Materials Characterization

Dr. Asma Salman

 Materials paradigm
• Processing
• Structure
• Properties
• Performance

Material is defined as a substance (most often a solid, but other condensed phases
can be included) that is intended to be used for certain applications
 Materials paradigm
• Properties
Physical, Chemical, Thermal, Mechanical, Manufacturing,
Magnetic, Electrical etc.
• Processing
(1) Shaping processing
Solidification, particulate, deformation
(2) Property enhancing (heat treatments, sintering)
(3) Surface processing operations
cleaning, surface treatments ( mechanical, diffusion),
coating deposition processes
• Structure
• Characterization Techniques
• Performance/Applications
 Characterization
Characterization
A scientific way to examine the structure of a material
Microscopy
Prob and map surface and sub- surface structure of a material
Optical microscopy, Scanning Electron Microscopy (SEM),
Transmission Electron Microscopy (TEM), Atomic Force Microscopy
(AFM),
Macroscopic Techniques
Mechanical testing
Thermal analysis
Differential Thermal Analysis (DTA), Thermo Gravimetric Analysis
(TGA)
Spectroscopy
Compositional Analysis Techniques
Chemical composition, chemical compositional variations Techniques
includes
Energy Dispersive X-Ray Spectroscopy (EDX), Wavelength
Dispersive Spectroscopy (WDX), X-Ray Diffraction Analysis( XRD),
X-Ray Photoelectron spectroscopy (XPS)
 Microscopy
• Magnifying power is defined as the ratio
between the dimensions of the image and
the object.
• The process of magnification can occur in
lenses, telescopes, microscopes and even
in slide projectors
• Resolving power is the capacity of an
instrument to resolve two points which are
close together.
• An optical
instrument used for
viewing very small
objects, such as
mineral samples or
animal or plant
cells, typically
magnified several
hundred times.
 Light
Microscope
• The light microscope, so
called because it employs
visible light to detect small
objects, is probably the
most well-known and well-
used research tool in
biology.
• The condenser lens is
responsible for formulating
the beam shape and size.
• The objective lens is
responsible for image
formulation and focusing.
 Light Microscope vs Electron
Microscope
• Both light microscopes and electron microscopes use radiation (light or electron
beams) to form larger and more detailed images of objects (e.g. biological
specimens, materials, crystal structures, etc.) than the human eye can produce
unaided.
• An electron microscope is a microscope that uses beams of electrons instead of rays
of visible light to form highly magnified images of tiny areas materials specimens.
• Comparing light , electron microscopes is more complicated
• There are different types of electron microscopes.
• The two main types of electron microscope are

– The Transmission Electron Microscope (TEM) and

– Scanning Electron Microscope (SEM).

• Scanning Electron Microscopes (SEM) use focused beam of electrons, scanning in

vacuum the specimen surface, imaging one point at a time.
• The interaction of the electron beam with every point of the specimen surface is
registered, forming the entire image.
Depth of Field or Depth of
Focus

OM Image SEM Image

 Scanning Electron Microscope
• The scanning electron microscope (SEM) is the most widely
used type of electron microscope.
• It examines microscopic structure by scanning the surface of
materials with much higher resolution and much greater depth of
field.
• An SEM image is formed by a focused electron beam that scans
over the surface area of a specimen.
• The most important feature of an SEM is the three-dimensional
appearance of its images because of its large depth of field.
Magnification up to 100,000 X Resolution up to 10 nm
• An SEM system obtain chemical information from a specimen by
using various techniques, including by equipping the X-ray energy
dispersive spectrometer (EDS).
Sample loading
SEM- Vacuum Environment
There are many reasons for requiring a
vacuum in an SEM. If the filament were
surrounded by air, it would quickly burn out,
like a light bulb. If the column were full of air,
the electrons would collide with the gas
molecules and never reach the sample. If
gas molecules react with the sample different
compounds could form and condense on the
sample. This can lower the quality of the
image. A good vacuum is required (10-7 torr)
for SEM.
The electron beam, which typically
has an energy ranging from
0.2 keV to 40 keV, is focused by
one or two condenser lenses to a
spot about 0.4 nm to 5 nm in
diameter. The beam passes
through pairs of scanning coils or
pairs of deflector plates in the
electron column, typically in the
final lens, which deflect the beam
in the x and y axes so that it scans
in a raster fashion over a
rectangular area of the sample
surface.
 SEM Sample Charging
• Sample charging is a common problem in
SEM imaging. Charging occurs when
there is no conducting path for electrons to
flow from the sample surface to ground,
typically the sample holder. Sample
charging causes all kinds of problems
such as drift, blur, and low contrast. In
other words, sample charging creates
blurry and/or false images.
 SEM Sample Charging
Charging is a problem because
electrons are repelled by other
electrons. SEM images are generated
by scanning an electron beam across
the sample. This effectively adds
electrons to the sample. If the electrons
remain on the sample, it will repel
electrons from the incoming beam. This
usually looks like the sample is moving
and/or the image is blurring.
SEM Sample Charging
 SEM Sample Charging
Non conducting sample

Fig.. It schematically illustrates the

emission of secondary electron during
SEM analysis of non-conductive
specimens depending on the coating
conditions.
In Fig.(a), sample is coated fully and
hence the developed charges are
passed to the ground via the
conducting layer for which negative
charges are not accumulated over the
specimen surface
But in case of Fig (b), the number of
the secondary electrons emitted from
the specimen may decrease due to the
decrease of incident electrons landing
to the specimen and hence image
quality is deteriorated.
 Signal Detection in SEM
• The electron signals from each pixel of the
raster are collected by a detector in order
to generate a corresponding point-to-point
image on a display screen.
• To understand signal detection, knowledge
of electron signal types that are useful in
an SEM is necessary:
• Backscattered electrons and
• secondary electrons.
Mechanisms of emission of secondary
electrons, backscattered electrons, and
characteristic X-rays from atoms of the
sample
• When high energy electrons strike a specimen,
they produce either elastic or inelastic scattering.
• Elastic scattering produces the backscattered
electrons (BSEs), which are incident electrons
scattered by atoms in the specimen.
• Inelastic scattering produces secondary electrons
(SEs), which are electrons ejected from atoms in
the specimen.
• BSEs are typically deflected from the specimen at
large angles and with little energy loss; they
typically retain 60–80% of the energy of incident
electrons.
• In contrast, SEs are typically deflected at small
angles and show considerably low energy
compared with incident electrons.
During inelastic scattering, an incident electron
transfers kinetic energy to an electron in a
specimen atom.
Any electron in atoms in the specimen with
sufficient kinetic energy will leave its orbital to
become a secondary electron.
The SE energy is usually in the range of about
3–5 eV.
In terms of usefulness, SEs are the primary
signals for achieving topographic contrast,
while BSEs are useful for formation of
elemental composition contrast.
• Secondary electrons are very useful for
the inspection of the topography of the
sample’s surface
• Secondary electrons originate from the
surface or the near-surface regions of the
sample. They are a result of inelastic
interactions between the primary electron
beam and the sample and have lower
energy than the backscattered electron
• Secondary electrons originate from the
atoms of the sample:

• Backscattered electrons are reflected back

after elastic interactions between the
beam and the sample
• BSE come from deeper regions of the
sample, while SE originate from surface
regions. Therefore, BSE and SE carry
different types of information. BSE images
show high sensitivity to differences in
atomic number: the higher the atomic
number, the brighter the material appears
in the image
 Electron–Specimen Interactions
• Both SEs and BSEs
generated by scattering are
used as signal sources for
forming SEM images.
• However, SEs and BSEs,
which are collected by a
detector, escape from
different locations in the
specimen.
• Figure illustrates the
interaction zone where
electrons scatter under the
specimen surface.
Electron–Specimen Interactions

The zone is usually described as pear-shaped, and

its size increases with the energy of incident
electrons in the probe.
Besides SEs and BSEs, characteristic X-rays are
also produced in the interaction zone, and these are
useful for chemical analysis.
Electron–Specimen Interactions
• In the interaction zone, SEs can escape only from a volume
near the specimen surface with a depth of 5–50 nm, even
though they are generated in the whole pear-shaped zone.
• In contrast, BSEs are the products of elastic scattering, and
they have an energy level close to that of incident electrons.
• Their high energy enables them to escape from a much
deeper level in the interaction zone, from depths of about 50–
300 nm.
• The lateral spatial resolution of an SEM image is affected by
the size of the volume from where the signal electrons
escape.
• As a result, an image formed by SEs should have a better
spatial resolution than that formed by BSEs.
 Traditional detectors
• Secondary electrons: Everhart-Thornley
Detector
• Backscattered electrons: Solid State
Detector
• X-rays: Energy dispersive spectrometer
(EDS)
Secondary electron image of a coating
Comparison of SEM techniques (secondary and Backscattered
images) top : back scattered image bottom: secondary image
 SEM BSE image of an Al/Cu sample,
Copper atoms (higher Z) scatter more electrons back towards the
detector than the lighter aluminum atoms and therefore appear
brighter in the SEM image.
(a) Backscattered cross-sectional image of coating (b)
Backscattered high magnification cross-sectional image of
coating
BSE image
 EDX analysis in SEM
Energy dispersive x-ray spectroscopy, also referred to
as EDX, EDS or EDAX, provides additional
understanding of the surface material during the SEM
analysis process

EDX analysis is used to acquire the elemental

composition of a sample
A method of obtaining an information on the elemental
analysis and it is not chemical - it is physical - by the
energy spectrum.
 Electron – matter interaction
• Most of the scanning electron
microscope signal detection systems
are also built into the column.
• Common signal detectors include
those for
– high energy (backscattered)
electrons,
– low energy (secondary) electrons,
– excited (characteristic) X-rays, and
some other signals.
• The detectors for characteristic X-rays
may be either The electron-matter interaction depicting
– energy-dispersive (EDS) or its different products.
– wavelength-dispersive (WDS)
• In Energy-dispersive spectroscopy (EDS)
The excited photons are collected as a function of their
energy and the spectrum of energy-dependent, photon
intensity is analyzed to determine the chemical
composition.
• In wavelength dispersive spectroscopy (WDS)
The intensity of the excited photoes is collected as a
function of the wavelength.
• EDS detectors collect the excited X-rays simultaneously
over a wide energy range, and are therefore highly
efficient.
 EDS analysis Principle
• Every atom has a unique number of
electrons that reside under normal
conditions in specific positions
• The generation of the X-rays in a SEM is a
two-step process. In the first step, the
electron beam hits the sample and
transfers part of its energy to the atoms of
the sample.
This energy can be used by the
electrons of the atoms to “jump” to an
energy shell with higher energy or be
knocked-off from the atom. If such a
transition occurs, the electron leaves
behind a hole. Holes have a positive
charge and, in the second step of the
process, attract the negatively-charged
electrons from higher-energy shells
When an electron from such a higher-
energy shell fills the hole of the lower-
energy shell, the energy difference of this
transition can be released in the form of
an X-ray. This X-ray has energy which is
characteristic of the energy difference
between these two shells. It depends on
the atomic number, which is a unique
property of every element

X-rays are a “fingerprint” of each element

and can be used to identify the type of
elements that exist in a sample.
• EDS can be used for qualitative (the type of
elements) as well as quantitative (the
percentage of the concentration of each element
of the sample) analysis.
• In most SEMs, dedicated software enables auto-
identification of the peaks and calculation of the
atomic percentage of each element that is
detected.
• One more advantage of the EDX technique is
that it is a non-destructive characterization
technique, which requires little or no sample
preparation.
 EDS analysis- An X-ray
Spectrum
• This is used primarily in order to identify the chemical
elements present from their characteristic X-ray ‘finger
prints.
• Such a spectrum may be collected with the beam
stationary, at a specific location on the sample surface
(point analysis).
• Alternatively, to reduce the effects of contamination build-
up, the spectrum may be collected while the beam is
scanned over a selected area.
• Typical signal collection times that are required to ensure
EDS detection of all the elements that are present in
concentrations exceeding one or two percent are of the
order of 100 s.
 EDS Analysis
The X-ray signal may be displayed in three
distinct formats

An X-ray Point/Area Analysis

An X-ray Line Analysis
An X-ray Elemental Concentration Map
 EDS- Point analysis

Typical EDX spectrum: y-axis

depicts the number of counts
and x-axis the energy of the X-
rays. The position of the peaks
leads to the identification of the
elements and the peak height
helps in the quantification of
each element’s concentration in
the sample.
 EDS- An X-ray Line-scan
• The signal may be in the form of an
entire EDS spectrum, recorded at each
point along the line (full-spectrum
mapping).
• Alternatively one or more characteristic
X-ray energies may be selected.
• In either case, the recorded intensity from
the characteristic X-ray peaks are
displayed as a function of the position of
the electron beam.
EDS/ An X-ray Line-scan
 Elemental Mapping- An X-ray
Chemical Concentration map
• In this case, the incident electron
beam is rastered across a selected
area of the sample, and photon
counts are collected for one or more
energy windows that are
characteristic of the chemical
components of interest.
• The photons detected for a particular
characteristic X-ray emission line are
then displayed as colour coded dots
in a position on the screen that
(a) SEM image
corresponds to the beam Elemental maps of
coordinates as it is scanned over the (b)oxygen, 9c) Zn and
area of the specimen surface chosen (d) Cu
for analysis.
(a) SEM micrograph of the surface coating, (b-d)
elemental maps of titanium, aluminium and oxygen
respectively
 Transmission Electron
microscpe
• A high energy beam of electrons is pass
through a very thin sample, and the
interactions between the electrons and the
atoms can be used to observe features
such as the crystal structure and features
in the structure like dislocations and grain
boundaries
• Magnification 50 million times
• Resolution 0.2 nm
SEM Vs TEM
 Difference Between SEM &
TEM
• SEM
• SEM is based on scattered
electrons
• SEM focuses on the sample’s
surface and its composition.
• SEM shows only the morphology of
samples.
• there is no specific need of cutting
with SEM sample
• SEM has lower resolution than
TEM.
• SEM allows for large amount of
sample to be analyzed at a time
• TEM
• TEM is based on transmitted
electrons.
• whereas TEM provides the details
about internal composition.
• Therefore TEM can show many
characteristics of the sample, such
as morphology, crystallization,
stress or even magnetic domains
• The sample in TEM has to be cut
thinner
• TEM has much higher resolution
than SEM.
• with TEM only small amount of
sample can be analyzed at a time.
 Difference Between SEM &
TEM
• SEM is used for surfaces, • TEM is used for imaging of
powders, polished & etched dislocations, tiny
microstructures, IC chips, precipitates, grain
chemical segregation. boundaries and other defect
• SEM also provides a 3- structures in solids
dimensional image • TEM provides a 2-
• SEM is used for looking at dimensional picture.
surfaces, and backscatter • TEM can observe close to
mode can observe atomical structure as well
compositional differences as obtain crystallographic
(and with EDS obtain information.
chemical differences)
Comparison between Optical, SEM and TEM images
for a samples at different temperature