Materials Characterization

Scanning Electron Microscopy (SEM)

Energy Dispersive X-ray analysis (EDX)
(OR)
Energy Dispersive Spectrometer (EDS)

http://www.cti-cert.com/en/business/index.aspx?bid=50
Electron- Specimen interaction

Energy dispersive X-ray analysis

 History- EDX

In 1913, Moseley found out that the frequency of emitted

characteristic X-rays is a function of the atomic number of
the emitting element.

ν = 2.481015 (Z −1)2 K-level

E = hν

Elements present in the specimen could be identified by

examining directly or indirectly the excited X-ray spectra
1887-1915
 Energy Dispersive X-ray (EDX) analysis
Analytical method used for determination of elements/chemical composition

EDX involves measuring X-

rays energies

•Plot of X-ray energies (KeV) vs number of X-rays emitted (relative counts) is

composed of all the possible signals for that given set of elements.
•Specific peak reflect the presence of specific element
 X-rays Emission

X-rays are produced by inelastic scattering of beam electrons

1) Bremsstrahlung or continuous radiation

Emitted when a fast electron is rapidly slowed down as it passes through an
electric field around an atomic nucleus.

2) Characteristic X-rays (Inner shell ionization process )

Emitted from elements when electrons make discrete transitions to lower
atomic energy levels.
 Continuous X-rays (Bremsstrahlung)

• “Bremsstrahlung” (German) means

“braking radiation”
• Radiation which is emitted when electrons
are decelerated or “braked” when they
interact with the specimen.
• They are non-specific and contribute to
background
• They contribute to the total X-ray signal
Characteristic X-ray Production
 Characteristic X-ray Production
Many intershell transitions can occur - the common transitions encountered
are:

2p (L) - 1s (K), known

as the Kα line
3p (M) - 1s (K), known
as the Kβ line

(in fact Kα is a close doublet, associated with the two spin states of 2p
electrons)
Family of X-ray lines

There are wide variety of subsets of

these X-rays since each electron shell
has multiple orbitals
 Energy Dispersive X-Ray Spectroscopy (EDX)

Qualitative analysis

Elements with atomic numbers from that of

beryllium to uranium can be detected
 Energy Dispersive X-Ray Spectroscopy (EDX)

Qualitative analysis
 K- Lines
The K family consists of two recognizable line, Kα and Kβ with intensity
ratios 10:1 (when they are resolved). This is one important criteria for
identification of elements
 X-Ray Lines
At lower energy range (< 3 keV), the separation of the members of the K, L, M families
becomes so small that peaks are not resolved with an EDX system
 L- Lines

Lα(1), Lβ1(0.7), Lβ2(0.2), Lγ1(0.08), Lγ3(0.03)

M- Lines

Mα(1), Mβ(0.6), Mε(0.06)

 X-Ray Lines
Relative intensity of various energy level help to identify particular element
 Qualitative X-ray analysis-General guidelines
How to identify particular element

• Determine the energy of the most intense peak. If it corresponds

closely to Kα of an element, immediately look for Kβ line with
about 10% of the Kα peak height.

• If Kα and Kβ pair does not fit the unknown, try the L-series

• M family lines can be observed for elements starting at cerium. M

lines occur at energy of 3.5keV or less.
 Class Exercise

Qualitative analysis example Identify which element is present?

 EDS Detector
Lithium doped Silicon [Si(Li)] crystal detector (2-5mm thick)

Acts as a semiconductor. X-rays hitting the crystal generates electrons/holes

that carries current. Indirect measurement of the X-ray energy .
 EDS Detector

The Lithium-doped silicon crystal is mounted

on a cold finger connected to a liquid-nitrogen
reservoir stored in the dewar

Low temperature is required to limit the

mobility of the lithium ions initially introduced
in the silicon crystal and to reduce noise
 EDX Spectrum

Number of X-rays
emitted (relative counts)

X-ray energies (KeV)

 Intensity of Characteristic X-rays
The peak intensity Ip is a function of the excitation voltage (Eo), critical
excitation voltage (Ec), beam current (i) such that

I p≅ i(Eo −Ec )n ; where n ≅1.7

Ec :Minimum required voltage produce radiation.

No radiation is produced if Eo < Ec

In practical microanalysis we need “Overvoltage” to ensure adequate

intensity of X-ray lines in the EDX spectrum
 Overvoltage

Overvoltage (U) is the ratio of accelerating (gun) voltage to critical

excitation energy for particular line.

E0 : gun accelerating voltage

U = E0/Ec Ec : critical excitation energy

Overvoltage is needed to induce a high probability of X-ray emission

In practical microanalysis the over voltage U = Eo/Ec should be ~2 to

ensure adequate intensity.
EDX simulation – Effect of accelerating voltage
Software for EDX
simulation

http://www.mikroanalytik.de/index_d.phtml
Overvoltage and Characteristic X-ray Emission
 Applications - EDS
Example 1 : CdS nanowire composition
CdS wires were found to be composed of only Cd and S.

Si peak from substrate. Spectrum collected from red spot

 Applications - EDS
Example 2 : Au nanoparticle on SiO2 wire
 Applications - EDS
Example 4 : Gun shot residue (GSR) analysis

Bullet particles normally consist of Pb (lead), Sb (antimony) and Ba (barium). therefore

presence of these particles at the crime scene forms evidence of firing a gun
 Applications - EDS
EDS Mapping
 Applications - EDS
EDS Mapping
Archeological case study
 Applications - EDS
EDS Mapping
High Resolution EDS
Sample Preparation - SEM