# Decay of iron pentacarbonyl clusters upon interaction with heavy ions

Leo Sala, Hlib Lyshchuk, Pamir Nag, Patrick Rousseau, Sylvain Maclot,

Alicja Domaracka, Jaroslav Kočišek

► To cite this version:

Leo Sala, Hlib Lyshchuk, Pamir Nag, Patrick Rousseau, Sylvain Maclot, et al. Decay of iron pentacarbonyl clusters upon interaction with heavy ions. Physica Scripta, 2025, 100 (2), pp.025402. 10.1088/1402-4896/ada205. hal-05097136

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PAPER

# Decay of iron pentacarbonyl clusters upon interaction with heavy ions

Leo Sala¹, Hlib Lyshchuk¹,², Pamir Nag¹, Patrick Rousseau³, Sylvain Maclot³, Alicja Domaracka³,*, and Jaroslav Kočiček¹,*,

¹ J. Heyrovský Institute of Physical Chemistry of the CAS, Dolejškova 3, 18223, Prague, Czech Republic

² Department of Physical Chemistry, University of Chemistry and Technology, Technická 5, 16628 Prague, Czech Republic

³ Normandie Univ., ENSICAEN, UNICAEN, CEA, CNRS, CIMAP, 14000 Caen, France

* Authors to whom any correspondence should be addressed

E-mail: domaracka@ganil.fr and kocisek@jh-inst.cas.cz

**Keywords:** clusters, ions, iron pentacarbonyl, mass spectrum, fragmentation, environment

Supplementary material for this article is available [online](#)

## Abstract

The present work is a continuation of our studies with iron pentacarbonyl, a model organometallic precursor for Focused Ion Beam-Induced Deposition (FIBID). Interactions of He²⁺(16 keV), Ne⁺(6 keV), Ne⁴⁺(40 keV), Ar²⁺(12 keV) and Ar⁸⁺(64 keV) projectile ions with [Fe(CO)₅]n clusters are studied using TOF mass spectrometry. The clusters represent an intermediate between the gas phase and the bulk environment and can be used as a proxy for the processes in complex environments such as e.g. the nanostructure deposition. The addition of environment in the present study results in the observation of fragments with high kinetic energies ejected from clusters, an overall reduction of the fragmentation, and observation of a range of fragments associated with C-O bond dissociation, not observed for isolated molecules. On the other hand, the high efficiency of the Ne⁺ projectile in fragmenting the Fe(CO)₅ isolated molecule is also observed in clusters.

## 1. Introduction

The number of fundamental studies of physicochemical processes in organometallic molecules is increasing due to their application in the additive techniques for the production of nanostructures such as focused electron [1] and ion beam-induced deposition [2]. Particularly, this fundamental information could be used to design novel precursors [3, 4], modify the deposition techniques [5, 6], or develop codes for more precise control of the deposition process. [7, 8] One of the most popular precursors for these fundamental studies is iron pentacarbonyl. On the one hand, it is a well-known precursor for the focused particle beam-induced deposition [9–11]. On the other hand, its properties such as high vapor pressure, the inertness of the ligands, or symmetry make it well-suitable for fundamental studies. Examples include the studies of bond dissociation energies [12], electron affinities of fragments [13], photoionization [14, 15], and a large amount of fundamental spectroscopic studies from IR to XUV region(e.g. [16–18]).

In relation to the particle beam-induced deposition, the most interesting information is provided by fragmentation patterns upon collisions with electron and ion projectiles. The first fundamental studies date back to 1970s [19], already showing the efficiency of low-energy electrons in decomposing the molecule. Over the last years, electron attachment [20], excitation [21], and ionization [22] were explored in detail. These processes are believed to play an important role in the deposition process, particularly in deposit broadening, due to the large amount of secondary low energy (0 eV-100 eV) electrons produced in the substrate during the electron and ion beam deposition process. [11, 23–25] Studies of ion interactions with isolated Fe(CO)₅ were performed in our previous collaboration [26] showing that the fragmentation proceeds via ejection of fast CO ligands against the static Fe atom, a fragmentation mechanism gainful for the deposition process. Use of a range of projectile ions irradiating the sample, available from the ARIBE facility (GANIL, Caen, France) allowed us to demonstrate also
an unusually high fragmentation efficiency of neon ions and reduced fragmentation efficiency for multiply charged ions interacting via resonant electron capture process.

As a next step, the processes during the deposition were modeled by experiments with clusters, which represent an intermediate between the isolated molecules and bulk [27]. Novel mechanisms were observed, particularly upon interactions with low-energy electrons. First, non-dissociative electron attachment resonances could become dissociative in clusters via a self-scavenging process [28]. Therefore, electrons in a broad range of energies could actively decompose iron pentacarbonyl in bulk in contrast to the narrow (resonant) energy band observed for isolated molecules. On the other hand, the energy transfer to the cluster environment can also reduce the number of dissociative events resulting in iron pentacarbonyl decomposition as demonstrated in our follow-up article studying the deposition of iron pentacarbonyl on Ar clusters as a proxy of the deposition substrate [29].

The same reduction of fragmentation was also observed for positive ions forming after electron ionization [30, 31], even though, the Fe⁺ and FeCO⁺ remain dominant fragment ions, same as observed for the isolated molecule [22]. Additionally, the formation of pure iron Fe⁺₂ and Fe⁺₃ ions was reported, similar to W⁺₂ previously reported for the tungsten hexacarbonyl dimer [32]. Finally, when iron pentacarbonyl is deposited on Ar clusters as a proxy of the deposition surface, hole transfer processes may induce its fragmentation due to the fact that Ar ionization energy is much higher than that of iron pentacarbonyl. The selection of substrate may therefore significantly influence the result of the ion deposition process.

Indeed, the strong influence of the substrate on post-irradiation chemistry and fragment desorption was demonstrated in the surface experiment of Massey and co-workers, studying low-energy electron irradiations of thin Fe(CO)₅ films on a Pt substrate with Xe matrix spacer [33]. The combined study with low-energy electrons and slow ions in a nuclear-stopping regime [34] demonstrated that even though the fragmentation efficiency of the second mentioned is higher (80% vs 50% CO loss), the final deposit is subject to sputtering by the impacting ions. It will be interesting to compare the possible thermal and recombination-induced desorption effects enhanced in high CO content deposits with the sputtering efficiency by ions.

The present study tries to provide an interlink between the isolated molecule studies and studies on the surface. This may provide a fundamental insight into the role of the primary ion beam processing of iron pentacarbonyl molecules in the deposition process.

## 2. Methods

The experiments were carried out at the ARIBE [35] facility of the GANIL [36] infrastructure. TOF mass spectrometry of [Fe(CO)₅]ₙ clusters was performed at the COLIMACON experimental setup [37].

The clusters were prepared using the gas aggregation technique in a liquid nitrogen-cooled He flow channel, producing a broad log-normal distribution of cluster sizes [38]. The temperature of the source was kept at 88 K, He flow at 150 l/min through a 0.5 mm aperture at the end of the 8 cm long channel with 1.2 cm internal diameter. The Fe(CO)₅ sample was kept in a glass cylinder at 295 K and added into the He flow using a heated needle valve kept at 323 K. The pressures during measurements were 3 × 10⁻⁵ mbar and 2.6 × 10⁻⁸ mbar in the cluster source and the collision region, respectively as measured by cold cathode ionization gauges.

The beam of (Fe(CO)₅)ₙ clusters was crossed by a beam of ions from the ARIBE beamline. The used projectiles were 16 keV ⁴He²⁺, 6 keV ²⁰Ne⁺, 40 keV ²⁰Ne⁴⁺, 12 keV ⁴⁰Ar²⁺, 64 keV ⁴⁰Ar⁸⁺. Figure 1 shows the ratio between the electronic and the nuclear-stopping power for the ion interaction with a gas phase Fe(CO)₅ target using the SRIM code [39]. The calculated values of the stopping powers depend on the target density as well as on the ion equilibrium charge state. Therefore, we use the ratio only as a guide to show that the interaction of He ions with the target will be driven by the electronic excitation of the target (electronic stopping) while the Ne or Ar projectiles will rather activate the motion of atomic nuclei (nuclear stopping).

Cationic products of the interaction were analyzed using a linear Wiley-Mclaren time-of-flight (TOF) spectrometer with a spatially extended extraction region [40]. The energy focusing in Wiley Mclaren TOF depends on the time ions are allowed for expansion under field-free conditions. Independent of the ion kinetic energy, the optimal ‘lag’ for reducing the TOF spread due to the initial kinetic energy of ions depends on m¹/² [41]. When a broad range of m/z ions is detected, the lag will be optimal only for a range of masses. In the present study, we therefore used the lag to obtain well-resolved mass spectra in different spectral ranges of m/z. The ‘lag’ is set as a delay between the ion pulse and the extraction pulse ΔTₗ as shown in figure 2.
<figure><img src="image_4.png" /><figcaption>**Figure 1.** Ratio of electronic to nuclear stopping power for individual projectiles used in the present work interacting with Fe(CO)₅ target calculated using SRIM [39].</figcaption></figure>

<figure><img src="image_5.png" /><figcaption>**Figure 2.** Projectile pulse (red) and reaction product extraction pulse (blue) timing in the present experiment. The time Δ*T*<sub>L</sub> between the projectile pulse and the extraction pulse was used for energy focussing in different mass regions of the measured fragmentation spectra according to the time-lag focusing originally proposed by Wiley and McLaren [41].</figcaption></figure>

**3. Results and discussion**

The main experimentally obtained results are the mass spectra for interaction with various ion projectiles
measured at different delays Δ*T*<sub>L</sub> allowing for the resolving of individual mass peaks and their shapes. First,
figure 3 shows the spectra in the region of the monomer fragmentation pattern in *m/z* = 0 to 255 range.

In comparison to the previous study of isolated molecule upon ion [26] as well as electron collisions [22], less
CO ligands are removed in clusters. The main ions observed correspond to parent ions +/− CO ligand and
CO⁺ cations, in contrast to the fragmentation pattern of the isolated molecule where the Fe⁺ and FeCO⁺ ions
are dominant. Interesting is also the fact that the clustering smears the differences in the fragmentation pattern
under the monomer mass, the spectra look very similar except in the case of Ar²⁺ projectiles. This is caused by
slightly different clustering conditions, which we experienced during this particular measurement (see
supporting information). The spectra at higher masses, which will be shown later as well as the strong and
narrow Fe⁺ signal indicate that much smaller clusters were present in the beam during this particular
measurement in comparison to the rest of the measurements. The conditions for this particular measurement
may be actually similar to that of the previous electron impact study [30], where the Fe⁺ remains dominant in
the spectra, despite the overall reduction of fragmentation due to clustering. The remaining measurements were
done under conditions with larger clusters.

Also visible in figure 3 are the fragment ions resulting from the dissociation of C-O bonds. In isolated
Fe(CO)₅ these were observed only as FeC⁺ or FeO⁺ fragments upon dissociation of all other CO ligands. In the
present cluster case, we can see the C-O bond cleavage products also for larger fragment ions. This may be
associated with energy transfer to solvent upon dissociation stabilizing this type of ion, which normally decays
<figure><img src="image_6.png" /><figcaption>**Figure 3.** Mass spectra in the range from *m/z* = 5 to *m/z* = 255 of fragment ions resulting from the interaction of Fe(CO)₅ clusters with ions, measured at delay Δ*T*<sub>L</sub> = 6μs.</figcaption></figure>

and cannot be detected in isolated molecule experiments. Such stabilization can be associated with the neutral molecule or CO functional group ejection from the initially formed M<sub>n</sub>Fe(CO)<sub>x</sub>C<sup>+</sup> or M<sub>n</sub>Fe(CO)<sub>x</sub>O<sup>+</sup> cations.

The signal of individual m/z fragment ions under the parent mass has the structure of a central narrow peak accompanied by doublets resulting from the high kinetic energy gained by these fragments during decay. This means that the fragments are ejected against the remaining cluster. We can see this behavior in the case of two particular ions that are zoomed in figure 4 Fe<sup>+</sup> and FeCO<sup>+</sup>. In the case of isolated molecules [26], we discussed that CO<sup>+</sup> ligands fly away from the Fe central atom with relatively high kinetic energies, with the remaining Fe atom practically frozen. In clusters, representing a more complex environment, the iron as well as iron-containing fragments can be ejected against the cluster mass with quite significant kinetic energy. In the case of Ar<sup>2+</sup>, again this effect is not so pronounced due to less clustering, even though the peak is slightly wider. In the case of a Coulomb explosion induced by highly charged Ar<sup>8+</sup> ions, the fast fragments dominate the Fe<sup>+</sup> as well as FeCO<sup>+</sup> ion peaks. Considering the kinetic energy value, this is highest for the Ne<sup>+</sup> projectile, even though the relative contribution of fast fragments to the total peak signal is lower than in other cases.

The influence of the fragment kinetic energy on the real FIBID process was recently discussed in the work of Abdel-Rahman [42]. The projectiles with higher nuclear stopping in the material actually penetrate less inside the surface and the product ions are ejected with higher kinetic energies from relatively large area, significantly complicating the FIBID process. We can see here a very similar trend. Additionally, we can see that this process will be even more pronounced for multiply charged ions due to Coulomb explosion.
<figure><img src="image_7.png" /><figcaption>**Figure 4.** Mass spectra in the range from *m/z* = 50 to *m/z* = 90 of fragment ions resulting from the interaction of Fe(CO)₅ clusters with ions, measured at delay Δ*T*<sub>L</sub> = 3μs.</figcaption></figure>

What remains similar to the previous gas phase study [26] is the higher fragmentation induced by the Ne⁺
projectile. We do not have a clear explanation for such behavior. Several studies have been devoted to the role of
projectile type on FIB deposition or etching [43, 44]. Most of the differences observed can be well attributed to
the changes in the ratio between nuclear and electronic stopping power (e.g. [45, 46]). However as discussed in
recent works, the form of energy transfer to the substrate is not the sole parameter to be considered during
deposition. A good example is the kinetic energy of fragments discussed in the previous paragraph [42]. In the
recent work of Herrer *et al* [47], Ga⁺ ions have been shown to be much more effective in the Pt deposition
process than Ne⁺ ions resulting in higher Pt purity at very low projectile doses. The behavior can be explained by
the higher nuclear-stopping power for the Ga⁺ projectile. At the same time, the work reports a completely
different morphology of the deposit prepared by Ne⁺ and Ga⁺ beams that can also influence the studied
conductivity of the deposit. The interpolation between the Ne⁺ and Ga⁺ projectiles is, therefore, not
straightforward and cannot be done based on one or two selected parameters. More complex studies are
required, with a wider range of projectiles, such as in the present work, and at different levels of complexity from
isolated molecules to bulk environments allowing for the rational design of the deposition process in the future.
Our studies show that Ne⁺ is more efficient in the initial iron pentacarbonyl fragmentation for both isolated
molecules and clusters. The effect may be therefore related to collision cross-sections for neon scattering on
individual Fe(CO)₅ atoms or the ionization mechanism. A thorough theoretical model of the interaction will be
beneficial.

To better support our conclusion about the Ne⁺ fragmentation efficiency in clusters, we will focus on a
higher mass range shown in figure 5. We cannot make conclusions from the region below the mass of monomer,
since the fragmentation in this region will strongly depend on the size of the cluster, as we discussed for Ar²⁺
projectile. We rather use a ratio that should be cluster size-independent, which is the ratio of signal intensity of
[Fe(CO)₅]₂Fe⁺ ions to that of [Fe(CO)₅]⁺ ions. This is based on the assumption that the formation of
<figure><img src="image_8.png" /><figcaption>**Figure 5.** Mass spectra in the range from *m/z* = 350 to *m/z* = 650 of fragment ions resulting from the interaction of Fe(CO)₅ clusters with ions measured at delay Δ*T*<sub>L</sub> = 12μs.</figcaption></figure>

[Fe(CO)₅]₂Fe⁺ will be dominated by the decay of [Fe(CO)₅]三分 ion [48–50]. Then the ratio of I([Fe(CO)₅]₂Fe⁺)/I([Fe(CO)₅]三分) will give us information about the relative fragmentation efficiency. To include the fact that the intensity of I([Fe(CO)₅]三分) to that of I([Fe(CO)₅]₂分) depends on the distribution of precursor cluster sizes, we should additionally multiply the result by the ratio of I([Fe(CO)₅]三分)/I([Fe(CO)₅]₂分). Combining the two, we end up with the ratio I([Fe(CO)₅]₂Fe⁺)/I([Fe(CO)₅]三分), which is shown in figure 6. The error bar was obtained by comparing the ratios for the Ne⁺ projectile at two different clustering conditions, one corresponding to the conditions reached for the 12 keV ⁴⁰Ar²⁺ measurement and another to the conditions used for the rest of the measurements. Even though in this case the effect is not so pronounced as for the isolated molecule (see figure 4 in the work of Indrajith *et al* [26]), the present work suggests that the Ne⁺ remains particularly efficient in the decomposition of Fe(CO₅) even if placed in a complex environment.

**4. Conclusions**

A series of ion irradiation experiments for [Fe(CO)₅]ₙ clusters demonstrate that fragment ions could gain significant kinetic energies when ejected against the cluster mass. This can be even more pronounced on rigid surfaces, resulting in sputtering and reduced ability to build nanostructures. The influence of such energetic dissociation of the precursor molecules on FIBID was recently discussed by Abdel-Rahman and co-workers [42].
<figure><img src="image_9.png" /><figcaption>**Figure 6.** Ratio of the integrated intensity of mass peaks assigned to $[Fe(CO)_5]_2Fe^+$ and $[Fe(CO)_5]_2^{+}$ ions in the TOF mass spectra presented in figure 5.</figcaption></figure>

The second interesting observation is the fragmentation pattern below the mass of the monomer. This is strongly dominated by $CO^+$ ions in the case of Ne projectiles but for all other projectiles, this channel is less intense than the $Fe(CO)_5^{+}$ fragment. One can see that the fragmentation pattern is not a smooth function of the ratio between electronic and nuclear stopping and exceptions occur.

Finally, we can see in all the spectra that fewer pure $Fe^+$ ions are produced in clusters in comparison to isolated molecules, reflecting the protective effect of the environment as discussed in many previous works.
[51–56]

## Acknowledgment

This work has been supported by the OP JAK project CZ.02.01.01/00/22_008/0004558 "AMULET" co-financed by EU. J.K. and L.S. acknowledge the support from the COST action CA20129 Multichem. H.L. acknowledges support from the EU H2020 program via the RADON project (GA 872494). The experiment was performed at Grand Accélérateur National d'Ions Lourds (GANIL) by means of CIRIL Interdisciplinary Platform, part of CIMAP laboratory, Caen, France.

## Data availability statement

All data that support the findings of this study are included within the article (and any supplementary files).

## ORCID iDs

Leo Sala https://orcid.org/0000-0003-1091-4386

Hlib Lyshchuk https://orcid.org/0000-0003-3964-4164

Pamir Nag https://orcid.org/0000-0002-1530-6104

Patrick Rousseau https://orcid.org/0000-0001-7217-2707

Sylvain Maclot https://orcid.org/0000-0001-5587-7182

Alicja Domaracka https://orcid.org/0000-0003-1585-2436

Jaroslav Kočíšek https://orcid.org/0000-0002-6071-2144

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