Energy-dispersive Spectroscopy equipped with

SEM
X-rays: Production

An inelastic collision between

a primary beam electron and
an inner orbital electron
results in the emission of that
electron from the atom, the
energy released from an
electron replacement event
produces a photon with an
energy exactly equal to the
drop in energy.
 X-ray: Nomenclature

When an electron from a K-shell is replaced

by one from the next closest shell (L), it is
designated as a Kα event
 X-ray: Nomenclature

When an electron from a K-shell is replaced by one from

the second closest shell (M), it is designated as a Kβ event
 X-ray: Nomenclature

When an electron from a L-shell is replaced by one from the next

closest shell (M), it is designated as a Lα event. The K shell will
never donate its electron as this would require an increase in energy,
not a drop.
 X-rays: Nomenclature

Certain events such as Mα, Lβ, and Kγ are only possible in

atoms of sufficient atomic weight
Family of Characteristic X-rays
 EDS/EDX

X-ray microanalysis enables the SEM and TEM to be used as

analytical instruments. Limitations include the quantities of given
element and an inability to distinguish isotopes. By placing a
focused beam over an object allows one to carry out micro-
chemical analysis on very small or very discrete objects or to map
the presence of various elements within a specimen.
 X-ray Microanalysis:
Energy Dispersive Spectroscopy (EDS)
 X-ray Microanalysis

X-rays can have an energy nearly equal to that

of the primary beam electron and thus can
escape from very deep within the specimen
 EDS/EDX

Collimator to limit BSE and stray

X-rays
Window usually made of beryllium
(limited to sodium, atomic number
11) or thin plastic to detect down to
boron (Atomic number 5) protects
cooled crystal from air.

Detector crystal silicon wafer with lithium added in. For each 3.8 eV
from an X-ray, produce an electron and hole. This produces a pulse of
current, the voltage of which is proportional to the X-ray energy. Must
keep the crystal at LN temperature to keep noise to a minimum.
 How it works: energy gap

A semi-conductor like Si has a

fully occupied valence band
and largely unfilled conduction
band, separated by an energy
gap (1.1 eV). Incident energy
can raise electrons from the
valence to the conduction band.

X-ray hits the Si(Li) crystal, producing a specific number of electron-hole pairs
proportional to X-ray energy; e.g. one pair for every 3.8* eV, so for incident Fe
Kα, 6404 eV, 1685 e-hole pairs are produced. With a bias** applied across the
crystal, the holes are swept to one side, the electrons to the other, producing a
weak charge.

* 1.1 eV + energy wasted in lattice vibrations, etc

Goldstein et al, Fig 5.19
**bias: a voltage is applied between 2 points; e.g. one +1500 v, other -1500 v.
Si(Li) detector with LN cooling
Si(Li) detector with Peltier cooling
 EDS: PRINCIPLE
• EDS is an analytical technique used for the elemental analysis or chemical
characterization of a sample.
• The secondary x-rays (X-ray florescence) are directed to a detector.
• A detector is used to convert X-ray energy into voltage signals; this information is sent to
a pulse processor, which measures the energy of the signals and passes them onto an
analyzer.
• The analyzer converts the analog into a digital signal which is proportional to the energy
of the incoming pulse.
• Received pulses are actually amplified, converted into digital signals and then sorted by
energy with the help of multi-channel analyzer (energy is characteristic for each element)
and frequency of appearance (characteristic for concentration) and sent to data display
and analysis.
• The most common detector now is Si(Li) detector cooled to cryogenic temperatures with
liquid nitrogen
• However newer systems are often equipped with silicon drift detectors (SDD) with
Peltier cooling systems.
 EDS: PRINCIPLE

1μm

Elements Weight% Atomic%

Cu K 64.56 69.36

Se L 35.44 30.64
Totals 100.00  100.00
Qualitative Analysis with EDS
Positive identification of an element is best
done by collection of the entire family of peaks
for a given element.
 Qualitative Analysis by EDS
• Photons not electrons
• Each element has a fingerprint X-ray signal
• Poorer spatial resolution than BSE and SE
• Relatively few X-ray signals are emitted and the detector is
inefficient
 relatively long signal collecting times are needed
Chrysotile Asbestos Fibers
Chrysotile Asbestos Fibers
Quantitative Analysis with EDS
 Quantitative Analysis

If one wants to quantify the relative amounts of different

elements present in a complex sample one has to account
for a number of factors and carry out a correction of the
data
 Quantitative Analysis
Background subtraction
Bremsstrahlung X-rays are the major part
of the continuum X-ray signal that can
escape from the deepest portion of the
interaction region.
"Bremsstrahlung" means "braking radiation" and comes from the
original German to describe the radiation which is emitted when
electrons are decelerated or "braked" when they interact with the
specimen. Although they contribute to the total X-ray signal they
contain no useful information because their energies are
nonspecific and therefore are considered as part of the background.
.
 Quantitative Analysis
Converting peak areas to concentrations
 Quantitative Analysis

• Several methods to correct the spectra

• ZAF takes into account the Atomic Weight (Z), effects
of Absorbance (A) and effects of Fluorescence (F) in
adjusting the data to give the correct values.
 EDX

• Most common spectrometer: EDS

• Signal overlap can be a problem
One must account for other elements present in the
sample and whether their individual peaks overlap with
each other creating a “shoulder” that can mask the
presence of one element or distort the midpoint of
another.
Operating Modes of EDS
 EDX Modes

We can analyze our sample in different modes:

•Spot scan
•Line scan
•Area scan
•Elemental mapping
 EDX: Spot Analysis

Stoichiometry: Ca3-xAgxCo4-yFeyO9

Elements Weight % Atomic %

Co K 3.52 6.26

Ag L 96.48 93.74

Total amount 100.00

 
 EDX: Scan along a line
C O

Stoichiometry: Ca3-xAgxCo4-yFeyO9

Na S

Fe
Ca

Co
Ag

Pt
 EDX: Area scan

Stoichiometry: Ca3-xAgxCo4-yFeyO9

Elements Weight % Atomic %

CK 7.37 17.02

OK 30.08 52.14

Ca K 16.38 11.33

Fe K 0.91 0.45

Co K 36.53 17.19

Ag L 5.44 1.40

Pt M 3.29 0.47

Total amount 100.00

Elemental Mapping
 X-ray analysis of paint fragments

Combined with (a) backscatter imaging and X-ray maps of (b)

Au, (c) Ba and (d) Ca, in different layers of paint can be identified
X-ray Mapping
 Energy-dispersive Spectroscopy (EDS)

vs
Wavelength-dispersive Spectroscopy (WDS)
EDS vs WDS
 WDS vs EDS
WDS offers much higher energy resolution than EDS, better sensitivity, and better
reproducibility (precision) for quantitative analyses

Figures from McSwiggen and Associates, www.mcswiggen.com

X-ray Detection

EDS = Energy
Dispersive
Spectroscopy

WDS = Wavelength
Dispersive
Spectroscopy
WDS vs EDS
 Summary
Different signals in SEM and their Utility
 Secondary electrons (SE): mainly
topography
 Low energy electrons, high resolution
 Surface signal dependent on curvature
 Backscattered electrons (BSE): mainly
chemistry
 High energy electrons
 Bulk signal dependent on atomic
number
 X-rays: chemistry
 Longer recording times are needed