Energy dispersive analysis of X-rays (EDAX)

Also known as energy dispersive spectroscopy, and can be abbreviated as EDS, EDX, EDXS or XEDS
sometimes it is termed energy dispersive X-ray microanalysis(EDXMA) or energy dispersive X-ray
analysis (EDXA). It’s an investigative method which is widely employed in elemental or chemical
characterization of objects. The sample may be of any form such as solid thin films, solid powder, liquid
sample or even a pellet etc.
Basic analysis principle of EDS
A typical set up of the EDAX is similar with that of SEM set up. More specifically, EDAX is actually
inbuilt within the SEM set up. The working of EDX is based on electron focusing same as in SEM.
Electron beam excitation is employed in SEM and scanning transmission electron microscopes (STEM)
whereas the X-ray beam excitation is present in X-ray fluorescence (XRF) spectrometers. A detector
converts X-rays into voltage signals; which feed a pulse processor, to measure the signals and pass them
to data analyzer for display and investigation. Si(Li) detector cooled at cryogenic temperatures by liquid
nitrogen is often emploed; additionally, some modern systems come with silicon drift detectors (SDD)
employing Peltier cooling systems.

To produce characteristic X-rays from an object, it is bombarded by either a highly energetic beam of
charge carriers (electrons or protons) or X-rays. The atoms of the sample contain ground state
(unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. An electron from
an inner shell may be excited by an incident beam, thereby removing it from its shell and generating a
hole where electron was present before excitation. This hole can be occupied by an electron of a higher-
energy shell. The difference in energies of the higher- and lower- energy shells is emitted as an X-ray.
Quantitative measurement of the energy and number of these X-rays can be done with energy-dispersive
analysis of X-rays. Since the energy of these X-rays is characteristic feature of energy difference
between two shells and atomic structure of discharging element, EDAX can be employed to identify the
elemental composition of an object.

Figure 2 Example of EDS spectrum.

Characteristic X-Rays Generation-

When a sample is irradiated with highly energetic beam of electrons then a characteristic X-ray is
generated. Due to irradiation when an electron is excited from the inner shell of its parent atom, the
vacant place is occupied by the higher energy electron from the outer shell and the energy difference
between the two shells is emitted as an X-ray. The joule of energy liberated in electron transfer is
dependent upon from which shell it is transferring to which shell. Emitted X-rays energy as well as
number through specimen is obtainable by an energy dispersive spectrometer.

Figure 3 Principle of characteristic X-Rays Generation.

These emitted X-rays are known as characteristic X-rays because their energies (wavelength) are
specific to the element from which it is emitted. Thus, this technique can be used for elemental analysis.
When K-shell electrons are excited, they emit characteristic X-rays which are termed as “K Lines” and
those emitted from L and M shells are called “L Lines” and “M Lines” respectively. When the element
is heavy then its characteristics X-rays energies are also higher, therefore incident electrons of higher
energy are required. Different types of X-rays are emitted when incident electrons strike the atomic
nucleus and these are known as “continuous X-rays”, “white X-rays” and “background X-rays”.

Sample’s qualitative compositional data can be known from the respective peak positions with
appropriate energies. The X−ray quantanumber measures the concentration of the elements, i.e., the
height of thepeak, but there is no linear connection between quantum numbers and elemental
concentration portions. The concentration calculation requires the net count rates and characteristic X-
ray energy of a specimen is the marker of the specimen atomic number.

Instrumentation of the EDAX

Figure 4 shows the working arrangement of EDS with SEM. This instrument is mainly composed of
four components:

 Electron beam source

 X−ray Detector
 Pulse Processor
 Analyzer

Figure 4 Working arrangement of EDAX (Energy dispersive analysis of X−rays)

Brief Description of Components-

 Electron beam source: As EDS is employed with the scanning electron microscope
therefore the same electron gun (Field Emission) is used as the incident electron source and
to focus the beam lenses are used along with aperture. The energy of the electron beam has to
be carefully selected to overcome the compromise between the resolution requirements and
the production efficiency of X- rays. The produced X-rays are detected bytwo crystal
spectrometers.

 X−ray Detector: The X-rays counts (which is the abundance of emitted X-rays) versus X-
rays energies are measured by the EDS detector. Detector, a solid state device which is based
on lithium drifted silicon. As X−rays strike the surface of the detector, a charge pulse is
created. This charge pulse is directly proportional to the energy of the incident X−ray.

Parts of Detector:

Figure 5 Illustrative diagram of X-Ray Detector showing its components.

Collimator assembly: The purpose of the collimator is to providerestrictiveaperture through

which X-rays should pass in order tomake a way to detector. The collimator ensures that
only X-rays from the region being excited by the beam of electron are detected.
 Electron trap: Background artefacts are created when electrons penetrate the detector. The
purpose of the electron trap is to guarantee that only X-rays should enter the detector. It
comprises a pair of permanent magnets to strongly deflect the passing electrons.
Window: The purpose of the window is to provide isolation from the microscope chamber to
maintain vacuum inside the detector, at the same time being as transparent as possible for
allowing low energy X- rays. It accomprises a thin window composed of polymer and
transmits X-rays from elements which are heavier in comparison to Beryllium.
Crystal: In detector crystal material used is silicon (Si), drifted with lithium (Li) [around 3mm
thickness] for small levels of impurity compensation. When X-rays are incident on the crystal
of detector then its energy gets absorbed by a series of ionizations within the semiconductor
to generate electron-hole pairs. The absorption of every 3.76eV of X-ray radiation generates
an electron-hole pair. Therefore, 1,966 electrons are generated by a Ni Kα X-ray photon
(7,471 eV). The electrons promoted to the conduction band can freely move in the crystal
lattice. Every excited electron leaves behind a ‘hole’ in the valence band, which acts as a free
(positive) charge carrier within the crystal. When the front and back face of the crystal are
biased with high voltage, these electrons and holes are swept towards the opposite poles,
thereby generating a charge signal, whose size is proportional to the incident X-ray energy.

Figure 6 Diagrammatic illustration of X-ray interaction with crystal.

FET: The FET (Field Effect Transistor) performs first stage amplification which
measures the charge released within the crystal by the incident X-ray and converts
it to a voltage output. FET is nowadays integrated with the chips in order to
greatly enhance the resolution along with the throughput which is achieved by
reducing noise through minimizing the capacitance between FET and anode.
During operation, charge is accumulated by each incident X-ray on the feedback
capacitor, thereby producing sharp voltage steps. The step size of this voltage is
proportional to the energy of the incident X-ray. Restoration of the build-up
charge is required periodically to avoid preamplifier saturation.

Cryostat: EDS detector is a self-enclosed vacuum system (called cryostat) with

liq. N2, or a cryogenic pumping. The crystal and FET are mounted on cold finger
within cryostat to reduce the noise by cooling. The cooling is necessary as the
detector produces small charge pulses. At low voltages, there solution of the
detector depends upon the noise. The X-ray peaks are typically 2-10 eV wide
(FWHM). However, due to noise, this width can increase by at least an order of
magnitude. The vacuum level should be maintained such that the condensation of
molecules on crystal can be avoided.

 Pulse Processor: A charge−sensitive preamplifier is employed to convert the

charge pulse to a voltage pulse.
 Analyzer: Multi-channel analyser is used to sort pulses by voltage in the
signals which are received by the analyser. The energy of the X-ray can be
 obtained by measuring the voltage of the charge pulses. This energy is then
sent for display and data processing. Here, data is displayed as histogram of
intensity vs voltage.
Table 1: Features of EDS

Application

Qualitative Analysis-

X- rays generated EDS spectrum helps to carry out qualitative analysis to identify

whatever elements are present in the sample when it is irradiated with high energy
beam of electron. There are 3 methods of examination:

 Point Analysis: Spectrum is obtained from a point which is radiated with electron
probe.

 Line Analysis: Spectrum is obtained from a specified line displaying one–

dimensional desired elemental distribution.

 Mapping:Spectrum is obtained from a specified area displaying two-

dimensional desired elemental distribution. It is often called as “Area
Analysis”.

X- Ray Mapping-

It is used to study particular elemental distribution. For analysis purpose, electron

beam is scanned over a particular area and the related characteristics X-rays are
acquired. If the peak to background ratio is very low then X-ray Map does not show
 the distribution of desired element, i.e., it shows the distribution of continuous X-rays.
Sometimes X-Ray Map may not show the distribution of elements which are not of
interest because characteristics X-Rays of elements of interest are close to those of not
desired. It happens when energy difference between the desired element and
undesired element is equal to the spectrometer energy resolution. It takes more time to

acquire one X-ray picture as intensities of X-rays are less in comparison to that of
secondary and backscattered electrons. The resolution of X-Ray Mapping is limited
by “Area Analysis”. .
Figure 8 shows an example of X-Ray Mapping
The procedure which quantitatively evaluates the points upon the sample gradually while
scanning the electron beam is called “Quantitative mapping”. Precise elemental
distribution can be acquired using “quantitative analysis” method even if Peak to
Background ratio is low. It is a great advantage of this method.

Analysis Area-
Incident electrons when strike the specimen surface, get diffused and lose their energy by
generating characteristic X-rays. This X-ray generation is spread over an area of around a few
micrometers under standard operating condition. Thus, a larger area needs to be analyzed in
order to examine the particle of the order of few nm range in a SEM image. The analysis area
can be decreased by reducing the accelerating voltage. However, accelerating voltage cannot
be reduced below a certain level, since the generation of X-rays requires high accelerating
voltages. Another strategy to reduce the analysis area is by reducing the thickness of the
sample under investigation.
Quantitative Analysis-
As characteristic X-rays intensities are proportional to the particular element’s concentration,
therefore quantitative analysis can be performed. The concentrations of unknown elements in
a sample can be obtained by matching the intensities of characteristic X-ray of standard
sample with that of the unknown sample. However, X-Ray generated in the sample may be
either absorbed within thesample or excite the X-rays from other elements before being
emitted in vacuum. Therefore, correction is required in this analysis method for which the
following requirements are prerequisite:

 Flat specimen surface

 Electron probe should enter the samplein perpendicular direction
 Distribution of elements in the X-ray generation area should be uniform

There are always some appreciable errors in this analysis method because some
specimens do not meettheserequirements.

Non-Conductive specimen Analysis-

For non-conducting sample, metal coating is required in order to prevent the charging
but if requirement is to detect light element then it is suggested to use thin coating
film, as heavy metal coating can block the X-ray emission through the sample because
the X-ray intensities are less in comparison to secondary and backscattered electrons.

Analyzing sample with low incident accelerating voltage can cause some problems like:

 High excitation energy based characteristics X-rays cannot be detected

 Quantitative analysis accuracy is degraded
 While performing “line analysis” or “X-ray Mapping” – position shift in
incident electron probe occurs

Suggestion for such problem: low vacuum SEM can be used to analyze non-
conducting sample because residual gas molecules present in the sample chamber
scatter the high energy electron beam thereby increasing the analysis area.