Materials Characterization

Scanning Electron Microscopy (SEM)

 SEM- Basic Construction
1. Electron Production
Entire system is
under vacuum 2.Electron Acceleration

3. Electron Focusing

4. Electron Scanning
7. Signal Display
6. Signal Detection

6. Signal Detection 5. Electron Interaction

 Electrons Need Vacuum
In Air In Vacuum

Complete scattering No scattering

 Vacuum inside SEM

Atmospheric pressure (STD) = 760 torr or 1.01x105 Pascal.

One torr = 133.32 Pascal.
 How scanning electron microscope works?
Basic steps involved:
1.A stream of electron is formed and
accelerated towards the specimen using a
positive electrical potential

2.This stream is confined and focused using

metal apertures and magnetic lenses in to a
focused beam

3.Electron – matter interaction occur inside the

specimen giving rise to various signals.

4.These interactions (signals) are detected and

transformed in to an image
 SEM components
Electron gun : Filament, Wehnelt cylinder,
anode

Lens system: condenser and objective lenses

(electromagnetic lenses)

Detection system : Electron/Xray collector

Vacuum systems : Pumps

 Electron Gun
Electron gun consists of :

Filament (or cathode) : produces

electrons by thermionic (W,LaB6) or
field emission (FE)

Wehnelt cylinder : used to concentrate

electron beam

Anode plate : Used to accelerate the

electrons down the column by producing
high differential between it and the
cathode
 Electron Gun

 Wehnelt Cap
negative bias

 Anode
positive bias
Filament
 Electron sources

W
 Electron sources
Field Emission: Source is a sharp tungsten tip. Electrons are extracted by a
strong electric field.
 Comparison of electron sources at 20kV

Source Brightness Lifetime Source size Cost (US$) Vacuum

(A/cm2.sr) (h) (torr)
W 105 40-100 30-100 µm 15 10-4 – 10-5

106 200-1000 5-50 µm 400 10-6 – 10-7

Field 108 >5000 < 10 nm 6000 10-9 – 10-10

emission

sr - Steradians
 Condenser lenses

Reduces the diameter of the electron

beam

Two condenser lenses (C1, C2)

Need two lenses to set the spot size

(C1) and focus the spot on the
specimen (C2) ―Spot size‖

knob controls these lenses

 Electromagnetic Lenses

Electromagnetic lens : consists of coils of copper wire inside iron pole

pieces (solenoid). Current through the coils creates magnetic field
 Electromagnetic Lenses
Electrons are charged particles and their paths are
changed in passing through a magnetic field.
where F = force

F = q*(VxB) V = velocity
B = magnetic field
q = electron charge

c
 Scan coils
 Electromagnetically shift the
electron beam to produce scan
pattern

 Scans beam across the specimen

Controls image magnification

 For high magnification, scan over

small area
 Objective lens

 Final focusing of the beam on to

specimen

 Mostly, microscope resolution depends

on quality of the objective lens

 The ―Focus‖ knob controls/ adjusts this

lens
 Detector System
 Collect signals:secondary electrons(SE), backscatter electrons
(BSE), Xrays

 Amplify signal and feed to monitor/computer

 Everhart-thornley detector (SE) Solid state

diode detector (BSE)
 Electron- Specimen interaction
Incident electron

Backscatter electron

Secondary electron
Characteristic X-rays

Bremsstrahlung Auger electron

Specimen
 Electron- Specimen interaction

•Elastic scattering events :Affects the trajectories of the electron beam

without altering the kinetic energy of the electrons
— Backscattered electrons

•Inelastic scattering events : results in transfer of energy from the beam

electrons to the atoms of the specimen.
— Secondary electrons
— Auger electrons
— Characteristic and continuum X-rays
Electron- Specimen interaction volume
 Secondary electrons (SEs)
• Produced by inelastic interactions of high energy electrons with valence electrons of atoms
in the specimen which cause the ejection of the electrons from the atoms.

• Arbitrarily, such emergent electrons with energies less than 50 eV are called secondary
electrons; 90% of secondary electrons have energies less than 10 eV; most, from 2 to 5 eV.

• It is relatively independent of the atomic number of the scattering atoms (unlike the
situation for backscattered electrons)

• Because of their low energies, secondary electrons generated more than certain distance,
called the maximum escape depth (ᶓ) below the surface cannot escape from the specimen.
 Secondary electrons
• Low energy electrons arising from inelastic scattering
• Emitted from the top 1-50 nm zone of the pearshaped excitation area.
• Imaging specimen morphology
 Secondary electron detector

•Consists of plastic scintillator coated with a film of evaporated aluminium

which emits light when struck by electrons
•Light is guided by total internal reflection in a light pipe to a photomultiplier
which converts the light and amplifies to an electronic signal
•Faraday cage (metal box with grid mesh) covers the scintillator and it draws
majority of the secondary electrons leaving the surface
Secondary electron detector
 Backscatter electrons
Primary electrons striking the sample are deflected without energy loss (elastic
scattering) giving rise to backscatter electrons

Fraction of electrons that backscatter is given by Backscatter electron

coefficient (η).

η increases as a function of atomic number (Z) since amount of elastic

scattering also increases
 Backscatter electron coefficient (η)
For a monatomic surface the backscattered electron signal can be approximated
in terms of a polynomial expression.

η(Z) = -0.025 + 0.0162 Z - (1.8x 10-4) Z2 + (8.3 x 10-7) Z3

 BSE contrast
In a sample, with mixture of phases or elements, the magnitude of the
compositional contrast, called atomic number contrast, ‗C’, can be determined
between two phases or elements

η2 − η1
𝐶𝑜𝑛𝑡𝑟𝑎𝑠𝑡 = η2 > η 1
η2

η1 – backscatter electron coefficient of element 1

η2 – backscatter electron coefficient of element 2

Contrast observed in BSE image is proportional to atomic number thus

allowing compositionally different regions to be distinguished
 Backscatter electron image (BEI)
Al- Cu eutectic

Bright - ? Cu

Dark - ? Al
 Exercise
Calculate the atomic number BSE contrast (%) between Al and a) Si, b) Fe,
c) Au and d) Cu.

Given ηAl=0.153, ηSi=0.164, ηFe=0.279, ηAu=0.487, ηCu=0.314.

η2 − η1
𝐶𝑜𝑛𝑡𝑟𝑎𝑠𝑡 =
η2
 Exercise
Atomic number
contrast
Z1 Z2 η1 η2 C (%)
13 (Al) 14 (Si) 0.153 0.164 0.0670
13 (Al) 26 (Fe) 0.153 0.279 0.4516
13 (Al) 29(Cu) 0.153 0.314 0.5127
13 (Al) 79(Au) 0.153 0.487 0.6858

Greater difference between the atomic number Z of the constituent

elements higher the contrast. Easy to differentiate the bright and dark
regions
Atomic number contrast : Adjacent elements
 Atomic number contrast : Adjacent elements

ZA ZB η𝐴 η𝐵 C (%)
5 (B) 6 (C) 0.055 0.067 0.17
13 (Al) 14 (Si) 0.153 0.164 0.067
26 (Fe) 27 (Co) 0.279 0.287 0.028
41 (Nb) 42 (Au) 0.375 0.379 0.013
57 (La) 58 (Ce) 0.436 0.439 0.0068
78 (Pt) 79 (Au) 0.485 0.487 0.0041

Contrast is very less in elements whose atomic numbers are very

close, so might be difficult to differentiate them in BEI
 Atomic number contrast-example

Al-Cu alloy (C= 51%) Al-Si alloy (C = 7%)

Bright region – Bright region –

Dark region - Dark region -
 Backscatter electron detector
Solid State Diode Detector

• Mounted just below the objective lens pole piece.

• Located around and near the optic axis.
• Incident energy is measured as charge and converted to brightness.
Backscattered Electron Image (BEI)

BEI (TOPO)

BEI (COMP)
 SEI vs BEI
Red blood cells with silver stained nuclei

Secondary electron
mode

Backscattered electron
mode

Blood cells with nuclei stained with a silver compound are visible in backscatter
mode even though they are beneath the surface of the cell membrane
Topics of interest

• Lens Aberrations
• Spherical Aberration
• Chromatic Aberration
• Astigmatism
• Choice of accelerating voltage
• Influence of spot size
• Optimum contrast and brightness
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
 Quantitative EDX
Quantification of peak areas / heights of each element
 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