MS3014: Analysis of Materials

Dr. Eileen Fong

 Analysis of materials
Chemical Composition Molecular Structure
Types of elements present Bonding information

Crystal Structure Morphology

Arrangement of atoms Porosity
Crystal size, lattice parameters Particle size and shape

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 Analysis of materials
Chemical Composition Molecular Structure
Types of elements present Bonding information

o XRF (bulk) o IR (chemical bonds)

o XPS (Surface) o XPS (chemical states)
o UV-VIS
o SEM-EDX
How & Why
does it form?

Crystal Structure Morphology

Arrangement of atoms Porosity
Crystal size, lattice parameters Particle size and shape

o XRD (X-ray diffraction) o SEM/TEM

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 MS3014: Course content

Operating Principles
Instrumentation
Data collection / Data analysis Techniques covered in this course
Real-world Applications 1. Scanning Electron Microscopy
2. Fourier transform infrared spectroscopy
3. UV-Vis spectroscopy
4. Fluorescence spectroscopy
5. X-ray diffraction
6. X-ray Fluorescence spectroscopy
7. X-ray photoelectron spectroscopy

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 Course learning outcomes
You should be able to:
• describe working principles of electron microscopy and the
theory of image formation.

• explain basic principles of UV-Vis, fluorescence and vibration

spectroscopy, and to derive material properties from the data
acquired.

• describe the working principles of x-ray diffraction, x-ray

fluorescence spectroscopy and x-ray photoelectron
spectroscopy, and to derive material properties from the data
acquired.

• identify suitable applications for each of the techniques

covered and provide justifications for the choice.

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MS3014 Class Schedule AY24/25 (S2)
Wk Topic Date Time/Venue Tutorial
1 L1 : SEM – Part 1 (EF) Mon, 13 Jan 2.30 pm/LT6 -
2 L2 : SEM – Part 2 (EF) Mon, 20 Jan 2.30 pm/LT6 -
3 Virtual SEM lab + online assignment Mon, 27 Jan 2.30 pm/LT6 -
4 L3 : IR spectroscopy (EF) Mon, 3 Feb 2.30 pm/LT6 SEM
5 L4 : UV-VIS spectroscopy (EF) Mon, 10 Feb 2.30 pm/LT6 IR
6 L5: Fluorescence spectroscopy (AB) Mon, 17 Feb 2.30 pm/LT6 UV-Vis
7 CA1 Mon, 24 Feb 2.30 pm/LT6 -

Recess week (1 Mar – 9 Mar)

8 L6 : X-ray Diffraction (AB) Mon, 10 Mar 2.30 pm/LT6 Fluorescence

9 L7 : X-ray fluorescence spectroscopy (AB) Mon, 17 Mar 2.30 pm/LT6 XRD

10 No class Mon, 24 Mar 2.30 pm/LT6 -
11 L8 : X-ray Photoelectron spectroscopy (AB) Mon, 31 Mar* 2.30 pm/LT6 XRF
12 CA 2 Mon, 7 Apr 2.30 pm/LT6 -
13 Revision & Tutorials Mon, 14 Apr 2.30 pm/LT6 XPS

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 Tutorials
Tutorial group Day Time Venue

T1 Monday 10.30 AM – 11.30 AM TR+22

T2 Wednesday 9.30 AM – 10.30 AM LT11

T3 Wednesday 1.30 PM – 2.30 PM LT10

Got Questions?

Eileen Fong (EF) Annalisa Bruno (AB)

[email protected] [email protected]
Office: N4.1-02-09 Offices: SPMS 04-12/
N4.1-02-20
 Course assessments

Continual Assessments (40%)

CA1 (20%)
CA 1 quiz (15%) : 24 FEB (MONDAY) at 2.30 PM (LT3)
Topics : SEM, IR & UV-Vis

Online Assignment (5%): Due 31 Jan (Fri) 2359h

(will only be counted if you attempt CA1)

CA2 (20%)
CA 2 quiz: 7 APR (MONDAY) at 2.30 PM (LT3)
Topics : Fluorescence, XRD, XRF (XPS NOT INCLUDED)

--------------------------------------------------------------
Final exam (60%)
All Topics and content from lectures and tutorials. 4 Questions in 2 hours
Scanning electron microscopy (SEM)
Part 1
 Lecture outline
1. Introduction to scanning electron microscopy

2. Instrumentation: SEM
o Electron gun
o Condenser lenses
o Scan coils
o Objective lenses
o Detectors
o Vacuum

3. Common problems in SEM

Suggested reading for SEM/EDX

Scanning Electron Microscopy and X-Ray Microanalysis

Goldstein, Joseph (Chapters 1, 2 & 7) 10
1 Scanning Electron Microscope (SEM)

An instrument in which the specimen surface is scanned by a

focused beam of electrons by sweeping it across a rectangular
shaped area (called “Raster”), the signals generated from electron
sample interaction forms image on the screen.
Analysis modes in SEM
 Applications of SEM

Localized elemental composition of the sample

 Features of SEM
SEM offers several key advantages over Optical
optical microscopy:
• Greater resolution
OM: ~0.2 mm
SEM: 1.5 nm OM SEM

(400x as much detail as light microscope)

• Higher magnification
OM: 4x - 1400x SEM
SEM: 10x - 500,000x (TEM~250,000x)

• Larger depth of field

OM: 0.5 mm
SEM: 30 mm
Nanofibers visualized using
optical (top) and SEM (bottom)
 Resolution
Resolution is the amount of detail you can see in an image

Resolution is defined as the smallest distance at which two objects

can be distinguished and recognized as individual objects

partially resolved
unresolved resolved
 Resolution
0.61𝜆 Smaller the ‘d’ value :
Abbe’s equation: 𝑑= better resolution
𝑛 sin 𝛼
d = minimum resolvable distance (smallest separation of two points that are
visible as distinct entities)
 = wavelength of the energy source
n = refractive index of the medium between lens and object
α = aperture semi angle

α
n sin  = Numerical Aperture (NA) of the objective lens,
and is typically inscribed on the lens by the
manufacturer(constant)

0.61𝜆
𝑑=
𝑁𝐴
 Electron wavelength
0.61𝜆
Recall 𝑑=
𝑛 sin 𝛼
The wavelength of an electron is dependent on the accelerating
voltage used to accelerate the electrons and is given by

where
ℎ h = Planck’s constant (6.626 x 10-34 J s)
𝜆= m = electron mass (9.109 x 10 -31 kg)
2𝑚𝑒𝑉 e = electronic charge (1.60 x 10-19 C)
V = accelerating voltage (0.5 - 3 x 104 V)

Voltage (kV) λ (Å) d (Å)

5 0.173 10.553
200 0.025 1.525
Light 4000 2440
 Magnification in SEM
• Magnification is the enlargement of an image, or portion of an image.

• In a SEM, this is achieved by scanning a smaller area. In the images, the

beam is indicated by arrows on a sample

Magnification
 Magnification in SEM
Magnification : defined by the ratio of the length (or area) of the scan on
the screen (Lmonitor) and length (or area) of the scan on the specimen
(LSpecimen).

SEM magnification can be changed by adjusting the length of the scan on

the specimen corresponding to a constant length of scan on the CRT
 Depth of field
The range of heights (distances) on the specimen surface for which the
image is in focus
Depth of Field (D)
4 × 105 𝑊
𝐷=
𝐴𝑀
A : Aperture size
M : Magnification
W : Working distance
(The distance between the
objective lens and specimen)

A SEM typically has orders of

magnitude better depth of focus
than a optical microscope
making SEM suitable for studying
OM SEM
rough surfaces
Screw length: ~ 0.6 cm
2 Instrumentation: SEM

Electron gun

screen
Sample chamber
 How the SEM works?
Basic steps involved

1. A beam of electron is generated and

accelerated towards the specimen
using a positive electrical potential

2. This beam is confined and focused

using metal apertures and magnetic
lenses into a focused beam

3. Electron – matter interaction occur

inside the specimen giving rise to
various signals

4. These interactions (signals) are

detected and transformed to an
image
 Instrumentation: SEM

1. Electron Production

2. Electron Acceleration
Electron gun

3. Electron Focusing
Sample chamber

4. Electron Scanning

7. Signal Display
6. Signal Detection

5. Electron Interaction
6. Signal Detection
Everything is
under vacuum!
Components in SEM
 Electron gun
Produces Electrons (our probe beam).
We want many electrons per time unit
per area (high current density)

(1) Thermionic Gun

(2) Field Emission Gun
 Electron gun
Electron gun consists of :
Filament (or cathode) which
produces electrons by either
• Thermionic gun, or
(heated using a high filament current)

• Field emission gun (FEG)

(electrons are pulled off the cold filament
by a strong electrostatic field called
an extraction voltage)
 Thermionic Emission
• Filament (source) is heated until electrons overcome work function (E W).
• When the emitter material is heated to a high temperature, a small fraction
of the electrons at the Fermi level acquire enough energy to overcome Ew
and escape into the vacuum

E :Energy (work) necessary to place an electron in

the vacuum from the lowest energy state in the
metal.

EF :Electrons have a range of energies, and the

highest energy state in the metal is called the
Fermi level, EF

Ew :Energy required to remove an electron from the

solid to vacuum .
 Thermionic Emission
The cathode current density Jc obtained from an emitter by thermionic
emission is expressed by the Richardson equation Jc (A/cm2)

𝐽𝑐 = 𝐴𝐶 𝑇 2 exp(− 𝐸𝑤 Τ𝑘𝑇)
Ac : Area of the cathode (constant for all thermionic emitters ~120 A/cm 2K2)

T(K) : Absolute emission temperature,

Ew(eV) : work function of the filament material, (W= 4.5 eV, LaB 6= 2.5 eV )

k : Boltzmann's constant (8.6 x 10-5 eV/K)

• Both the temperature T and the work function Ew have a strong effect on
the emission current density (Jc) that can be obtained from the filament.

• It is desirable to operate the electron gun at the lowest possible

temperature to reduce evaporation of the filament, and use materials of
low work functions.
 Thermionic Emission
• In order to maintain a constant beam of electron, the filament should
operate at saturation.

• Since the filament has to be maintained at white hot, thermionic gun

filaments have short lifetimes

• Typical filaments are Tungsten (W) and lanthanum hexaboride(LaB6)

 Thermionic Emission

W LaB6

New Used New Used

LaB6

• LaB6 is more expensive than tungsten . W has higher melting point (3695 K)
than LaB6.

• Repeated heating and cooling of the filament causes more damage to

thermionic filaments as compared to FEG
 Field emission gun (FEG)
• Electrons are extracted by a strong external electric field.
• Electrons tunnel through a potential barrier. Source is a sharp
pointed tungsten emission tip

• FEGs provide significant advantages over

thermionic filaments including:
o a much smaller electron virtual source size
o higher brightness (100x)
o lower energy spread, and
o a longer filament lifetime.

• These advantages make the FEG SEM (a.k.a. FESEM) a high

resolution machine for high magnification work.
 Field Emission gun
Source Brightness Lifetime Source Cost Vacuum
(A/cm2.sr) (h) size (US$) (torr)
W 105 40-100 30-100µm 15 10-4 - 10-5
LaB6 106 200-1000 5-50µm 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
C1
• Two condenser lenses (C1, C2)

• Need two lenses to set the spot C2

size (C1) and focus the spot on
the specimen (C2)

• “Spot size” knob controls these

lenses (C1)

Spot size:
diameter of the electron beam
 Electromagnetic lenses
Electromagnetic lens : consists of coils of copper wire inside iron
pole pieces (solenoid). Current through the coils creates magnetic
field
 Scan coils
• Electromagnetically shifts the
electron beam in X and Y
directions to produce scan
pattern

• Scans beam across the specimen

• Fed from scan generators

• Controls image magnification

(higher magnification, smaller scan area)
 Objective lens
• Final focusing of the beam on
to specimen
• The “Focus” knob controls/
adjusts this lens
 Working distance (W)
• The distance between the
objective lens and specimen

• Larger WD = lower resolution

= greater depth of field

• Use the smallest possible WD

where possible for best resolution

W
 Working distance & Depth of field
4 × 105 𝑊
Depth of Field: 𝐷 =
𝐴𝑀
Short WD Long WD

Small-diameter aperture Large-diameter aperture

Electron-specimen interactions
 Detectors
• Collect signals: secondary
electrons(SE), backscatter electrons
(BSE), X-rays

• Amplify signal and feed to

monitor/computer

• Everhart-thornley detector(SE)

• Solid state diode detector (BSE)

 Electrons need a vacuum
Air Vacuum

Complete scattering No scattering

Scattered electron Focused electron
beam which cannot beam on
interact with the sample
sample to produce
meaningful analyzed
beam
Sample Sample

• Scattering of the beam will also

increases the probe size (reduces
resolution especially in SEI mode)

• High vacuum also ensures

maximum collection efficiency of
secondary electrons
 Components in SEM

Please review the animation again online.

3 Common problems in SEM imaging
1. Lens Aberration (defects)
Astigmatism: Non-spherical electron beam

Cause:
Strength of lens is asymmetrical, dirty apertures

Effect: Out of focus “stretched” images

1. Lens Aberration (defects)
SOLUTION FOR Astigmatism

Stigmator : is a device that applies a weak supplemental magnetic field to

compensate the asymmetry and make the lens appear symmetrical to the
electron beam

Ring of electromagnets positioned around the beam to “push” and “pull”

the beam to make it more perfectly circular
1. Lens Aberration (defects)
SOLUTION FOR Astigmatism

Astigmated
images

Stigmator
Corrected
2. Specimen charging
• Charging of the sample is the greatest impediment to good
images in the SEM.

• The simple explanation of charging is that there is a build up of

excess electrons on the surface of the sample.

• Typically the majority of the electrons in the beam go into the

sample and out through the electrical ground of the SEM.

Abnormal contrast, appearance of abnormal lines or shifts/breaks within the image.

2. Specimen charging
• If the specimen is a good conductor and a suitable
connection/pathway exists, this charge flows to ground

• If the ground path is broken, even a conducting specimen quickly

accumulates charge on the surface

SOLUTION FOR Specimen charging

Specimen coating –Gold/ carbon/ platinum

10kV

Charging No charging
3. Specimen damage
Cause: Undamaged specimen
• The loss of electron beam energy in the
specimen occurs mostly in the form of
heat generation at the irradiated point

• Polymer and biological specimens are

easily damaged by the electron beam
(low heat conductivity)

Damaged specimen
Solution:
• Use low accelerating voltage
(this may compromise resolution)
 Summary
1. Introduction to scanning electron microscopy

2. Instrumentation: SEM
o Electron gun
o Condenser lenses
o Scan coils
o Objective lenses
o Detectors
o Vacuum

3. Common problems in SEM

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