d”. The preferential depletion of species “d” is a direct

• FEBID precursor tetraethyl orthosilicate (TEOS, Si(OC2H5)4) chemisorbs onto SiO2 as a mixture of (SiO)2Si(OC2H5)2 and (SiO)Si(OC2H5)3 [72][73][74]. Chemisorption of gas phase precursor molecules can take place if their thermal energy is sufficiently high to surmount the barrier Econv − Ep (see Figure 12

Focused electron beam induced deposition: A perspective

• Michael Huth,
• Fabrizio Porrati,
• Christian Schwalb,
• Marcel Winhold,
• Roland Sachser,
• Maja Dukic,
• Jonathan Adams and
• Georg Fantner

Beilstein J. Nanotechnol. 2012, 3, 597–619, doi:10.3762/bjnano.3.70

Spontaneous dissociation of Co₂(CO)₈ and autocatalytic growth of Co on SiO₂: A combined experimental and theoretical investigation

• Kaliappan Muthukumar,
• Harald O. Jeschke,
• Roser Valentí,
• Evgeniya Begun,
• Johannes Schwenk,
• Fabrizio Porrati and
• Michael Huth

Beilstein J. Nanotechnol. 2012, 3, 546–555, doi:10.3762/bjnano.3.63

• dissociation of the precursor molecule. In view of these calculations, we discuss the origin of this dissociation and the subsequent autocatalysis. Keywords: Co2(CO)8; deposition; dissociation; EBID; FEBID; precursor; radiation-induced nanostructures; Introduction In recent years, focused electron beam