SECONDARY

EC ND RY ION
N MASS
M
SPECTROSCOPY
I t d ti
Introduction
y Bombardment of a sample surface with a primary
ion beam followed by mass spectrometry of the
emitted secondaryy ions constitutes secondary
y ion
mass spectrometry (SIMS)
y The measured mass spectrum then yield
information about the chemical composition of the
surface

Primary Ion Secondary Ion

(to mass spectrometer)

Sample
The secondary ion emission from
a solid
l d surface
f
y When a sol
solid
d surface iss bombarded w
with
th pr
primary
mary ions
ons in
n the keV
range for example, various processes take place in the surface
region.
y Provided that it will not be reflected at the surface,
surface the so
so-called
called
primary ion (PI) will penetrate to a certain depth into the solid and
will transfer its energy to the lattice atoms. Further impacts
distribute this energy to an extended lattice zone. A fraction of
this energy reaches the surface again where it can induce the
emission of a surface particle, which may be an atom or a cluster of
atoms in a charged
g or uncharged
g state. The p
processes takinggpplace
in the surface area can be divided into two groups :
y -changes of the surface near the primary ion
impact;
y - emission processes
The ion impact
p on the solid surface p
produces the following g changes
g in a
region
i around d the
h point
i of f impact:
i
y - the primary ion will be integrated into the lattice;
y - the energy transmitted to the lattice can give rise to lattice
dis rders and
disorders nd chemical
chemic l reactions,
re cti ns especially
especi ll att the surface,
surf ce which
hich is
very often covered with an adsorption film;
y - particles are removed from the surface (sputtering effect).
As a result of the various processes taking place in the vicinity of the
primary ion impact the following emission products can be observed:
y - secondary electrons; neutral atoms and clusters of atoms;
y _ positively and negatively charged atoms and clusters [so [so-called
called
secondary ions (SI)] ;
y - photons.
In secondary y ion mass spectroscopy
p py onlyy the p positive and negative
g
secondary ion emission is used for the investigation of the surface
composition.
 S tt i
Sputtering
oThe energy tranfer from the incoming
primary ion to a target atom near the
surface occurs via a cascade of two body
collision.
lli i

oThis collision cascade is more or less

destrucutive to the sample

Lattice defects, implanatation of primary

ions, removal of adsorbate atoms as
neutrals or secondary ions

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

 Classification
l f of
f sputtering events

oSingle-knock-on-regime

•Atoms recoiling from the ion-target

collision receive sufficient energy to be
sputtered out of the sample, but not
enough to generate recoil cascades.

• Typical threshold energies are in the 10 -

30 eV range.

•The Single knock-on sputtering may be

expected, if a target is bombarded under
low energy or for light projectile such as H,
He. In that case the projectile may be
The single knock-on regime: Recoil atoms from
reflected from a sub-surface atom.
ion-target collisions receive sufficiently high
energy to be sputtered

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

 Linear cascade regime

o If the target is bombarded with projectiles

of medium or high masses with energies
exceeding
exceed ng a few hundred eV, large energ
energies
es
are transferred to atoms in the surface
target leading to the evolution of larger
collision cascades; it can still be assumed
that the collisions take place between a
moving
i atom
t and
d an atom
t att rest.
t

o In this regime the sputtering yield was

pred cted to scale llinearly
predicted nearly w
with
th the energy
deposited in elastic collisions at the target
surface

The linear cascade regime: recoil

atoms from ion-target collisions receive
sufficiently high energy to generate
recoil cascades

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

 S ik regime
Spike i
oAt higher recoil densities, when the majority of
atoms within
i hi the
h cascade
d volume
l are simultaneously
i l l
in motion, the cascade is said to have entered the
spike regime.

I this
oIn hi case the
h projectile
j il must have
h sufficiently
ffi i l
high energy up to 10 keV and heavy atomic mass, to
generate highly recoil densities of atoms in target
surface.

o For such a spike regime, experiment shows and

theory predicts that the sputter yield rises non-
linearly with the energy deposited at the target
surface,
f andd thus
th suchh a cascade
d has
h been
b t
termedd
nonlinear .

oThe difference between a linear collision cascade

andd a spike
ik regime
i i that
is th t only
l a small
ll fraction
f ti of
f
the atoms are motion in a certain cascade volume in The spike regime: the density of
a linear cascade, whereas all atoms move in a certain recoil atoms is so high that the
majority atoms within a certain
spike volume.
volume are in
n mot
motion
on

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

 S tt i efficiency
Sputtering ffi i
o Sputter yield,
ld Y=number
b of f sputtered
d surface
f particle
l per incident
d particle
l

o With a primary ion beam of current density jPI [Charge (e) x flux (υ)], For current densities of 10-4 and
the number of particles sputtered during time dt is 10-9 A/cm2 the average life
times are in the order of 0.3 s
and
d 9 h respectively
s ti l i.e.
i about
b t3
A=surface area hit by the beam and 3.10-5 monolayers of atoms
are removed per second
N=desity of surface atoms respectively
o For an adsorbate layer wh
which
ch iss sputtered off, the coverage θ (t) iss
given by the ratio N(t)/Nmax

i.e, the sputtering efficiency can be described by the average life time

Static & Dynamic SIMS

The p
primary
y ion current density
y jPI controls the sputtering
p g rate

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

I t
Instrumentation
t ti

[Link]
P i
Primary i sources
ion
y Modern SIMS instruments are equipped with a
duoplasmatron, a Cs ion source, or a Ga ion
source. The free electrons are produced by boiling them
off of a heated cathode which is charged, along
with an intermediate electrode (IE) to ~ -50 kV.
Atoms of the gas are injected into a chamber
containing the cathode and a positively charged (-
50 kV) anode.d AsA the
th electrons
l t fl toward
fly t d the
th
anode, they collide with the atoms of the gas,
producing ions. An electron can either be absorbed
by the atom thereby creating a negative ion, or it
can knock an electron off of the atom p producing
ga
positively charged ion.

The duoplasmatron can operate with virtually any gas,

but oxygen is the most common because oxygen
implantation into the sample surface enhances
ionization efficiency for electropositive elements.
Diagram of Duoplasmatron showing Before this oxygen enhancement effect was
formation of carbon ions. discovered, argon was commonly used. The oxygen
plasma within the duoplasmatron source contains both
O- and O2+, and either can be extracted.

[Link]
 C Ion
Cs I Source
S

Cesium in the reservoir is

heated to a temperature where
it is volatilised and the vapour
drifts through the porous
tunsten frit.
frit The frit is heated
to temperature of 1100°C. The
hot frit surface ionises the
atoms with high degree of
efficiency These ions can be
efficiency.
extracted from the source with
a properly designed extraction
electrode to form a high
current beam of cesium
 Q d
Quadrapole
l mass spectrometer
t t
The two opposite rods in the quadrupole have a
potential of +(U+Vcos(wt)) (labelled '+' on the Fig)
and the other two -(U+Vcos(wt)) where 'U' is the
fixed potential and Vcos(wt) is the applied RF of
amplitude 'V'V and frequency 'w' w . The applied
potentials on the opposed pairs of rods varies
sinusoidally as cos(wt) cycles with time 't'. This
results in ions being able to traverse the field free
region along the central axis of the rods but with
oscillations amongst the poles themselves. These
oscillations result in complex ion trajectories
dependent on the m/z of the ions.

Specific combinations of the potentials 'U' and 'V' and

frequency 'w' will result in specific ions having a stable
trajectory through the quadrupole to the detector. All
other m/z values will have unstable trajectories and will
Schematic of a quadrupole
hit the quadrupoles and not be detected. The mass range m ss analyser.
mass n l s
and resolution of the instrument is determined by the
length and diameter of the rods.
Mathematical Analysis of the
Q d
Quadrupole
l Mass
M Filter
Filt
y The X- and Y-motions of an ion with mass m and charge
g q are
d
described
ib d by
b the
h ffollowing
ll i equationsi of
f motion
i f for the
h three
h
separate coordinate axes:

-------(a)
( ) Mathieu
M thi type
t p
differential
-------(b) eqn.

-------(c)
y where 2r0 is the closest distance between the four electrodes of
the QMS and e is the magnitude of the electron charge (assuming
singly charged ions). These equations are simply Newton’s equations
of motion with:
y Force = ((ion charge)*(electric
g ) ( field).
)
y The motion along the z-axis is unaffected by the potential on the
quadrupole electrodes.

[Link]
labs/Mass_Spectrometer/[Link]
 S l ti
Solution
y The important characteristic
of the solutions is that they
are only stable (real) for a
certain range of values of U
and V. The regions of stable
solutions
u are shown
w beloww as
a function of U and V. The
region (in pink) where the
stable solutions of both
eqn.(a) [x-motion] and eqn.(b) Range of stability for QMS
[y-motion] intersect is where trajectories obeying Mathieu’s
the quadrupole mass filter q
Equation. X-motion is stable in the
operates. purple band and Y-motion in the
magenta band. The stable operating
condition for a given mass/charge is
where these two bands overlap (pink).
SIMS Analysis Modes
y Static SIMS are used to determine
surface concentrations of elements
and molecules without significantly
altering the analyte.
analyte
y Dynamic SIMS involves the use of a
much higher energy primary beam
(lar er beam current).
(larger current) It is used to
generate sample depth profiles.
y Imaging
g g SIMS like static SIMS does
not alter the analyte appreciably. This
mode is used to generate images or
maps
p of
f analytes
y based upon
p
concentrations of one secondary ion
representing either an element or
molecule.
St ti SIMS
Static
y Low primary ion current densities are
used
d (10-99 to
t 10-10
10 A/cm
A/ 2). )
y Therefore sputtering rate will be
extremely
m y small
m ((10-4 to 10-5 m monolayers
y
per second).
y Low primary ion current densities
results in low secondary ion current
densities (<10-16 A/cm2) ~ requires
sensitive detection techniques
y M i l used
Mainly d to
t studyt d theth top
t mostt
atomic layer, investigate surface
composition, adsorption process and
surface
f chemical
h i l reaction ti
y Detection limit of adsorbed atoms ~ 10-6
monolayers: better than XPS; AES; etc
monolayers
 Static SIMS: an example

y F
Figure
gur shows th
the n
negetive
g t ssecondary
con ary ion
on sp
spectrum
ctrum of Mo
surface, which was exposed to 10-4 [Link] (100 Langmuir)
oxygen. The spectrum was obtained by sputtering off less than
1% of a monolayer with 3keV Ar+ ions at a current density 10-9
A/cm2. The observation of MoO-x indicates oxidation of Mo

y Interpretation of SIMS data may be difficult for complex systems

because a certain fraction of observed ions may originate from
interaction between primary beam and target atoms
Dynamic SIMS
y The higher ion flux used in dynamic SIMS
removes the surface of the sample,
sample burying
the beam steadily deeper into the sample and
generating secondary ions that characterize
the composition at varying depths.
y Primary ion current densities (10-4 to 10-5
A/cm2)
y High sputtering rates (several monolayers per
second)
y Ion yield changes with time as primary
particles build up on the sample effecting the
ejection
eject on and path of secondary ions.
ons.
Dynamic SIMS generated depth Profile

Monitoring the secondary ion count

rate
t of f selected
l t d elements
l t as a
function of time leads to depth
profiles. Figure shows the raw data
for a m
f measurement
m of
f p
phosphorous
p
in a silicon matrix. The sample was
prepared by ion implantation of
phosphorous into a silicon wafer.
Th analysis
The n l sis uses
s s Cs+ primary
p im i ns
ions
and negative secondary ions.

[Link]
R l ti S
Relative Sensitive
iti Factor
F t (RSF)
y SIMS quantitative analyses are performed by generating relative sensitivity
f t
factors (RSF ) for
(RSFs) f elements
l t off interest
i t t in
i substrate
b t t of f interest.
i t t We
W can
write the concentration of element i with respect to a reference element m
as

y where
h Ci and
d Cm are theh concentration of f impurity species i and
d matrix
species m, Ai and Am are the isotopic abundances for these ions, Yi and Ym
are the respective ion yields, and Ii and Im are the measured ion intensities.
Then we can define the quantity in brackets as the RSF,
y .

y Thus in SIMS analysis, if we have an RSF for the element of interest in the
substrate of interest,
interest the concentration of the element can de derived by
measuring the intensities of the impurity element and the reference
element. The RSF are generally derived from the measurement of ion
implanted standards or other calibrated standards.
 Imaging SIMS
y The mass spectrometer is set to only detect one mass.

y The particle beam traces a raster pattern over the

sample with a low ion flux beam, much like Static SIMS.

y The intensity of the signal detected for the particular mass

is plotted against the location that generated this signal.

y Absolute quantity is difficult to measure, but for a relatively

g
homogeneous sample,
p , the relative concentration differences
are measurable.

y Images or maps of elements can be generated.

generated
Images
g created using
g the Imaging
g g SIMS
mode.
Examplep images show a py
pyrite (FeS2) grain from a sample
p of gold ore with gold located in the
rims of the pyrite grains. The image on the right is S and the left is 197Au. The numerical scales
34

and the associated colors represent different ranges of secondary ion intensities per pixel. Three-
dimensional analyses are possible by acquiring images as a function of sputtering time (image depth
profiles).

Gold (left) and sulfur (right) distribution in a pyrite (FeS2)

grain.

[Link]
 SIMS Advantages
SIMS-Advantages
o The elements from H to U may be detected.

o Most elements may be detected down to concentrations of 1ppm or 1ppb.

o Isotopic ratios may be measured,

measured normally to a precision of 0
0.5
5 to 0
0.05%.
05%

o Two dimensional ion images may be acquired. A secondary ion leaves the surface at a point
close to its original location. This enables localized analysis of the sample to be undertaken
and is the cornerstone of ion imaging.

o The volume of material sputtered is small. Using a high-energy and high primary beam
densities (dynamic SIMS) a volume of a 100 to 1000 μm3 is analyzed.

o In contrast, using low energy and low primary beam densities (static SIMS) the material
sputtered is exceedingly small,
small with surface mono-layers
mono layers lasting hours or days.
days

o Three dimensional ion images may be acquired by scanning (rastering) the primary beam and
detecting the ion signal as the sample is gradually eroded.
eroded

o Little or no sample preparation may be needed.

SIMS-Things
h to be kept
k in mind
d
y The material sputtered from the sample surface consists not only of mono-atomic ions
but molecular species that in places can dominate the mass spectrum, making analysis of
some elements impossible.

y The sputtering
Th s tt i process
ss is poorly
l understood.
d st d No N quantitative
tit ti m d l currently
model tl exists
ists
that can accurately predict the secondary ionization process.

y In order to obtain quantitative information a suitable standard has to be used and

empirical corrections applied.

y The sensitivity
y of an element is strongly
g y dependent
p on the composition
p of the matrix
and the type of primary beam used. Standards should, therefore, be close to the
composition of the unknown. This is particularity true for isotopic analysis.

y S
Samples
l mustt be
b compatible
tibl with
ith an ultra
lt high
hi h vacuum.