Secondary Ion Mass Spectrometry

SECONDARY ION MASS
SPECTROMETRY (SIMS)
Presented by:- Guided by
Atulya Shawat Minz Mr. P.K.MALLICK
Roll no- 25611
P.k
Metallurgical and materials Engineering Department

Indira Gandhi Institute of Technology
Sarang-759146, Dhenkanal, Orissa
CONTENTS
Introduction
Overview
Application
Drawback
Conclusion
Reference
INTRODUCTION
What is SIMS?
SIMS is a surface analysis technique used to characterize the surface and
sub-surface region of materials.
It effectively employs the mass spectrometry of ionised particles which
are emitted when a solid surface is bombarded by energetic primary
particles.
The primary particles may be electrons, ions, neutrals or photons .
COLLISION CASCADE
THE SPUTTERING PROCESS
The process of sputtering can be described by the principles of classical
mechanics through binary collisions of primary ions with single target atoms.
Depending on the energy range of the primary particle, elastic and inelastic
collisions take place. Dominating interactions in the keV range are elastic
collisions. They can be described by a value known as nuclear stopping
power which is defined by the energy loss of the primary particle per path
length:
The number of inelastic collisions increases with rising energy. Inelastic

collisions dominate in the MeV energy range. The corresponding value to
describe this interaction is the electronic stopping power.
Nuclear stopping contributes to the collision cascade.

SECONDARY ION YIELDS
(PRIMARY BEAM EFFECTS)
Other factors affecting the secondary ionization efficiencies in SIMS:
Oxygen bombardment increases the yield of positive ions .
Cesium bombardment increases the yield of negative ions.
The increases can range up to four orders of magnitude.
POSITIVE SECONDARY ION YIELDS
O2+ BOMBARDMENT
The variation of positive ion yield as a function of atomic number or 1nA, 13.5KeV O
Bombardment
YIELD
CS+ BOMBARDMENT
The ratio of negative ion yield (M-)under Cs+ bombardment to positive ion yield (M+) ion under
O bombardment as a function of atomic number
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.
EQUATION OF SIMS
Secondary ion current of species A detected (cps):
I(A q) = Ip.Y.a(Aq).c(A).T
q = Charged state (e.g. + or -)

Ip = Primary current density (ions/sec)
Y = Total sputtered yield
a(A q) = Ionization probability to charge state q
c(A) = Fractional concentration of A in matrix
T = Instrumental transmission function
SIMS DEPTH RESOLUTION
The definition of depth resolution

USES
SIMS widely used for analysis of trace elements in solid materials,
especially semiconductors and thin films.
Static SIMS: extremely low sputtering rate allowing better sensitivity to the
characteristics of the top monolayer. Primary ion dose is kept below 10 12ions/
Cm2 and the mass spectrum reveals MOLECULAR information.
D-SIMS: Dynamic Secondary Ionization Mass Spec, high sputtering rate
gives ELEMENTAL and ISOTOPIC information.
TOF-SIMS: Time of Flight SIMS (newest). MOLECULAR data, excellent
depth profiling.
To determine the composition of the sample at varying spatial and depth
resolutions depending on the method used.
MASS ANALYZERS
Quadrupole
Magnetic sector
Time-of-Flight
Comparison of mass analysers for SMIS

Types Resolution Mass Transmission Mass Relative
range detection sensitivity
Quadrupole 102 -
103 < 103 0.01 – 0.1 Sequential 1
Magnetic 104 >104 0.12-0.5 Sequential 10
Sector
Time of 103 103 -104 0.5-1.0 Parallel 104
flight
QUADRUPOLE, MAGNETIC SECTOR,
TIME OF FLIGHT
Quadrupole is a mass filter which uses both D.C and R.P electric field
when applied to four parallel rods in order to separate ions according
to there m/z.
Magnetic Sector : It is a radius of curvature are often ion of m/z ratio
travelling through perpendicular field B after being accelerated by
potential V.
1
1  2mV  2
R   
B z 
Time of flight –It is the time allowed to drift through a field free space
before reaching the detector. Time time-of-flight t down a flight path
length L is given by
STATIC VS. DYNAMIC SIMS
Sputtered species include :

mono and poly atomic particles
of sample, (+, -or neutral )
Resputtered primary species
(+,-,neutral)electron proton
TOF-SIMS
In the spectroscopy and imaging modes
only the outermost (1-2) atomic layers of
the sample analyzed
To ensure the analysis secondary ions

originate from the outer surface of the
sample ,a primary ion does of less than one
1012 ions / Cm2 is employed . Below this “static
limit “ roughly less than one in one thousand
surface atom or molecules are struck by a primary
ion .
The actual desorption of material from the surface

caused by a “ collision cascade “
which is initiated by the primary ion

impacting the surface
APPLICATION
Quantitative application of SIMS
 Molecular weight determination
 Determination of molecular formula
 Formula from isotopic ratio
 Identifications of compound from fragmentation patterns
Qualitative application of SIMS

o Qualitative analysis of organic mixtures
o Precision and accuracy
o Component analysis
o Component type determination
o Inorganic trace analysis
o Isotope abundance measure
DRAWBACKS
Depth analysis is limited by the embedding of primary ions into the
sample. This can cause charge build up, which will especially distort
the path of secondary ions of an electrical insulator.
Resolution of the analytes is decreased by the fact that the surface may
wear down differently throughout the sample.
Stoichiometric and matrix properties of the analyte must be known to
interpret the data.
Inconsistencies in sputter yield.
Inconsistencies in atomic ionization.
Sample is at least partially destroyed in the analysis process.
CONCLUSION
 Secondary ion mass spectroscopy essentially plays a major role in the
determination of composition of complex compound.
 It helps in determining the scanning of images of compound
&the molecular weight determination of polymers to a large
extent.
 Apart from all these points it essentially helps in scanning of internal
structure of the biomaterials, sputtered phase of elements. Thus it is a
great instrumental analysis is characterization of materials.
REFERENCE
Dr. Marx. Surfaces and Contact Mechanics http://
www.siu.edu/~cafs/surface/file6.html
Arizona State University SIMS Lab
http://www.asu.edu/clas/csss/SIMS/
Charles Evans & Associates. Secondary Ion Mass Spectrometry
Theory Tutorial. http://www.cea.com/cai/simstheo/caistheo.htm
University of Arizona. Secondary Ion Mass Specrtoscopy.
http://www.u.arizona.edu/~xiuminj/web/SIMSdefault.htm
Rubinson, KA and Rubinson JF. Contemporary Instrumental Analysis.
Prentice-Hall, Inc., Upper Saddle River, New Jersey. 2000. Pp. 536-
555.
Montana State University Dept of Physics. SIMS.
http://www.physics.montana.edu/ical/Pages/sims.htm
THANK YOU
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SECONDARY ION MASS

Roll no- 25611

Metallurgical and materials Engineering Department

The number of inelastic collisions increases with rising energy. Inelastic

Nuclear stopping contributes to the collision cascade.

q = Charged state (e.g. + or -)

The definition of depth resolution

Comparison of mass analysers for SMIS

Sputtered species include :

To ensure the analysis secondary ions

The actual desorption of material from the surface

which is initiated by the primary ion

 Determination of molecular formula

 Formula from isotopic ratio

 Identifications of compound from fragmentation patterns

Qualitative application of SIMS

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