Assignment – MM505

JAGANATH GAONKAR (2023MEZ0014)

Background
In Scanning Electron Microscopy (SEM) when electron beam interacts with sample different
electrons comes out of samples like Secondary electrons, backscattered electrons, x rays, light
etc (Figure 1). And in EDS and WDS we use X-rays to generate the qualitative and quantitative
information about the sample. X rays are characteristic of a particular atom or element present
in the sample as x-ray has specific energies which correspond to that atoms or elements in the
sample. We know that the wavelength and energies are related to
each other by equation

nm,

When we use energies of the X-ray to generate information about

sample it is called Energy Dispersive x-ray Spectroscopy (EDS), and
when we use wavelength to generate information about the
sample it is called Wavelength Dispersive X-ray Spectroscopy
(WDS). Figure 1

Energy Dispersive x-ray Spectroscopy (EDS)

Operating Principle
In EDS when we collect the X-rays we actually collect the EDS spectrum which has two
components those are background called as continuum and characteristic x-ray called as peak
coming out of sample and both together forms the experimental spectrum which is used to
analyze the sample quantitatively and qualitatively.

When electron beam falls on the sample and passes through the atoms it decelerates or slows
down and changes the direction due to the electric field present inside the atom and during this
interactions some x-rays comes out of sample these are called breaking radiations and they
forms the continuum background on the EDS spectrum. When Electron beam while passing
through the atom, if knocks out the electron from the K shell the atom becomes unstable and
electron from the next higher energy shell i.e L shell comes to K shell and during this
transections some x-rays are generated and these are characteristic x-ray called as Kα x-rays
which gives a corresponding peak on the spectrum. Similarly if electrons from even more higher
energy shell i.e M shell comes to K shell, the x-ray generated is called Kβ x-rays and shows peak
at a particular energy. Similarly if electron from L shell is knock out and Electron from next
higher energy shell i.e M shell comes to L shell the X-rays generated are called Lα x-rays and is
shown with a peak on spectrum. This is how characteristic lines are generated and the resultant
spectrum is obtained containing both background and energy line in form of peaks (Figure 2).

Figure 2

Minimum excitation potential is required to excite KLM shells, so in graph of excitation

potential against atomic number (Figure 3) for higher atomic number higher excitation potential
is required to excite the shell. Since in SEM the excitation potential is limited to 30 kV so the
higher atomic numbers which has kV of K shell is above 30kV only L and M shell lines are visible
in the spectrum. There is generally a thumb rule that the excitation potential should be at least
2-3 times the energy level of KLM shell. Also as the kV reduces the peak height also reduces.

Figure 3. Oxford Instruments plc, 2023

Instrument Configuration
To acquire x-ray spectrum from the sample there are three components used in every EDS
system, 1. X-ray detector which collects the x-ray and converts and converts the x-ray into
electrical signals. 2. Pulse processor which amplifies the electrical signals and process the x-ray
pulse coming out of the detector and 3. Software which takes the output of the pulse processor
and nicely displays the EDS spectrum and essentially this is the microanalysis.
 a. X-ray Detector, utilizes a SDD to b. Pulse Processor, measures the
c. Analysis Software, displays the
detect X-ray and converts them electrical signals captures within
acquired spectrum, performing
into electronic signals the detector, calculating the
automatic peak deconvoluting and
energy of the detected x-rays
background removal
Figure 4. Oxford Instruments plc, 2023

X-ray detector
It is the heart of the EDS system, it has the small
opening from where x-rays enters the in the area
where collimator assembly ensures that the parallel
beam of x-ray enters the EDS detector and filter outs
the x-rays coming from the components from the
sample chamber. Collimator is followed by the electron
trap which is a physical magnet that creates the Figure 5. Oxford Instruments plc, 2023
magnetic field to deflect the high energy electrons
which enters along with x-ray. Then comes the window, which isolates the sensor from outside
and maintain vacuum inside and is extremely thin. Then there is sensor which is kept inside the
window, sensor is made up of crystal which receives the signals and converts them to electrical
signals and we have FET connected to the sensor to amplify the electrical signals (Figure 5).

In old EDS Si(Li) detectors with Dewar where nitrogen was put were used but now modern
detectors use silicon drift detectors (SDD) (Figure 6), their construction is quite different from
old detectors. There is no Lithium but only p and n type silicon is used. A large cathode from
where x-rays enters into the sensor and a small anode which is directly connect to the FET.
There are rings kept around anode and every ring is feed with the voltage called as drift voltage.
The incoming x-rays produces the electron-hole pairs in the silicon in crystal and this electrons
travels towards anode and holes towards cathode and the electrical signals are generated equal
to the amount of the x-rays received in the sensor. Drift voltage creates the potential path for
diverting the electrons towards anode once the x-rays hit the sensor, hence the name silicon
drift detector. We get a very small noise compare to the old Si(Li) detectors.
 Figure 6. Oxford Instruments plc, 2023

Pulse Processor
Pulse processing is the measuring the x-ray energy. A capacitor is connected across the FET;
this capacitor is charged and discharged which creates the voltage ramp. This ramp is then used
to create the electrical signals. The incoming x-rays creates the voltage ramp as shown (Figure 7)
and at the same time it also induces the noise on the ramp. This voltage ramps are measured as
the x-ray energies and noise decides the shape of the peak there by it also decides the
resolution. This noise is averaged during the processing; the process time is the measure of how
much time is applied to the noise. Higher the process time, better is the noise averaging,
sharper are the peaks and better are resolution.

Figure 7.Voltage ramp signals and peak resolution Oxford Instruments plc, 2023

Software
From EDS system we gets the qualitative analysis where system labels the peak automatically.
Most EDS systems got strong auto identification algorithms and this algorithms finds out the Kβ,
Kα, Lα lines and names the peak accordingly. Also EDS system provides with the quantitative
analysis. It is a comparative technique where the intensity of the unknown sample is compared
Where C is the concentration and I is the intensity
with the intensities acquired from the standard sample. This is not the simple comparison and
has to be applied by the matrix corrections.

In general algorithm follows the steps, first apply the filter least square fitting by removing the
background using Top Hat digital filter and then de convolute the peaks and use peak fitting.
Then find the apparent concentration and then apply the matrix corrections to get the
element’s concentration in sample by wt %. This is the process used (Figure 8).

Figure 8. Oxford Instruments plc, 2023

The electron beam raster on the sample and it also give the corresponding digital image. That is
it collects the EDS spectrums from every pixel and gives another information called as mapping
information or distribution information. Software creates the window and collects x-rays
coming in this window and plots them as particular elements signals and gets the distribution
all along the SEM image (Figure 9).

Figure 9. Elemental mapping /

Distribution Oxford Instruments
plc, 2023
Wavelength Dispersive X-ray Spectroscopy (WDS)

Operating Principle
When we use wavelength of the x-ray to generate information about sample it is called
Wavelength Dispersive X-ray Spectroscopy (WDS). It is much older compare to the EDS
technique. WDS is based on the Bragg’s law nλ = 2dSinθ, where n represents the diffraction
number, λ is the wavelength of the x-ray that will be diffracted, d is the interatomic spacing for
the diffracting crystal and θ is the angle crystal plane and the diffracted x-ray.

Bragg’s law
nλ = 2dSinθ

Figure 10

WDS also uses a focusing technique called as the Rowland Circle. When the WDS is of the fully
focusing geometry type then the sample, crystal and the
detector they form a circle called as the Rowland circle
and distance between sample, crystal and detector are
always kept the same. Two more geometries are also
used namely Johann Geometry where x-ray diffracted
from the crystal are not focused at a point on the
detector and the Johansson Geometry where the x-rays
after the diffraction are focused on the detector.

Figure 11 Oxford Instruments plc, 2023

Different diffracting crystals are used based on the range specified by the 2d spacing.

Table 1
Instrument Configuration
Heart of the WDS is the detector (Figure 12). The x-ray enters the detector and falls on the
reflecting crystal. Crystal diffracts the crystal and only one wavelength is made to fall on the
sensor.

The detector used in the WDS is the gas based detector, there is a first detector called as gas
proportional counter which uses (p-10) gas and is very sensitive to low energy x-rays coming
out of light elements (low atomic number). Then there is a sealed proportional counter
detector is used which is filled with ozone gas and sealed. It is very good for the high energy x-
rays and these two detectors are connected in the tendon one after another. There is also a
anode wire which carries the high voltage and incoming x-rays ionizes gas and then ions
accelerated towards anode and further increasing the voltage and get the highly amplified
output signals.

Figure 12. Oxford Instruments plc, 2023

Further processing and software process is similar to that of the EDS and then at the end we get
the qualitative and quantitative analysis. There arises the question on why do we need the WDS
system on the SEM. Because there are some overlaps in the energy peaks that the EDS cannot
resolve. EDS is needed for the fast analysis and for major elements but if we have overlaps or
minor trace elements where EDS does not do good job, for high resolution and high sensitivity
quantitative analysis we need WDS system. In practice we use combination of EDS and WDS
system on SEM which makes whole setup full fledge analytical SEM (Figure 13).
 Figure 13. Oxford Instruments plc, 2023

References
Goldstein, Joseph I., et al. Scanning electron microscopy and X-ray microanalysis. springer, 2017.

Russ, John C. Fundamentals of energy dispersive X-ray analysis: Butterworths monographs in materials.
Butterworth-Heinemann, 2013.

https://research.engineering.ucdavis.edu/cnm2/wp-content/uploads/sites/11/2017/04/EDXS-
SOP_033017.pdf

https://utw10193.utweb.utexas.edu/InstrumentManuals/Oxford%20EDS%20AZtec%20User%20Manual.
pdf

https://nano.oxinst.com/assets/uploads/AZtecWave_WDS_and_EDS_Hardware.pdf