Secondary Ion Mass Spectrometry for Surface

Analysis

 Secondary ion mass spectrometry (SIMS) examines the mass of ions, instead of
energy of electrons, escaped from a solid surface to obtain information on surface
chemistry. The term ‘‘secondary ion’’ is used to distinguish ‘‘primary ion’’ that is
the energy source for knocking out ions from a solid surface.

The advantages of SIMS over electron spectroscopy are:

• detection of all the chemical elements in the periodic table, including hydrogen that
cannot be detected by the AES or XPS
• detection of elements in concentrations as low as 10-6, while AES or XPS
detection limits are concentration levels of 0.1 at%
• limitation of the detection to the top one or two atomic layers of a solid surface (<1
nm); and
• distinguish between different isotopes of elements.
 SIMS as a surface analysis technique has not yet reached a mature stage because it is still
under development in both theoretical and experimental aspects.

 Lack of maturity is attributed to the complicated nature of secondary ion yield

from a solid surface. Complexity of ion yield means that SIMS is less likely to be used for
quantitative analysis because the intensity of secondary ions is not a simple function of
chemical concentrations at the solid surface.

SIMS can be either destructive or nondestructive to the surface being analyzed.

 The destructive type is called dynamic SIMS; it is particularly useful for depth
profiling in chemistry.
 The nondestructive type is called static SIMS.

Both types of SIMS instruments are widely used for surface chemical
examination.
Basic Principles
SIMS uses energized primary particles, usually ions such as Ar+, Ga+, and Cs+, to
bombard a solid surface in order to induce sputtering of secondary particles from
an area

Figure: Secondary particle generation by an energetic primary

particle.
The interactions between primary ions and the solid are rather complicated.

 First, the secondary particles include electrons, neutral species of atoms

or molecules, and ions. The majority of the secondary particles are neutral
and not useful in SIMS. Only the secondary ions generated by the bombarding
process carry chemical information.

 Second, the interactions are often more than a simply one-to-one knock-
out of a surface ion by a primary ion.

Commonly, the primary ions induce a series of collisions (collision cascade) in

a solid because the energy of a primary ion is transferred by collisions between
atoms in a solid before secondary ions on the surface are emitted.

The generation of secondary ions involves sputtering and ionization.

Secondary Ion Generation

Emission of secondary particles can result from

-collision sputtering:
• direct collision sputtering and
(extremely fast)
• slow collision sputtering

-thermal sputtering
(slower than the collision sputtering)

-A sputtered particle faces competition between Figure: The sputtering process in SIMS: (a) direct
collision sputtering; (b) collision cascade; and (c)
ionization and neutralization processes when thermal sputtering.
it escapes a sample surface.

-The ionization probability represents the chance of a sputtered particle being an ion.

-Under the same experimental conditions, the yield of elemental secondary ions
can vary by several orders of magnitude across the periodic table. The secondary ion yield
for a particular element dramatically varies with chemical state. For example, the
positive Al ion yield in its oxide state is 100 times higher than in its pure state.
Dynamic and Static SIMS

 The energetic primary ions remove atoms, atom clusters, molecules, or molecular
fragments from the surface region of a sample. Thus, the chemical structures of the
surface may be destroyed during SIMS examination.

 SIMS with high flux of primary ion bombardment is referred to as dynamic SIMS.

 Dynamic SIMS is able to remove many layers of atoms in the surface region and provide
elemental distributions in a depth profile, similar to AES and XPS.

In order to analyze surface chemical structures, static SIMS has been developed
in which a low flux of primary ions is used in order to avoid the possibility that any
surface area is bombarded by primary ions twice. The dose of primary ions never exceeds 10 13
ions cm−2 of surface area. The density of surface atoms as about 10 15 atoms cm−2 by assuming
the area of each atom as about 0.1 nm2. The low dose of primary ions used in static SIMS
means that less than 1% of the surface atoms or molecules are bombarded. A primary ion
bombardment only generates damage to a zone with a cross section (σ) less than 10 nm2 (= 10−13
cm2) on the surface. A damaged surface area is defined as a region that includes the impact
point of a primary ion and escape point of a secondary ion. Thus, static SIMS is considered as
a nondestructive method for surface analysis.
Instrumentation

 SIMS requires an ultrahigh vacuum environment,

similar to AES and XPS.

 SIMS structure in a vacuum chamber in which there

are two main components: a primary ion system and
a mass analyzer system.

• The primary ion system includes a

primary ion source, a Wien filter and ion-
beam deflector. Figure: SIMS instrumentation

• The mass analysis system includes a secondary ion extractor filter, mass
analyser (Magnetic Sector Analyzer, Quadrupole Mass Analyzer, Time-of-Flight
Analyzer), and ion detector.