9 Fast Atom Bombardment

When particles of kiloelectronvolt kinetic energy are impinging on a surface, they

cause the ejection of neutrals and secondary ions from that surface. Secondary ion
mass spectrometry (SIMS) employing the sputtering effects of a beam of impact-
ing ions on bulk, inorganic materials, 11-3] 252Cfplasma desorption (PD) time-of-
flight (TOF) mass spectrometry effecting desorption/ionization of biomolecules by
impact of single megaelectronvolt nuclear fission fragments, [4-6] and molecular
beam solid analysis (MBSA) using energetic neutrals [7,8] had already been
known when SIMS was applied to organic solids for the first time. [9,10] How-
ever, the organic surfaces tended to cause electrostatic charging upon ion impact,
thereby disturbing the ion source potentials. Employing a beam of energetic neu-
tral atoms in analogy to the MBSA technique circumvented such problems and
gave an impetus to the further development of this promising method. [11,12] The
term fast atom bombardment (FAB) was coined [11-13] and prevailed. l7] It
turned out that intact molecular or quasimolecular ions could be generated even in
case of highly polar compounds that were definitely not candidates for electron
ionization (EI, Chaps. 5, 6) or chemical ionization (CI, Chap. 7). Those FAB
spectra still suffered from rapid radio lytic decomposition of the samples upon ir-
radiation and from the comparatively harsh conditions of desorption/ionization.
The use of a liquid matrix where the analyte was dissolved for analysis brought
the awaited improvement. [14,15] Thus, "matrix-assisted fast atom bombardment"
.- as one now would probably term it - started its career in organic mass spec-
trometry [16,17] and soon became a powerful competitor of field desorption
(Chap. 8). It turned out that the properties of the liquid matrix are of key impor-
tance for the resulting FAB spectra. [18-20J Due to some electric conductivity of
the matrix, primary ions could now be successfully employed again. [21-24] If
primary ions instead of neutrals are used to provide the energy for secondary ion
ejection from the liquid matrix, the technique is termed liquid secondary ion mass
spectrometry (LSIMS). Parallel to FAB and LSIMS, inorganic SIMS has tremen-
dously developed to become a highly regarded method for surface analysis. [25-
27] Although being soft, extremely versatile and still relevant ionization methods,
FAB and LSIMS have widely been replaced by matrix-assisted laser desorp-
tion/ionization (MALDI, Chap. 10) and electrospray ionization (ESI, Chap. 11).

Note: Besides their momentum, the nature of the primary particles is of minor
relevance for the spectral appearance [28] because little difference is observed
between FAB and LSIMS spectra. Otherwise not explicitly distinguished from
LSIMS, here the usage of the term FAB will also implicate LSIMS.

J. H. Gross, Mass Spectrometry

© Springer-Verlag Berlin Heidelberg 2004
382 9 Fast Atom Bombardment

9.1 Ion Sources for FAB and LSIMS

9.1.1 FAB Ion Sources

A FAB ion source basically is an EI ion source (Chap. 5.2.1) modified to give free
acceSs to the fast atom beam. The electron-emitting filament and the ion source
heaters are switched off during FAB operation (Fig. 9.1). The FAB gas is intro-
duced via a needle valve into the lower part of the FAB gun mounted above the
ion source. From there, it effuses into the ionization chamber of the FAB gun and
into the ion source housing. The saddle field gun [29] is the most common type of
FAB gun, delivering a primary particle flux of some 10 10 S-l mm- 2. [30,31] The
gas is ionized and the ions are accelerated by a high voltage (4-8 kV) and focused
onto the sample. [11,l3,17,32] Neutralization of the energetic noble gas ions is ef-
fected by charge exchange with incoming neutrals (Chaps. 2.12.3, 7.3). The ki-
netic energy of the atoms is mostly conserved during charge exchange, and thus
the neutrals hit the exposed surface with high kinetic energy. Of course, neutrali-
zation is not quantitative, but this is not an issue as long electrostatic charging of
the sample is avoided. [28] Ion guns for the generation of energetic noble gas ions
can therefore be employed without disadvantage. [33] Xenon is preferred over ar-
gon and neon as FAB gas, [34,35] because it transfers a higher momentum when
impacting onto the surface at equal kinetic energy (Fig. 9.2). Consequently, even
mercury has been tried as FAB gas. [36]

electron ionIZation
of FAB gas '--'>-.0;:--- anode

v.' 0
filament
acceleration and /\ /
focusing of

-~=~::~
energetIC IOns

beam of
z... . .j ,
:j~ Xe gas supply
energetIC atoms /1 . . . effUSing neutral gas
Ij'/'llill
FAB ~
~ I
target
II I I r .. secondary ions
to mass analyzer

Ion volume lenses for ion

acceleration

Fig. 9.1. Schematic of a FAB ion source and a FAB gun.