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

• assessment but shows that multiple electron collisions may play a role in FEBID, while the gas-phase experiments are conducted under single collision conditions. In the last decade, interest in organometallic FEBID precursors containing higher amounts of halogens, chlorine, bromine, and iodine has increased

• monolayer is high. This could be probed in a non-steady-state experiment similar to those reported for Pt(CO)2X2 (X = Cl, Br) and several other potential FEBID precursors [57]. Conclusion In the current study, we evaluated the performance of [Au(CH3

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

• and their efficiency, and they induce different fragmentation patterns. Thus, in order to better understand the performance of individual FEBID precursors, studies on their interaction with low-energy electrons are important. Metal carbonyls are generally well suited for the use in FEBID as many of

Irradiation-driven molecular dynamics simulation of the FEBID process for Pt(PF₃)₄

• Alexey Prosvetov,
• Alexey V. Verkhovtsev,
• Gennady Sushko and
• Andrey V. Solov’yov

Beilstein J. Nanotechnol. 2021, 12, 1151–1172, doi:10.3762/bjnano.12.86

• surface diffusion data for Pt(PF3)4 on hydroxylated or pristine SiO2 are not available, the obtained value of the surface diffusion coefficient, D = 2.85 × 10−7 cm2/s at 300 K, is within the range of values known for the typical surface diffusion coefficient of FEBID precursors [6][7][13]. Figure 2 shows

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

• 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

• applications from plasmonics [10] to optoelectronics [13]. Gold FEBID precursors (Figure 1) have had a similar history as other metal precursors, as the first tested compounds were taken from the existing library of gold precursors for chemical vapour deposition (CVD). The first compounds tested were gold

• gold(I) complexes has been explored, such as Au(PF3)Cl [27][28][29][30] and Au(CO)Cl [31], which gave high-purity deposits. Unfortunately, the high instability of these precursor molecules has severely hindered their use as FEBID precursors. For the compounds [AuMe2Cl]2 and Au(PMe3)Me [32], it was

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

• main challenges associated with FEBID is the typical low purity of the deposits. Many FEBID precursors are organometallic, leading to high carbon content in the deposit [6][8][9]. Often, unwanted fragments of the precursor molecules remain in the deposits [10]. Some precursors perform better in this

• in the carbon content, which supports that the carbon in the deposits does not originate from contamination of the SEM chamber. Conclusion The main conclusion of this study is that the two compounds Pt(CO)2Cl2 and Pt(CO)2Br2 can both be successfully used as FEBID precursors to make platinum

Chemistry for electron-induced nanofabrication

• Petra Swiderek,
• Hubertus Marbach and
• Cornelis W. Hagen

Beilstein J. Nanotechnol. 2018, 9, 1317–1320, doi:10.3762/bjnano.9.124

• must rely on a detailed understanding of all relevant aspects of FEBID. This includes the fundamental electron–precursor interactions leading to precursor fragmentation, surface reactions initiated by these interactions, the design and synthesis of novel FEBID precursors, as well as parameters inherent

• -induced dissociation of FEBID precursors. However, it is also important to investigate how these processes change in the presence of a surface or of other molecules. Therefore, it is also shown that DEA at near-thermal energies (which has previously received the most attention among electron-induced

• [27]. However, purification processes in FEBID are also studied with regards to their fundamental chemical processes. For instance, as halide ligands appear promising for future development of FEBID precursors, purification protocols that help to remove them are needed. Using deposits prepared from Pt

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

• ; focused electron beam induced deposition; heteronuclear FEBID precursors; surface science; Introduction Direct-write technologies using electron beams for nanostructure deposition can surpass the limitations of standard lithography techniques, such as the growth of three-dimensional nanostructures with

• dependence of the absolute and relative cross sections for low energy electron induced decomposition of a number of potential and currently used FEBID precursors. These include Co(CO)3NO [30][31], Pt(PF3)4 [32][33], W(CO)6 [34], MeCpPtMe3 [35], Fe(CO)5 [36], and more recently (η3-C3H5)Ru(CO)3Br [37][38] and

• effective in elucidating electron triggered decomposition of several FEBID precursors including Pt(PF3)4 [42], W(CO)6 [43], MeCpPtMe3 [44][45], Co(CO)3NO [46], Fe(CO)5 [47] and potential new precursors such as cis-Pt(CO)2Cl2 [48] and (η3-C3H5)Ru(CO)3Br [49]. From these surface science studies, it can be

Electron interaction with copper(II) carboxylate compounds

• Michal Lacko,
• Peter Papp,
• Iwona B. Szymańska,
• Edward Szłyk and
• Štefan Matejčík

Beilstein J. Nanotechnol. 2018, 9, 384–398, doi:10.3762/bjnano.9.38

• with some commonly used FEBID precursors [22] and have shown that in some cases a single ligand loss dominates the initial fragmentation following electron induced ionization or attachment. This may then induce other surface interactions. They also conclude that dissociation through neutral

• nanocrystals dispersed in a polymeric carbonaceous matrix, which contains all the ligand elements: carbon, oxygen, fluorine and silicone [29][30]. Therefore, new copper FEBID precursors are still necessary. When designing such new precursors, it should be considered that copper(II) derivatives are more user

• both the proper choice of ligands and the knowledge of elementary processes under DI and DEA in gas phase are important for the understanding and development of FEBID precursors. In the present experiments electron impact ionization, electron attachment, and subsequent dissociation processes have been

Gas-assisted silver deposition with a focused electron beam

• Luisa Berger,
• Katarzyna Madajska,
• Iwona B. Szymanska,
• Katja Höflich,
• Mikhail N. Polyakov,
• Jakub Jurczyk,
• Carlos Guerra-Nuñez and
• Ivo Utke

Beilstein J. Nanotechnol. 2018, 9, 224–232, doi:10.3762/bjnano.9.24

• often contaminate the metal deposit via ligand co-deposition or incomplete precursor dissociation [6]. Metal content for typical metal organic FEBID precursors without further processing ranges from 5 to 40 atom % [7]. In order to use FEBID for applications such as plasmonics [8][9][10], defined

• poisoned crystal surfaces which could not be exactly verified in the scope of this work. However, autocatalytic growth as known for other FEBID precursors [19][20][21], i.e., continued growth without electron beam exposure, could be experimentally disproven (Supporting Information File 1). Figure 3 shows

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

• , metallic nanostructures produced by FEBID are often contaminated by considerable amounts of carbon, preventing them from fulfilling their desired functionality [1][9]. The main source of this impurity is the precursor itself that is used for the process. FEBID precursors typically contain atoms of the

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

• for ligands fragmentation allow one to envisage the use of the two precursors for FEBID studies. Keywords: amines; copper(II); electron-stimulated desorption; FEBID precursors; HREELS; low-energy electrons; perfluorinated carboxylates; Introduction The high electrical conductivity of copper makes it

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

• uneven surfaces. Although FEBID is a promising technique, improvements are still needed in order to get pure and highly resolved deposits. CVD precursors are normally used as FEBID precursors; however, their performance is limited, leading to co-deposition of ligands and ligand fragments together with

• distribution characterised by a substantial fraction close to the ionization energy of FEBID precursors, peaking well below 10 eV and extending with appreciable intensities down to 0 eV [4]. The quality of the formed nanostructures is controlled and influenced by the interactions of the secondary and

Electron beam induced deposition of silacyclohexane and dichlorosilacyclohexane: the role of dissociative ionization and dissociative electron attachment in the deposition process

• Ragesh Kumar T P,
• Sangeetha Hari,
• Krishna K Damodaran,
• Oddur Ingólfsson and
• Cornelis W. Hagen

Beilstein J. Nanotechnol. 2017, 8, 2376–2388, doi:10.3762/bjnano.8.237

• into applicable design criteria for superior FEBID precursors. In this context a considerable number of gas-phase studies have been conducted, mainly on DEA and DI of different organometallic FEBID precursors. Complementary surface science studies have been carried out to better relate the gas-phase

• heteroleptic precursor [21][24][25][26] and on large heteronuclear carbonyl cluster compounds [22][23][30] that have partly proven to perform well in the FEBID deposition of magnetic alloys [31]. In fact, both DEA and DI cross sections of typical metal-containing FEBID precursors can be very high [32][33]. The

• current experiments are thus largely confined to DEA and DI of FEBID precursors. Despite this, significant insight has been provided by the gas-phase and surface-science studies and in individual cases a distinction between the role of DEA and DI in the deposition process has been achieved

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

• been observed in DEA to (η6-C6H6)Cr(CO)3. On the basis of our results it seems to be plausible to consider a multicentered benzyl group as a promising leaving group within FEBID precursors. Structure of (A) chromium(0) hexacarbonyl and (B) benzene-chromium(0) tricarbonyl. Yield of the fragment anions

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

• above 5 eV (self-scavenging). On the other hand, the presence of a few hundreds of argon atoms suppresses the low-energy channel completely. This low-energy behavior complements our previous results on clusters of FEBID precursors. For example, we have recently shown [13] that the positive ionization

Modelling focused electron beam induced deposition beyond Langmuir adsorption

• Dédalo Sanz-Hernández and
• Amalio Fernández-Pacheco

Beilstein J. Nanotechnol. 2017, 8, 2151–2161, doi:10.3762/bjnano.8.214

• various growth regimes when considering a single adsorbate, and has been restricted to physisorption processes, except for a few exceptions [28][29]. Relevant effects present in common FEBID precursors, such as autocatalytic effects [15][16][30][31][32] cannot be described either. Moreover, current

• physi-adsorption when E1 ≠ E2. This is essential when working on surfaces which may be chemically activated by electron irradiation [48]. Chemisorbed adsorbates are common, for instance, when using FEBID precursors leading to highly metallic deposits, such as Co2(CO)8, Co(CO)3NO and Fe(CO)5, where

• temperature. Examples of ν2, νe and νGAS values for standard experimental FEBID conditions. σ = 5·10−21 m2 for Co2(CO)8 is used from [19]. F is calculated for a Helios FEI dual beam system with a Pfeiffer TMH 262 turbo-molecular pump. Typical vaporization enthalpy values for FEBID precursors, associated to E2

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

• low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must

• be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface

• mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in

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

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

• be 10−2 to 10 mbar for organometallic precursors, but this can only serve as a very crude guideline. A very detailed account on FEBID precursors and their properties can be found in Utke et al. [6], ordered according to the respective type of organic ligand. Quite generally speaking, once supplied to