Secondary Ion Mass Spectrometry

1-10 keV

Bombardment of a sample
surface with a primary ion
beam followed by mass
spectrometry of the emitted
secondary ions constitutes
secondary ion mass
spectrometry (SIMS).

Static with low energy for surface. Dynamic with high energy for
depth study
The best SIMS reference is Secondary Ion Mass Spectrometry: Basic Concepts,
Instrumental Aspects, Applications, and Trends, by A. Benninghoven, F. G. Rdenauer, and
H. W. Werner, Wiley, New York, 1987 (1227 pages).

Ion beam-solid interaction

Ion Beam Sputtering

The bombarding primary ion beam
produces monatomic and
polyatomic particles of sample
material and resputtered primary
ions, along with electrons and
photons. The secondary particles
carry negative, positive, and
neutral charges and they have
kinetic energies that range from
zero to several hundred eV.

Primary beam species useful in SIMS include Cs+, O2+, O , Ar+, and Ga+ at energies between 1
and 30 keV. Primary ions are implanted and mix with sample atoms to depths of 1 to 10 nm.
Sputter rates in typical SIMS experiments vary between 0.5 and 5 nm/s. Sputter rates depend on
primary beam intensity, sample material, and crystal orientation.
The sputter yield is the ratio of the number of atoms sputtered to the number of impinging
primary ions. Typical SIMS sputter yields fall in a range from 5 and 15.

Three theoretical models for sputtering

The collision cascade model has the best success at quantitatively

explaining how the primary beam interacts with the sample atoms.
In this model, a fast primary
ion passes energy to target
atoms in a series of binary
collisions. Energetic target
atoms (called recoil atoms)
collide with more target
atoms. Target atoms that
recoil back through the
sample surface constitute
sputtered material. Atoms
from the sample's outer
monolayer can be driven in
about 10 nm, thus producing
surface mixing. The term
knock-on also applies to
surface mixing.

Sputtering Yield VS Ion Yield

(1) Sputtering yield S:
Sputtering is quite efficient, S>1 for Ar+ of few keV

(2) Ion Yield = # secondary ions/# atoms sputtered

The SIMS ionization efficiency is called ion yield, defined as the
fraction of sputtered atoms that become ionized.
(3) Sputtering Yield in SIMS (Y) = # secondary ions / # incident ions
= Sputtering yield S x Ion yield

Bombard surface with high energy ions and desorb ions (<1
%) and neutrals (> 99%) (SNMS)

Energy of sputtered atoms is low (1 keV in, 10-20 eV out)

A Schematic diagram of the energy distribution of residual gas ions, secondary ions,
sputtered neutrals, electrons and other particles

Energy distribution of sputtered atoms

Secondary Ion Energy Distributions

The sputtering process produces secondary ions with a range of (translational)
kinetic energies. The energy distributions are distinctly different for atomic
and molecular ions. Molecular ions have relatively narrow translational
energy distributions because they have kinetic energy in internal vibrational
and rotational modes whereas atomic ions have all kinetic energy in
translational modes. The following figure shows typical energy distributions
for mono, di, and triatomic ions

Incident ion Energy dependence of sputtering yield (S)

S(E) peaks at 10-30 keV depending upon material

Sputtering yields also vary with incident particle mass incident ion type

Sputtering yields vary considerably between elements (for fixed

incident particle and energy) - depends on cohesive energy U (
heat of sublimation)

Sputtering yield varies for element in different matrices

elements, oxides

Sputtering yield varies as ~1/cos

for moderate incidence angles
(more energy concentrated at surface) but falls off at very
grazing incidence (scattering dominates, no penetration)

Secondary Ion Yields -- Elemental Effects

Ion yields vary over many orders of magnitude for the various elements. The
most obvious influences on ion yield are ionization potential for positive ions
and electron affinity for negative ions.

This figure shows the logarithm of positive ion

yields plotted as a function of ionization
potential. The ion yields are relative to silicon in
a silicon matrix with oxygen sputtering.

This figure shows a similar treatment for negative ions

where the logarithms of relative ion yields are plotted
against electron affinities. The ion yields are relative to
silicon for measurements in a silicon matrix with
cesium ion sputtering. The four halides are the
elements that deviate furthest from the trend line.

The correlations of ionization potential with secondary ion yields are not perfect. Variations depend both on
the sample matrix and on the element itself. For example, the presence of oxygen in the sample enhances
positive ion yields for most elements, but fluorine exhibits anomalously high positive ion yields in nearly all
samples. Some elements, such as helium and neon fall outside the trend shown in the picture.

Secondary Ion Yields -- Primary Beam Effects

Oxygen bombardment increases the yield of positive ions and cesium bombardment
increases the yield of negative ions. The increases can range up to four orders of
magnitude.
Oxygen enhancement occurs as a result of metal-oxygen bonds in an oxygen rich
zone. When these bonds break in the ion emission process, the oxygen becomes
negatively charged because its high electron affinity favors electron capture and its
high ionization potential inhibits positive charging. The metal is left with the
positive charge. Oxygen beam sputtering increases the concentration of oxygen in
the surface layer.
The enhanced negative ion yields produced with cesium bombardment can be
explained by work functions that are reduced by implantation of cesium into the
sample surface. More secondary electrons are excited over the surface potential
barrier. Increased availability of electrons leads to increased negative ion formation.

Ion yield leads to different analysis conditions for different

elements as indicated on the periodic table - The choosing of
ions.

Summary
-

Sputtering in elements best understood

Sputtering in single crystals, complex materials less well
understood
Quantitation of sputtering or sputtering rate difficult
because of large number of variables
Sputtering very popular but

Leaves embedded incident particle in solid

Substantial damage and interlayer mixing
Preferential sputtering of one component