NIM B

Beam Interactions
with Materials & Atoms
Nuclear Instruments and Methods in Physics Research B 258 (2007) 218–225
www.elsevier.com/locate/nimb

Secondary ion mass spectrometry of MCsþ

n molecular ion complexes

Biswajit Saha, Purushottam Chakraborty *

Surface Physics Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700 064, India

Available online 12 January 2007

Abstract

Excellent detection sensitivity, high dynamic range and good depth resolution make the SIMS technique extremely powerful for the
analysis of surfaces and interfaces. However, a serious problem in SIMS analysis is its ‘‘matrix effect’’ that hinders the quantification of a
certain species in a sample and consequently, probing the composition of surfaces or interfaces by SIMS is greatly hindered. Appropriate
corrective measures are therefore, needed to calibrate the secondary ion currents into respective concentrations for accurate composi-
tional analysis. Working in the MCs+-SIMS mode (M – element to be analyzed, Cs+ – bombarding ions) can circumvent the matrix
effect. The quantitative potential of the MCs+-SIMS method is understood by assuming that an MCs+ ion is generated by the combi-
nation of a secondary neutral M0 atom with a re-sputtered Cs+ ion in the near-surface region. The emission process for the species M0 is
thus decoupled from the subsequent MCs+ ion formation process, in analogy with the ion formation in secondary neutral mass spec-
trometry (SNMS), resulting in a drastic decrease in matrix effect. Although this technique has found its applicability in direct quantifi-
cation, it generally suffers from a low useful yield. In such cases, detection of MCsþ
n (n = 2, 3, . . .) molecular ions offers a better sensitivity
as the yields of such molecular ion complexes have often been found higher than that of MCs+ ions. This is true in most of the cases
where the elements are strongly electronegative with respect to cesium. Several works have been reported on the emission of MCsþ n
molecular ions in the SIMS process, but a complete understanding on the formation mechanism of these ion complexes is still lacking.
The kinetic energy distributions of secondary MCsþ n molecular ion complexes has been found to be an effective approach to estimate the
local instantaneous surface work function changes under various surface exposure conditions, thereby enabling one to elucidate on the
probable formation mechanisms of these molecular complexes from their emission dynamics. The present paper addresses a brief review
on the MCsþ n molecular ion complexes that are emitted in the SIMS process, including various phenomenological approaches on the
subject.
 2006 Elsevier B.V. All rights reserved.

PACS: 79.20.Rf; 68.49.Sf

Keywords: Cs+ primary ions; Electronegative elements; Secondary ion mass spectrometry; MCsþ
n molecular ions; Formation mechanisms

1. Introduction trace (down to subparts per billion) amounts [1].

Quantitative analysis of the distribution of major/trace
elements across the interfaces is of significant importance
in materials science. Secondary ion mass spectrometry
(SIMS) is by far the most powerful technique for this pur-
pose because of its extreme detection sensitivity and high
depth-resolution. In fact, SIMS is most effective for detect-
ing elemental concentrations present in a sample in ultra-
*
Corresponding author.
E-mail address: purushottam.chakraborty@saha.ac.in (P. Chakra-
borty).
However, these advantages of SIMS are counter-balanced
by its strong matrix effect [2] i.e. the ionization probability
of a given species varies by several orders of magnitude
from one matrix to another, containing that particular spe-
cies. Consequently, the secondary emission of a given ionic
species is greatly affected by the instantaneous local surface
chemistry of the sample [3]. Since the ionization probability
of a certain species is entirely matrix dependent, the sec-
ondary ion yield of that species has no straight- forward
relationship with the concentration of the species in the
host, causing thereby a genuine hindrance to quantifica-
tion. This phenomenon is the so-called ‘matrix effect’ in

0168-583X/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2006.12.172
 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225
SIMS. By far, the strongest effects of matrix effects arise
from variations in the concentrations of those reactive spe-
cies that enhance ion yields strongly, e.g. oxygen and the
halogens for positive ions or the alkali metals for negative
ions. More generally, the presence of electro-negative spe-
cies on a surface enhances positive ion yield significantly.
The enhancement is larger, the larger the electro-negativity
of the species with respect to the emitted element. For
example, fluorine gives a larger enhancement of positive
ion-yield than oxygen of the same concentration. An anal-
ogous effect takes place in case of negative ion emission
when some electro-positive elements are present on the sur-
face. These effects are, however, very important in SIMS
analysis and very often deliberately utilized by bombarding
the surfaces with ions of electro-negative (or electro-posi-
tive) elements to get appreciable positive (or negative) sig-
nals of the emitted species that have extremely low
ionization probabilities.
Compensation of the matrix effect is needed for quanti-
fication in SIMS and is possible by several methods such as
calibration curve [4], ion implantation standards [1] etc. All
these approaches need ‘standards’ with matrix composition
close to that of the unknown sample. Moreover, it is very
difficult to make compositional analysis of the interfacial
regions using the above techniques. There is another tech-
nique known as ‘infinite velocity approach’ [5], which
makes use of the high energy part of the secondary ions
that are essentially unaffected by the instantaneous local
surface chemistry. The major difficulty in this method is,
however, the detection of high-energy secondary ions
because of their extremely low count-rates compared to
that of low-energy secondary ions.
In order to minimize the matrix effect a technique called
‘‘MCs+-SIMS’’ is gradually being used nowadays [6]. In
this technique, the sample to be analyzed is bombarded
with Cs+ ions and secondary MCs+ ions (where M stands
for the element to be analyzed) are detected instead of M
ions. Normally, bombardment by alkali ions of elements
that are electropositive with respect to the target elements
causes enhanced secondary negative ion emission from
the target owing to the lowering of metal surface work
function. As the alkali atoms get adsorbed onto the sur-
face, the measured work function decreases rapidly from
its initially high value and with continued adsorption, the
work function reaches a minimum and then rises to
approximately the bulk value with completion of the first
full layer of adsorbate atoms [7–9]. This phenomenon has
opened up a wide area of research owing to the general
interest of alkali adsorption as a way of enhancing the elec-
tron emission properties of a surface. Moreover, this sys-
tem attracts wide attention as one of the simplest
examples of chemisorption. Although the application of
‘‘MCs+-SIMS’’ technique is difficult for its poor sensitivity
(MCs+ molecular species are usually less abundant than
the atomic ions), MCs+ detection scheme is more favorable
in cases where matrix effects are most severe, particularly
for major components. This novel technique is referred to
219
as Cs+-assisted secondary ion mass spectrometry or simply
as MCs+-SIMS [10]. However, instead of Cs+ ions, other
alkali ion bombardment and monitoring of MA+ ions
(where A is alkali primary ion, such as K+, Rb+, Na+,
etc.) have also shown a similar small matrix effect [11]. This
technique has similarly been referred to as MA+-SIMS
approach.
In a comprehensive study on positive and negative sec-
ondary ion yields of atomic and molecular species sput-
tered from elemental and compound targets under
oxygen and cesium bombardment, Storms et al. [12] noted
that diatomic species of the type MCs+, composed of a tar-
get specific element M and Cs from the primary ion beam,
are sometimes emitted with surprisingly high yields, nota-
bly in the case of Zn. However, it was only until recently
that this finding gathered attention when several groups
reported on the usefulness of MCs+ ions, either for depth
profiling of inert gases [13], which are known to exhibit a
very low degree of ionization in SIMS, or for almost quan-
titative depth profiling of matrix and impurity elements in
III–V semiconductors [14]. Particularly attractive was the
observation that the MCs+ ion yields seem to depend very
little on the matrix from which the element M is emitted
[14]. This is in contrast to the severe ‘‘matrix effect’’ known
from SIMS measurements involving oxygen or cesium
bombardment and detection of atomic secondary ions.
The application of the MCs+ technique becomes more use-
ful when analyzing an interface of matrices of different nat-
ures, for instance the metal/semiconductor interface. Gao
et al. [11] showed that a very simple structure of a thin
(0.3 lm) gold over layer deposited on a GaAs substrate
exhibited least matrix effect while monitoring the AuCs+
ions. The obtained profile did not exhibit any interface
peak, which is characteristic of the typical matrix effect
(Fig. 1).
2. MCs+ ions: formation mechanisms and characteristics
Formation mechanisms of MCs+ secondary ions and
the analytical applicability of MCs+-SIMS technique have
been thoroughly examined by several workers. Based on
some experimental observations, it was proposed that an
MCs+ ion forms via a recombination between an indepen-
dently sputtered neutral M0 atom and a re-sputtered Cs+
ion in the close proximity of the sample surface. This pro-
cess essentially makes the MCs+ species to suffer less from
the matrix effect. Irrespective of the formation mechanism
of MCs+ ions, it is obvious that the binding energy between
M and Cs (either charged or neutral) plays a very impor-
tant role in the formation of MCs molecule and the polar-
izability of M plays the key role in the binding strength of
the two species. The fact that the emission intensity of
MCs+ depends linearly with the atomic polarizability of
M was established from the measurements of MCs+ ion
yields from silicon containing various low-concentration
elements [15]. The results showed that the ratio I(MCs+)/
I(SiCs+) increased monotonically with the polarizability
220 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225
Fig. 1. Au depth profiles obtained under different experimental conditions
for an Au layer (0.3 lm) deposited on a GaAs substrate. Condition (a)
Au+ secondary ion under Oþ +
2 bombardment. Condition (b) Au secondary
ion with an off-set of 80 eV under O2+ bombardment. Condition (c) Au
under Cs+ bombardment. Condition (d) Au+ post-ionized under O2
bombardment. Condition (e) AuCs+ under Cs+ bombardment [11].
of M. Dependence of the binding strength on the polariz-
ability can be modeled by an interaction potential between
an alkali ion and a neutral atom of the type [16]. In this
case the attraction arises between the ion and the ion-
induced dipole moment of the neutral species.
In order to fully exploit the analytical applicability of
the MCs+ technique, a thorough understanding of the for-
mation mechanism of these molecular ions is needed. Gna-
ser and Oechsner [15] showed that for a variety of
semiconductors the yield Y of these species exhibits a qua-
dratic dependence on the polarizability (a) of the atom M,
i.e. Y / an with n  2. The experimentally established cor-
relation between the yields and the polarizability was
explained in a quantitative fashion by employing an appro-
priate interaction potential between Cs+ and M; the argu-
ment is based on a distribution function U(2) developed for
the emission of small molecules in sputtering according to
the double-collision scenario. For a dimer, this distribution
function in the limit of large E, is
Uð2Þ ðE; hÞ / D3=2 E5 cos2 h; ð1Þ
where E and h are the dimer’s emission energy and angle,
respectively, and D is its dissociation energy. The interac-
tion between an alkali ion and a polarizable neutral atom
(or molecule) can be successfully modeled by applying for
the alkali ion-neutral atom interaction a potential of the
form [16]
V ðrÞ ¼ Ar12  0:5ae2 r4 ; ð2Þ
where r is the distance between the neutral atom and the
ion, a is the polarizability of the former and A is a constant
which characterizes the repulsive term. The attraction is of
the Langevin type and is that arising between the ion and
the ion-induced dipole moment of the neutral species. Of
particular concern is the depth of the potential well (i.e.
the value of V(r) at the equilibrium distance rm), which is
the dissociation energy D for the MCs+ molecule. The min-
imum of the potential is given by
D ¼ V ðrm Þ / a3=2 A1=2 : ð3Þ
Thus the dimer distribution function U(2) will exhibit a
dependence on the polarizability a given by
Uð2Þ / a3=2 A3=2 ð4Þ
with an exponent for a (n = 2.25) which is very close to
what has been observed experimentally (Fig. 2).
Clearly, the foregoing theoretical treatment includes
some assumptions: the interaction potential employed has
been used successfully to describe gas-phase reactions,
mostly at very high gas densities; its transferability to inter-
actions occurring at the surface of a solid is not obvious.
On the other hand, the pronounced dependence on the
polarizability found in the experiments indicates that the
latter is a key parameter in any kind of formation mecha-
nism of MCs+. Studies on elemental and compound semi-
conductors (Si, Ge, InP, InSb, ZnSe, CdS, CdSe and
CdZnTe) with Cs+ fluences ranging from 2 · 1015 cm2
up to saturation values (>1 · 1017 cm2) reveal interesting
emission characteristics of the molecular ions [17]. It has
Fig. 2. Yields of MCs+ ions sputtered from various elements as a function
of the atomic polarizability (a) of M. The solid line is a linear least-squares
fit with n = 2.07 ± 0.20 [15].
 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225 221

been observed that for all specimens with the exception of
Si, the flux of MCs+ ions scales linearly with the Cs+ inten-
sity over a wide range of cesium concentration (several
orders of magnitude in some cases); for silicon deviations
from this scaling are found at the highest Cs content and
are tentatively ascribed to changes of the sputtering yield
in the heavily doped Si specimens. The Csþ þ bþ
2 =Cs ratio, on
the other hand, has been found to decrease more than lin-
early (possibly exponentially) upon reduction of the Cs
concentration, indicative of a decreasing formation proba-
bility of Csþ 2 dimers at low concentrations due to an
increasing (average) distance between individual Cs atoms.
Theoretical studies carried out by Mootz et al. [18] show
that MCs+ ions have energy distributions, which are deter-
mined by the energy distributions of the sputtered neutral
M atoms. For both distributions the mean emission energy
is enhanced if the element’s surface binding energy is
enhanced too. In contrast, the energy distributions of the
re-sputtered Cs+ ions appear to be element independent.
The efficiency of MCs+ molecule formation monitored by
the MCs+ signals is maximum for low mean emission ener-
gies and low surface binding energies. This shows the
importance of a correlated emission of the partners form-
ing the molecule. The formation mechanism of the MCs+
clusters was investigated using a Monte Carlo model [19].
It was shown that the majority of the constituent particles
of the formed clusters are initially first or second neighbor
atoms at the surface and that the velocity distribution of
the MCs+ clusters becomes broader and peaked at higher
velocities with increasing surface binding energy of the M
atom. In addition, it was demonstrated that the interaction
potential between the M and Cs+ particle has no influence
on the velocity distribution of the MCs+ clusters. On the
other hand, the cluster formation probability, defined as
the probability that a sputtered M and Cs+ particle will
form a MCs+ cluster, is extremely sensitive to this interac-
tion potential. It is also shown that the cluster formation
probability decreases with increasing surface binding
energy. Finally, a good correspondence is obtained
between the calculated and experimental velocity distribu-
tions of MCs+ clusters sputtered from different mono-
atomic materials. As a consequence, the Monte Carlo
model and the discussed results could be validated [19].
ions. However, some earlier observations [20] have con-
firmed its almost constant value for low emission velocities.
Assuming the constancy in e0, if /þ þ
i and /j are the two val-
þ þ
ues of /, and bi and bj represent two values of b+, then
from Eq. (5)
þ
j =bi / exp½ð/j  /i Þ=e0 
ð6Þ
/ exp½D/=e0 ;
where D/ = /j  /i; the change in surface work function.
Eq. (6) implies that the normalized integrated count should
show an exponential dependence on D/. The normalized
Cs+ count, plotted as a function of D/, showed a very good
agreement with the theoretical prediction for e0 = 0.29 eV.
That is probably the first experiment to determine e0 for
Cs+.
Integrated counts of AgCs+ showed an overall fall with
increasing oxygen pressure. This observation apparently
contradicts the concept for MCs+ molecular ions, as it is
known that the formation of such molecular ions remains
almost unaffected by the change in instantaneous local sur-
face chemistry. This apparent discrepancy was answered by
taking into account the exponential fall of re-sputtered Cs+
ions. Theoretically, the intensity of MCs+ molecular ions
can be expressed as [17]
I MCsþ / YcM ð1  bMþ  bM ÞYcCs bþ fMCsþ ; ð7Þ
where cM is the concentration of M, Y is the global sputter-
yield of the target, cCs is the surface cesium concentration,
b+ is the ionization probability of Cs and fMCsþ is the for-
mation probability for MCs+. bMþ and bM are the ioniza-
tion probabilities for M+ or M secondary ions,
respectively. For most practical purposes, bMþ and bM in
the case of MCs+ ion intensities are negligible and all the
factors except b+ remains constant. fMCsþ , estimated at var-
ious oxygen exposures, has been found to be unchanged
[21]. Hence Eq. (7) can be rewritten as
I MCsþ ¼ Kbþ ; ð8Þ
1.0 Experimental data
Normalized AgCs intensity

We have recently studied the combined effect of electro- Linear fit

positive (cesium) and electronegative (oxygen) elements on
the sputtered-ion emission from silver. Kinetic energy dis- 0.8
+

þ
tributions of Cs+, Csþ +
2 , AgCs and AgCs2 ions measured
at different oxygen pressures have exhibited changing
slopes in their leading parts that hinted appreciable 0.6
changes in the local instantaneous surface work function.
The ionization probability b+ depends on the ionization +
0.4 IMCs+ = K
potential I of the sputtered atom and surface work function
/ according to the relation
0.5 0.6 0.7 0.8 0.9 1.0
bþ / exp½ðI  /Þ=e0 ; ð5Þ +
Normalized Cs intensity
where the parameter e0 is considered to depend on the nor- Fig. 3. Normalized AgCs+ intensity as function of normalized Cs+
mal component of the emission velocity of the secondary intensity.
222 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225
where K is a constant. In other words, the normalized
MCs+ intensity should show linear dependence on normal-
ized Cs+ intensity. The normalized AgCs+ intensity, plot-
ted against normalized Cs+ intensity, showed a linearity
(Fig. 3), which was in good agreement with the theoretical
prediction for all oxygen pressures. This observation, even
under a combined influence of electropositive and electro-
negative elements on the surface, strengthened the accepted
concept that MCs+ formation is essentially due to the com-
bination of a neutral M0 with a re-sputtered Cs+ ion.
3. MCsþ2 ions: importance, formation mechanisms and
characteristics
Although MCs+-SIMS technique has found its applica-
bility in direct quantification, it generally suffers from a low
useful yield. In such cases, detection of MCsþ 2 molecular
ions offers a better sensitivity to that of MCs+ ion
(Fig. 4), as the yield of MCsþ2 ions has been observed much
higher than that of MCs+ ions [11]. This is true in most of
the cases where the elements are strongly electronegative
with respect to cesium. Holliger et al. [22] investigated
the analytical usefulness of monitoring MCsþ 2 ions for
semiconductor profiling of n-type dopants such as P, Ge
or As with a primary (Cs+ beam) impact energy of
1 keV. They indicated that the MCsþ 2 technique has an
advantage over the MCs+ technique of providing higher
useful yields for electronegative elements by up to 102
and can therefore be applied to perform more precise junc-
Fig. 4. FCs+ and FCsþ
2 ions profiles for a Si wafer implanted with fluorine
at a dose of 8 · 1015 atoms cm2. The implantation peak concentration is
at 2.5 · 1021 atoms cm3 [11].
tion measurements in terms of concentration, dose, decay
length and detection limit. The quantification of the impu-
rities in GaN and AlGaN films by using the MCs+ and
MCsþ 2 ions enabled the detection of both electronegative
and electropositive elements in the same analysis run. It
was shown that the p-type dopant Mg and H could be mea-
sured together [23]. The detection limits of HCsþ þ
2 , CNs2
+
and MgCs were reported at the same level as the limit
of M ion detection. Further, the application of the MCs+
and MCsþ 2 ions suppresses the matrix effect in the
AlGaN/GaN films.
Although several works have reported the mechanism of
MCs+ formation [24–29], that of MCsþ n ions (where
n = 2, 3, . . .) still remains to be well understood. In view
of the fact that the kinetic energy distribution of a certain
emitted species is an effective diagnostic to understand the
formation mechanism of the species and its dynamics, a
systematic study on the kinetic energy distributions (EDs)
of MCsþ n (n = 0, 1, 2, . . .) of species emerging from various
metal targets under Cs+ ion bombardment was reported
to elucidate the probable formation mechanism of these
molecular complexes. [15]. Several previous studies have
investigated the energy distributions of MCs+ ions [24–
29] but corresponding data for MCsþ 2 appear to be lacking.
Several studies suggest the following three possible
routes for the formation of these ions.
M0 þ Csþ
2 ! MCs2
þ
ðiÞ
M þ Csþ þ Csþ ! MCsþ ðiiÞ
2
MCs0 þ Csþ ! MCsþ
2 ðiiiÞ
It was suggested that the first process seems dominant for
electropositive elements, and for the electronegative ele-
ments, the other two processes ((ii) and (iii)) could become
important in explaining the increased MCsþ 2 yield [29,30].
Most of the earlier works tried to investigate the formation
mechanism by studying the ion yields of MCsþ 2 ions with
respect to that of MCs+ ions. The fact that the changes
in instantaneous surface chemistry has less effect on the sec-
ondary emission of MCs+ and MCsþ 2 molecular ions was
established from a work on secondary ion emission from
copper under various Cs+ primary energies and chamber
pressures [31]. It was shown that under 3 keV Cs+ energy,
intensity of Cu increased with the gradual increase of oxy-
gen pressure in the chamber exhibiting a typical matrix ef-
fect, whereas the intensities of CuCs+ and CuCsþ 2 remained
almost uninfluenced by the changes in the oxygen pressure.
Another important observation was that for identical
chamber pressure, the intensity of CuCsþ 2 always exceeded
that of CuCs+ at any impact energy [31], supporting the
earlier observations that MCsþ 2 has a greater yield com-
pared to MCs+ ions. Since the emission intensity of Csþ 2
ions is generally less than that of Cs+ ions by orders of
magnitude, it was argued that the formation of a CuCsþ 2
ion could not be due to direct recombination of a neutral
Cu atom and a Csþ 2 ion in the sputtering process. The for-
mation of MCsþ 2 was explained [32] to be due to a recom-
 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225 223

bination of a sputtered M ion with two self-sputtered Cs+

0.0
ions (i.e. process (ii)). Furthermore, Cs being electroposi-
tive with respect to Cu caused enhanced emission of Cu
-0.2
ions under Cs bombardment thereby leading to increased
yields of CuCsþ 2. -0.4
Considering the fact that the kinetic energy distribution

(EDs) of a certain species emitted in the SIMS process is an
effective diagnostic to understand the formation mecha-
nism of the species and its kinematics, energy distributions
(EDs) of MCs+ and MCsþ 2 molecular species have been
made for various target materials under varying Cs envi-
ronments [31–33]. Instantaneous local surface work func-
tions estimated from the leading parts of the kinetic
energy distributions were found to play a major role in
the formation of these ion complexes. In the energy distri-
butions of M, MCs+ and MCsþ
2 ions for the elements Al,
Cu and Ag for a typical bombarding energy of 2 keV, it
was observed that for a given element the peak position
of the ED shifted to lower values in the order M+, MCs+
and MCsþ
2 ions (Fig. 5). This was found to be true for
any value of impact energy. From the bombarding energy
variations of EDs for M+ or MCs+ or MCsþ
2 , it was
observed that the peak of the ED for each species shifted
towards lower energy as the impact energy was increased
[32]. The peak position of the energy distribution for any
emitted species depends essentially on the surface binding
energy (U) of the species as well as the surface work func-
tion (/), as understood by the simple expression
 
E ðI  /Þ
Ion Yield / exp : ð9Þ
ðE þ U Þ3 e0
The sublimation energy of pure Cs being much lower
(0.83 eV) than that of the three metals, decrease of Cs
concentration (i.e. increase of impact energy) should tend
to increase the magnitude of the surface binding energy.
Since this was contrary to what was actually observed in
(eV)
-0.6
+
Al
-0.8 +
AlCs
+
-1.0 AlCs2
1 2 3 4 5
Impact Energy (keV)
Fig. 6. Surface work function change (D/) versus impact energy for Al+,
AlCs+ and AlCsþ 2 ions [33].
the study, the peak shift of the EDs towards lower energies
was due to the increase of surface work function (due to
lowering of Cs concentration with the increase of impact
energy). The lower the work function, the greater is the
shift of the energy distribution towards higher energies
[34]. Any change in the instantaneous surface work func-
tion should reflect the variation of the leading edge profile
of the energy distributions. By fitting tangents to the lead-
ing parts of the EDs and subsequently measuring the inter-
cepts of the tangents with the energy axis one does the
estimation of the work function changes. Fig. 6 shows
the variation of the measured surface work function
changes (D/) with impact energies for M+, MCs+ and
MCsþ 2 species, thus evidencing the role of surface work
function changes on the energy distributions. The effect is
more pronounced when the surface work function changes
become more significant and this was demonstrated for sil-
ver by changing the impact angle of the incident beam [33].
The impact angle variation on the work function change
was found to be more sensitive than the impact energy var-

Impact Energy = 2 keV

+ + +
M, MCs , MCs2 o o o o o
45 , 40 , 35 , 30 , 25 ,
Al a o
20 ,
o
15 ,
o
10 ,
o
5, 0
o

0.8
1.0 +
AlCs
Normalized Intensitay

0.4 0.8

0.0 0.6
Nomalized intensity

Cu b 0.4
0.8
0.2
0.4 0.0
+
1.0 AlCs 2
0.0
Ag c 0.8
0.8 0.6
0.4 0.4
0.2
0.0 0.0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 16 18 20
Energy (eV) θ (degree)

Fig. 5. Energy distributions of MCs+ and MCsþ 2 molecular ions for Au, Fig. 7. Energy distributions of AlCs+ and AlCsþ
2 ions for different impact
Cu and Ni targets at 2 keV impact energy [32]. angles [34].
224 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225
iation on the same. Fig. 7 shows the energy distributions of
AlCs+ and AlCsþ 2 ions for different impact angles [33].
So far, a handful of works has been done to reveal the
underlying formation mechanism of the MCsþ n molecular
ions. The study of energy distributions of the MCsþ 2 mole-
cules ions and its proposed constituents has been the key
probe to understand its formation mechanism. The energy
distribution of the MCsþ 2 molecules (where M = Zn, Cu,
Ge, Ni and Mo) has been found to depend on the surface
binding energy, which provides evidence that the energy
distribution of the neutrals is also responsible for the
MCsþ 2 distributions [18]. Furthermore, the narrower energy
distribution of the trimers compared to respective dimers’
energy distribution supported a recombination of the con-
stituents of the trimers subsequent to their sputter process.
Comparison of the energy distributions of the components
involved in the dimer formation process with the energy
distributions of components, which might be responsible
for the trimer formation, strengthened the belief that the
formation of an MCsþ 2 molecular ion was due to the recom-
bination of MCs0 with Cs+ (process (iii)). The MCs0 occur-
ring in this formation process results from the
neutralization of an MCs+ ion by electronic capture [27].
In another study of MCsþ n molecular ions formation from
silver surface under a varying oxygen environment, a linear
dependence of AgCsþ 2 intensity on the ionization probabil-
ity of Cs+ (Fig. 8) suggested that an AgCsþ 2 molecular ion
forms via the recombination of AgCs0 and Cs+ [21]. Fur-
thermore, the estimated mean emission energies of various
species also indicated that the formation of MCsþ 2 via pro-
cess (iii) seemed to be the most probable one in that partic-
ular case. A quantitative evaluation of the respective mass
signals, with respect to the spatial and temporal correlation
of the components forming the molecule, corroborated the
fact that in the case of the MCsþ 2 formation the spatial and
temporal correlation is one order of magnitude higher than
that in the MCs+ formation process [18]. Besides, it was
observed that in both the cases of dimer and trimer forma-
tion, the spatial and temporal correlation decreases with
increasing surface binding energy.
1.0 Experimental data
Normalized AgCs 2 intensity
Linear fit
0.8
+
0.6
0.4
0.5 0.6 0.7
Normalized Cs intensity
Fig. 8. Normalized AgCsþ
2 intensity as a function of normalized Cs
+ M and the surface environment where the formation actu-
intensity.
To explore the enormous quantitative potential of the
MCsþ n , in recent times, several experiments have been
reported where dual beam have been successfully used to
improve the MCsþ n signal. In a ‘‘Cesium-Xenon’’ co-sput-
tering experiment, performed on pure silicon, silicon oxide
and aluminum oxide, MCsþ n clusters’ signals were reported
to enhance significantly for a Cs beam concentration, with
maxima that varied from 10% to 30% [35] and the data rel-
ative to the silicon wafer were successfully interpreted by
models derived from the tunneling model. To optimize
the advantageous quantification technique consisting in
analyzing MCsþ n clusters, Writz et al. have developed the
Cation Mass Spectrometer (CMS), a new instrument espe-
cially dedicated to perform this kind of analysis [36]. In this
novel technique, collimated and adjustable stream of neu-
tral Cs atoms are deposited on the surface of the sample
while this one is being bombarded with Xy+ (where ‘X’
stands for any element excepting Cs). This experimental
technique permits a successful decoupling of the sputtering
and Cs introduction processes by avoiding the constraints
imposed by an energetic Cs+ ion bombardment. As a con-
sequence, it becomes possible to optimize simultaneously
the sensitivity of the analysis, by carefully adjusting the
Cs concentration to its optimum value, and the depth res-
olution of the analysis, by choosing adequate primary
bombardment conditions. For three samples (Al, Si and
Ni) covering an important range on the work function scale
(U = 4.28–5.15 eV), it has shown that the behavior of the
useful yields of the detected MCsþ n signals only depends
on the ratio between the erosion and deposition rates,
but not on the individual values of these two rates. This
characteristic becomes very important within the perspec-
tive of a low-energy primary bombardment with a view
to an improvement of the depth resolution. Furthermore,
the deposition of neutral cesium has been reported to
reduce the work function of the sample that increases the
useful yields significantly and helps avoiding the matrix
effect for elements with high electron affinity [37].
4. Conclusions
MCsþ n molecular ion complexes have great relevance in
the SIMS analysis because of their significant insensitivity
to the changes in instantaneous local surface chemistry.
Consequently, study of the formation mechanisms of these
molecular complexes is important to the researchers. Vari-
ous formation mechanisms reported so far have been dis-
cussed in the present article. The formation of MCs+ ions
via recombination of neutral M0 atoms with re-sputtered
Cs+ ions seems to be unquestionable whereas, the exact
+ mechanism of MCsþ 2 formation is still obscure. Three pos-
IMCs + = K
2 sible mechanisms, such as recombination of neutral M0

with Csþ +
2 , or M with two Cs ions or neutral MCs with
0
0.8 0.9 1.0 +
+
Cs appear to be independently viable depending on the
nature (electropositivity or electronegativity) of the element
ally takes place.
 B. Saha, P. Chakraborty / Nucl. Instr. and Meth. in Phys. Res. B 258 (2007) 218–225
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