134 Surface Science 156 (1985) 134-139

North-Holland, Amsterdam

Received 10 July 1984

Sputtered metal cfusters are energy analyzed, mass filtered and injected into a RF quadrupole
drift tube. This confinement allowed us to perform collision-induced dissociations, chemical
reactions and ph~~tofragmentatio~ experiments on clusters of a single site. The results give an
insight into the dynamic properties of charged metal aggregates.

1, Introduction

The investigation of the dynamic properties of metal aggregates as a

function of their size is one of the main objectives of cluster research. All
experiments, however, are handicaped by the fact that these relatively unstable
particles are only produced in very low abundances and in a mixture of sizes.
Supersonic molecular beam expansion combined with mass spectrometric
detection is a very powerful method for generating and invcst~gat~ng these
metal aggregates. All ionization effects, however, are accompanied by strong
fragmentation channels, even when very “soft” photoionization experiments
are performed flf. Since the technique generally does not allow one to
distinguish mother ions and fragments, the observed signals cannot easily be
attributed to the originating particles.
Furthermore, the expansion method is mainly restricted to metals which are
easily vaporized, and the investigation of interesting transition metals, for
example, is very difficult. For this reason we established a sputtering experi-
ment, which allows us to produce most types of metal clusters. The positively
and negatively charged particles, or reionized neutrals are energy analyzed,
mass filtered and injected into a HF quadrupole trap, where inelastic scattering
experiments are performed.

2. Experiment

The experimental arrangement is shown in fig. 1. The clusters are formed by

bombarding a metallic target with a high intensity ion beam (SIMS) f2]. The

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 P. Foyer, L. W&e / Metal cluster ions 135

Residual Ion
Gas Inlet

111

Target Energy - Ion Drift Tube QMS

Analyzer
Ion Deflector

Fig. 1. Experimental arrangement.

primary ion beam is generated in a cold reflex discharge ion source (CORDIS),
developed by Keller [3]. The ion source is placed inside a differentially pumped
vacuum chamber, at a distance of 50 cm from the target, and an angle of
incidence of 50’. Operating at an ion energy of 15 keV and a primary beam
diameter of 10 mm, typical ion currents of 3 mA were measured. The target
was bombarded with neutralized ions (FAB = fast atom bombardment) [4]
when non-conductive targets were used. To achieve this the argon ion beam is
passed through a 10 cm long argon gas cell. At a pressure of = 10e3 mbar
about 10% of the primary ion beam is neutralized by means of resonant charge
exchange. The remaining ions are extracted later from the neutral particle
beam with an extraction capacitor.
The target is mounted on a manipulator device for rapid exchange and
optimum positioning. It was temperature controlled. The corresponding vacuum
chamber contains window flanges on both sides of the target in order to
reionize sputtered neutrals by photoionization. The system is pumped with a
500 l/s turbomolecular pump.
The sputtered ions or reionized neutrals pass through an axial energy
analyzer [5] and are injected into a quadrupole mass filter (Extranuclear model
7-162-8). The energy- and mass-filtered cluster ions are guided directly into a
quadrupole trap 60 cm long, with an identical sectional view as the mass filter.
The relative electric potential of the rod system allows reduction of the kinetic
energies of the incident ions to almost thermal velocities, and storage times up
to 10 ms are reached. This is very favorable for performing photodissociation
experiments with pulsed lasers at a high duty cycle. Since the ion trap is
operated with RF only, all ion sizes are kept in confinement, which allows US
to observe photofragments and reaction products.
136 P. Fayet, L. Wiiste / Metal cluster ions

In order to avoid undesired collisions with background gas during the

storage time, the vacuum inside the quadrupole trap must be -C lop9 mbar.
This required a UHV system pumped by turbomolecular pumps. The quadru-
pole drift tube passes a reaction chamber, where a scattering gas was intro-
duced, when collision-induced fragmentation experiments or chemical reac-
tions on the stored cluster ions were performed.

Fig. 2. (a) Mass spectrum of positively charged particles sputtered from a silver target. Pure silver
clusters and unidentified mixed compounds from target impurities are observable. (b) Mass
spectrum of positively charged particles sputtered from a nickel target.
 P. Fayet, L. Wbste / Metal cluster ions 137

A second quadrupole mass filter is lined up (Extranuclear model 7-162-8) at

the ion exit of the quadrupole drift tube. This is used to analyze all inelastic
scattering events. The ions are recorded with a secondary electron multiplier,
which is mounted on an electrostatic ion deflector, in order to leave clearance
for a laser beam.

3. Results

Fig. 2 shows mass spectra of sputtered cluster ions, as they are obtained,
when the first quadrupole mass filter is tuned, and the second filter is held, like
the ion trap, in a non-discriminative mode on RF only. The spectrum in fig. 2a
was recorded with a silver target. The intensity distribution of the Ag:
particles shows a distinct odd-even alternation, this has been observed and
explained previously by Joyes and Leleyter [6]. The mass spectrum in fig. 2b
was obtained from a nickel target. The Ni: aggregates, up to Ni&, rather than
showing any alternations with growing cluster size, exhibit a monotonic
decrease.
Neutral particles which emerged from a potassium target were reionized
using a 1 kW Hg lamp as photoionization source. The mass spectra, which
were obtained in this way, showed a similar distribution to the sputtered ions
[7]. In order to determine the temperature of the sputtered molecules, one- and
two-photon ionization experiments were performed on the potassium dimer,
using tunable dye lasers. No precise temperature values could be deduced from
these measurements, however, due to a very high ground-state distribution,
which is an indication of a very high temperature (> 1000 K). Similar
observations were made by Van Veen et al. [8].
An example of a collision-induced fragmentation and a chemical reaction is
shown in fig. 3, where the drift tube was supplied with Nil. When oxygen was

Fig. 3. Collision-induced fragmentation and chemical reaction of Niz with oxygen.

138 P. Fayet, L. Wij,te / Metal cluster ions

inserted into the reaction chamber, Nii and Nif fragments appeared together
with Ni20+ as a reaction product.
Laser-induced photofragmentations were recorded using phase sensitive
detection of the ion signal while the laser beam was modulated. The resulting
fragment patterns, as they were obtained from Ag_T, Agl, Agq and Agg are
shown in fig. 4. The curves indicate clearly the depletion of the mother ion
peak (negative lock-in signal) and the formation of fragments (positive lock-in
peak). The results were taken with a laser power of 1.5 W at a wavelength of
488 nm. Similar results were also obtained at 514.5 nm. The kinetic energy of
the cluster ions was 17 eV, which corresponds to an interaction time with the
laser of about 6 ms.

b)
_

Size of fragment cluster ions

w
i 2 3 L 5 6 7 8 g “g:

Fig. 4. Phase sensitively detected photofragmentation of Ag;. Agl , Ag: and Agg’. The irradiated
laser wavelength was 488 nm.
 P. Fayer, L. W&te / Metal cluster ions 139

4. Discussion

With the triple quadrupole arrangement, chemical reactions as well as

collision- and laser-induced fragmentation experiments can be performed on
single size clusters. Although it is quite certain that the experiments were
performed on relatively hot particles, the strong photofragmentation phenom-
ena, which occurred even at moderate laser powers, are very surprising. This is
an indication, that the cross sections for electronic excitation of the ions into
repulsive electronic states are rather large. The explanation lies in the structure
of the excited states of ionic clusters, which tend to dissociate because the
molecular core seen by the excited electron is a doubly charged ion, which is
frequently unstable with respect to Coulomb explosion [9,10]. Ag:+ is an
example of an unstable doubly charged cluster ion, whereas Ni:+, for example,
is stable and can be observed by means of mass spectrometry.
Future experiments will concentrate on the energetic aspects of the observed
fragmentation processes by using tunable lasers, furthermore we will try to
cool down the cluster ions by expanding a carrier gas in the target area.

References

[l] G. Delacretaz, J.D. Ganiere, R. Monot and L. Waste, Appl. Phys. B 29 (1982) 55.
[2] G. Hortig, M. Miller, 2. Physik. 221 (1969) 119.
[3] R. Keller, Symp. on Act. Aspects of Heavy Ion Fusion, Darmstadt, 1983.
[4] F.M. Devienne and J.C. Roustan, Org. Mass Spectrom. 17 (1982) 173.
[5] W.D. Fite and M.W. Siegel, private communication.
[6] P. Joyes and M. Leleyter, J. Phys. B6 (1975) 150.
[7] P. Fayet and L. Waste, Spectrosc. Intern. J., in press.
[S] G. van Veen, private communication.
[9] M. Broyer, J. Chevaleyre, G. Delacretaz, P. Fayet and L. Waste, Surface Sci. 156 (1985) 342.
[lo] K. Sattler, J. Miihlbach, 0. Echt, P. Pfau and E. Recknagel, Phys. Rev. Letters 47 (1981) 160.