UNIT IV

MATERIAL CHARACTERIZATION TESTING

ELECTRON MICROSCOPE

Working Principle:

An electron microscope uses an ‘electron beam’ to produce the image of the object and
magnification is obtained by ‘electromagnetic fields’; unlike light or optical microscopes, in
which ‘light waves’ are used to produce the image and magnification is obtained by a system of
‘optical lenses’.

It has already been discussed that, the smaller is the wavelength of light, the greater is its
resolving power. The wavelength of green light (=0.55µ) is 1, 10,000 times longer than that of
electron beam (=0.000005µ or 0.05 Å; 1µ = 10,000 Å).

That is why, despite its smaller numerical aperture, an electron microscope can resolve objects as
small as 0.001µ (=10 Å), as compared to 0.2µ by a light microscope. Thus, the resolving power
of an electron microscope is 200 times greater than that of a light microscope. It produces useful
magnification up to X 400,000, as compared to X 2000 in a light microscope. Thus, the useful
magnification is 200 times greater in an electron microscope than that in a light microscope.

There are three types of electron microscopes as described below

(1) Transmission Electron Microscope (TEM):

(2) Scanning Electron Microscope (SEM):

(3) Scanning and Transmission Electron Microscope (STEM):

Transmission Electron Microscope (TEM):

In this microscope, an electron beam from an electron gun is transmitted through an ultra-thin
section of the microscopic object and the image is magnified by the electromagnetic fields. It is
used to observe finer details of internal structures of microscopic objects like bacteria and other
cells.

The specimen to be examined is prepared as an extremely thin dry film or as an ultra-thin section
on a small screen and is introduced into the microscope at a point between the magneti condenser
and the magnetic o bjective
(Figure 4.13).

The point is comparable to the stage of a light microscope. The magnified image may be viewed
on a fluorescent screen through an airtight window or recorded on a photographic plate by an in-
built camera. Modern variants have facility to record the photograph by digital camera.

(2) Scanning Electron Microscope (SEM):

In a scanning electron microscope, the specimen is exposed to a narrow electron beam from an
electron gun, which rapidly moves over or scans the surface of the specimen (Figure 4.13). This
causes the release of a shower of secondary electrons and other types of radiations from the
specimen surface.

The intensity of these secondary electrons depends upon the shape and the chemical composition
of the irradiated object. These electrons are collected by a detector, which generates electronic
signals. These signals are scanned in the manner of a television system to produce an image on a
cathode ray tube (CRT).

The image is recorded by capturing it from the CRT. Modern variants have facility to record the
photograph by digital camera. This microscope is used to observe the surface structure of
microscopic objects.

(3) Scanning and Transmission Electron Microscope (STEM):

It has both transmission and scanning electron microscope functions.

Limitations of Electron Microscopes:

The limitations of electron microscopes are as follows:

(a) Live specimen cannot be observed.

(b) As the penetration power of electron beam is very low, the object should be ultra-thin. For
this, the specimen is dried and cut into ultra-thin sections before observation.
The transmission electron microscope TEM

The transmission electron microscope is a very powerful tool for material science.

A high energy beam of electrons is shone 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.

Chemical analysis can also be performed.

TEM can be used to study the growth of layers, their composition and defects in
semiconductors. High resolution can be used to analyze the quality, shape, size and density of
quantum wells, wires and dots.

The TEM operates on the same basic principles as the light microscope but uses electrons
instead of light.

Because the wavelength of electrons is much smaller than that of light, the optimal
resolution attainable for TEM images is many orders of magnitude better than that from a light
microscope. Thus, TEMs can reveal the finest details of internal structure - in some cases as
small as individual atoms.

Figure 1 - General layout of a TEM describing the path of electron beam in a TEM (Taken from
JEOL 2000FX Handbook)

Figure 2 - A ray diagram for the diffraction mechanism in TEM

Imaging

The beam of electrons from the electron gun is focused into a small, thin, coherent beam
by the use of the condenser lens. This beam is restricted by the condenser aperture, which
excludes high angle electrons.

The beam then strikes the specimen and parts of it are transmitted depending upon the
thickness and electron transparency of the specimen.

This transmitted portion is focused by the objective lens into an image on phosphor
screen or charge coupled device (CCD) camera. Optional objective apertures can be used to
enhance the contrast by blocking out high-angle diffracted electrons.

The image then passed down the column through the intermediate and projector lenses, is
enlarged all the way.

The image strikes the phosphor screen and light is generated, allowing the user to see the
image. The darker areas of the image represent those areas of the sample that fewer electrons are
transmitted through while the lighter areas of the image represent those areas of the sample that
more electrons were transmitted through.

Diffraction

Figure 2 shows a simple sketch of the path of a beam of electrons in a TEM from just
above the specimen and down the column to the phosphor screen.

As the electrons pass through the sample, they are scattered by the electrostatic potential
set up by the constituent elements in the specimen.

After passing through the specimen they pass through the electromagnetic objective lens
which focuses all the electrons scattered from one point of the specimen into one point in the
image plane.

Also, shown in fig 2 is a dotted line where the electrons scattered in the same direction by
the sample are collected into a single point. This is the back focal plane of the objective lens and
is where the diffraction pattern is formed

Specimen Preparation

A TEM specimen must be thin enough to transmit sufficient electrons to form an image
with minimum energy loss.

Therefore specimen preparation is an important aspect of the TEM analysis.

For most electronic materials, a common sequence of preparation techniques is ultrasonic

disk cutting, dimpling, and ion-milling. 

Dimpling is a preparation technique that produces a specimen with a thinned central area
and an outer rim of sufficient thickness to permit ease of handling. 
 Ion milling is traditionally the final form of specimen preparation. In this process,
charged argon ions are accelerated to the specimen surface by the application of high voltage.
The ion impingement upon the specimen surface removes material as a result of momentum
transfer

ADVANTAGES

TEM offer the most powerful magnification,potentially over one million times or more

It have wide range of applications and can be utilized in a variety of different fields

It provide information on element and compound structure

They are easy to operate with proper training

Disadvantages

TEM are large and very expensive

Operation and analysis rewuires special training

TEM require special housing and maintenance

Images are black and white

Applications

TEM is ideal for a number of different fields such as

Life sciences

Nanotechnology

Medical

Forensic analysis

Gemology and metallurgy

SCANNING ELECTRON MICROSCOPE

A scanning electron microscope (SEM) scans a focused electron beam over a surface to

create an image. The electrons in the beam interact with the sample, producing various signals
that can be used to obtain information about the surface topography and composition.

Why use electrons instead of light in a microscope?

Given sufficient light, the human eye can distinguish two points 0.2 mm apart, without
the aid of any additional lenses. This distance is called the resolving power or resolution of the
eye. A lens or an assembly of lenses (a microscope) can be used to magnify this distance and
enable the eye to see points even closer together than 0.2 mm.

A modern light microscope has a maximum magnification of about 1000x. The resolving
power of the microscope was not only limited by the number and quality of the lenses but also by
the wavelength of the light used for illumination.

White light has wavelengths from 400 to 700 nanometers (nm). The average wavelength
is 550 nm which results in a theoretical limit of resolution (not visibility) of the light microscope
in white light of about 200 – 250 nm.

The figure below shows two points at the limits of detection and the two individual spots
can still be distinguished. The right image shows the two points so close together that the central
spots overlap.

The main SEM components include:

 Source of electrons
 Column down which electrons travel with electromagnetic lenses
 Electron detector
 Sample chamber
 Computer and display to view the images

Electrons are produced at the top of the column, accelerated down and passed through a
combination of lenses and apertures to produce a focused beam of electrons which hits the
surface of the sample. The sample is mounted on a stage in the chamber area and, unless the
microscope is designed to operate at low vacuums, both the column and the chamber are
evacuated by a combination of pumps. The level of the vacuum will depend on the design of the
microscope.

Schematic of a Scanning Electron Microscope

 The position of the electron beam on the sample is controlled by scan coils situated above
the objective lens. These coils allow the beam to be scanned over the surface of the sample.

This beam rastering or scanning, as the name of the microscope suggests, enables
information about a defined area on the sample to be collected.

As a result of the electron-sample interaction, a number of signals are produced. These

signals are then detected by appropriate detectors.

Sample-Electron Interaction

The scanning electron microscope (SEM) produces images by scanning the sample with a
high-energy beam of electrons. As the electrons interact with the sample, they produce secondary
electrons, backscattered electrons, and characteristic X-rays.

These signals are collected by one or more detectors to form images which are then
displayed on the computer screen. When the electron beam hits the surface of the sample, it
penetrates the sample to a depth of a few microns, depending on the accelerating voltage and the
density of the sample. Many signals, like secondary electrons and X-rays, are produced as a
result of this interaction inside the sample.

Schematic of electron beam interaction.

The maximum resolution obtained in an SEM depends on multiple factors, like the
electron spot size and interaction volume of the electron beam with the sample. While it cannot
provide atomic resolution, some SEMs can achieve resolution below 1 nm. Typically, modern
full-sized SEMs provide resolution between 1-20 nm whereas desktop systems can provide a
resolution of 20 nm or more.

ADVANTAGES

 Produces detailed three-dimensional and topographical images

 Easy to operate with training

 User-friendly software

 Can perform quick scans (BSE, EDS and SEI analyses can be performed within a few
minutes)

 Samples require a small amount of preparation

DISADVANTAGES

 Expensive to buy and run

 Large (takes up lots of space)

 Needs to be in an environment where there is no electric, magnetic or vibration interference

 Needs a trained operative to prepare the samples and operate the microscope

 Small risk of radiation exposure

 Restricted to samples small enough to fit into the vacuum chamber

 Requires cool water and a steady voltage

APPLICATIONS

 Materials science
 Nanowires for gas sensing
 Semiconductor inspection
 Forensic investigations
 Soil and rock sampling
 Medical science

DIFFRACTION TECHNIQUES

Diffraction methods are used for the identification and also for the quantification of
constituents of crystalline structures. Diffraction patterns are obtained with an object with
crystalline structure is irradiated by X-ray photons, or by other particles (electrons, neutrons,
etc.). The basic principle of diffraction methods is based on the Bragg equation, which defines
the relation between the wavelength of the radiation, the angle of the incident radiation and the
crystal lattice geometry of the object irradiated.

TYPES OF DIFFRACTION TECNIQUES

 X Ray diffraction technique4

 Electron diffraction
 Neutron diffraction

X-ray diffraction is based on constructive interference of monochromatic X-rays and a

crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample. 

The interaction of the incident rays with the sample produces constructive interference
(and a diffracted ray) when conditions satisfy Bragg's Law (nλ=2d sin θ). This law relates the
wavelength of electromagnetic radiation to the diffraction angle and the lattice spacing in a
crystalline sample.

These diffracted X-rays are then detected, processed and counted. By scanning the
sample through a range of 2θangles, all possible diffraction directions of the lattice should be
attained due to the random orientation of the powdered material. Conversion of the diffraction
peaks to d-spacings allows identification of the mineral because each mineral has a set of unique
d-spacings. Typically, this is achieved by comparison of d-spacings with standard reference
patterns.

All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays
are directed at the sample, and the diffracted rays are collected. A key component of all
diffraction is the angle between the incident and diffracted rays. Powder and single crystal
diffraction vary in instrumentation beyond this.

Applications

X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials (e.g. minerals, inorganic compounds).

Determination of unknown solids is critical to studies in geology, environmental science,

material science, engineering and biology.

Other applications include:

 characterization of crystalline materials

 identification of fine-grained minerals such as clays and mixed layer clays that are
difficult to determine optically
 determination of unit cell dimensions
 measurement of sample purity

Strengths
  Powerful and rapid (< 20 min) technique for identification of an unknown mineral
 In most cases, it provides an unambiguous mineral determination
 Minimal sample preparation is required
 XRD units are widely available
 Data interpretation is relatively straight forward

Limitations

 Homogeneous and single phase material is best for identification of an unknown

 Must have access to a standard reference file of inorganic compounds (d-spacings, hkls)
 Requires tenths of a gram of material which must be ground into a powder
 For mixed materials, detection limit is ~ 2% of sample
 For unit cell determinations, indexing of patterns for non-isometric crystal systems is
complicated
 Peak overlay may occur and worsens for high angle 'reflections'

Spectroscopy techniques

Spectroscopy is a general term for the science that deals with the interaction between the various
types of radiation and matter .Therefore, these types of measures are only possible if the
interaction between photons and matter causes some kind of change in one or more properties of
the sample. The electromagnetic spectrum can be divided into regions according to the
wavelength of the radiation, as shown in Figure 1.
TYPES OF SPECTROSCOPIC TECHNIQUES

X-ray

X-rays of sufficient energy are used to excite the inner shell electrons in the atoms of a sample.
The electrons move to outer orbitals then down into the vacated inner shells and the energy in
this de-excitation process is emitted as radiation.

The absorption or emission energies are characteristic of the specific atom and small energy
variations may occur that are characteristic of particular chemical bonding. The X-ray
frequencies can be measured and X-ray absorption and emission spectroscopy is used to
determine elemental composition and chemical bonding.

In X-ray crystallography, crystalline materials are analyzed by studying the way they scatter X-
rays aimed at them. Knowing the wavelength of the incident X-rays allows calculation and
eventually the intensities of the scattered X-rays give information about the atomic positions and
their arrangement within the crystal structure.

Flame

Usually the analyte is in solution form (or converted into one) that is then converted to a free
gaseous form in a multistage process (atomization). This method is often used for metallic
element analytes present at very low concentration ranges.

Atomic Emission Spectroscopy (AE)

This method uses atoms excited from the heat of a flame to emit light. The analysis can be done
with a high resolution polychromator to produce an emission intensity vs. wavelength spectrum
to detect multiple elements simultaneously.

Atomic absorption spectroscopy (AA)

Compared to AE spectroscopy, a flame of lower temperature is used so as not to excite the

sample atoms. Instead, the analyte atoms are actually excited using lamps which shine through
the flame at wavelengths adjusted according to the type of analyte under study. The amount of
analyte present in the study sample is determined based on how much light is absorbed after
passing through the flame.

Spark or arc (emission) spectroscopy

This is used for analyzing solid metallic elements or non-metallic samples made conductive by
being ground with graphite powder. Analysis requires passing an electric spark through it to
produce a heat that excites the atoms. The excited atoms emit light of characteristic wavelengths
which can be detected using a monochromator.

Analysis of these metallic elements in solid samples is qualitative as the spark conditions are not
well monitored on the whole however the recently introduced usage of spark sources involving
controlled discharges yields quantitative data.
Visible/Ultraviolet (UV)

This uses the fact that many atoms are able to emit or absorb visible light. The atoms must be in
a gaseous phase in order to obtain a spectrum just as those obtained in flame spectroscopy. It is
common for visible absorption spectroscopy to be combined with UV absorption spectroscopy in
UV/Vis spectroscopy.

UV spectroscopy can be used to quantify the concentration of protein and DNA in a solution.
Many amino acids (including tryptophan) absorb light in the 280 nm range whilst DNA absorbs
light in the 260 nm range. Using this knowledge indicates the ratio of 260/280 nm absorbance as
a good indicator of the relative purity of a solution in terms of these entities. UV spectroscopy
can also be used to analyze fluorescence from a sample in a form of absorption spectroscopy.

Infrared (IR) and Near Infrared (NIR)

IR spectroscopy is used to show what types of bonds are present in a sample by measuring
different types of inter-atomic bond vibrations at different frequencies. It relies on the fact that
molecules absorb specific frequencies which is dependent on their chemical structure. This is
determined by factors such as the masses of the atoms.

NIR shows a greater penetration depth into a sample than mid-infrared radiation. This indicates a
low sensitivity but also that it allows large samples to be measured in each scan by NIR
spectroscopy with little (if any) sample preparation. It has numerous practical applications that
include: medical diagnosis pharmaceuticals, biotechnology, various analyses (genomics,
proteomic) and chemical imaging of intact organisms, textiles, forensic lab application and
various military applications.

Nuclear magnetic resonance

This is a prominent method for analyzing organic compounds because it exploits the magnetic
properties of certain atomic nuclei to determine the properties (both chemical and physical) of
these atoms or the molecules containing them. It can provide extensive information about the
structure, dynamics, and chemical environment of atoms. Additionally, even different functional
groups are distinguishable, and identical functional groups in differing molecular environments
still give distinguishable signals.

advantages of spectroscopic techniques

the advantages of spectroscopic analytical techniques often include sensitivity, safety,

noninvasiveness and/or remote access, miniaturization, inexpensive running costs, and rapid,
automated sample turnover

applications of spectroscopic techniques

Spectroscopy is used as a tool for studying the structures of atoms and molecules.

Spectroscopy also provides a precise analytical method for finding the constituents in material

having unknown chemical composition.
Absorption spectroscopy measures the loss of electromagnetic energy after it illuminates the
sample under study. For example, if a light source with a broad band of wavelengths is directed
at a vapour of atoms, ions, or molecules, the particles will absorb those wavelengths that can
excite them from one quantum state to another.

Electrical techniques

introduction:

• Electrical property of the materials is one of the most important properties, which helps to
classify the materials. For instance, solids may be classified in terms of their resistivity or
conductivity as conductors, semiconductors or insulators.

• The electrical resistivity, an intrinsic property that quantifies how strongly a given material
opposes the flow of electrical current, can be measured using several ways depending on the
magnitude of the resistance involved in the materials. Two general methods involved for
measuring the resistance of the materials are:

• Two-probe method

• Four-probe method

• Based on the above methods, the materials are ranged over 25 orders of magnitude as shown in
Figure 24.01. We shall discuss the principles involved for the measurements of resistivity in next
few slides.

General Introduction:

Ohm's law: If physical conditions such as temperature, stress, strain remains unchanged in the
materials, then potential difference (V) across two ends of a conductor is proportional to
current (I) flowing through a conductor, i.e.,

           V ∝ I (or)

           V = I R

The constant of proportionality, R, is called resistance of the material.

Resistivity:
At a given constant temperature, the resistance R of the conductor is (i) proportional to its
length (L) and (ii) inversely proportional to its area of cross-section (A), i.e.,

           R ∝ L / A (or)

           R = ρ L / A

The constant of proportionality, ρ, is called resistivity of the material, which is defined as the
resistance offered by a wire of this materials of unit length and unit cross-sectional area.

Units of resistance and resistivity are Ohm (Ω) and Ohm-meter (Ω -m), respectively.

Two-probe method:

Let us consider a long thin wire of length, L and uniform cross section, A or the materials with a
long parallelepiped shape with uniform cross section as shown in Figure 24.02.

Figure 24.02: Schematic of two-probe setup.

The resistivity of the wire can be measured by measuring voltage drop across the wire due to
passage of known current supplied by the battery E through the probes 1 and 2.

The potential difference (V) between the two contacts at the ends of the wire can be measured by
a voltmeter. Therefore, the resistivity of the wire is, i.e.,

In general, we use a multimeter for measuring the resistance of the materials. The typical range
of resistance measured using the multimeter is 1Ω to 2MΩ, but varies with the models and
company. While the two-probe method is a simple and advantageous method for measuring
resistance above 1Ω directly, this method suffers from certain issues.

Two-probe method:
(i) Error due to contact resistance of the measuring leads,

(ii) Materials having random shapes,

(iii) Soldering of the test leads on some materials would be difficult,

(iv) Heating of the leads during soldering may inject additional impurities in materials such as
semiconductors and thereby affecting the intrinsic electrical resistivity largely.

In order to overcome the above problems, four-probe method is widely proposed.

This method provides the measurement of the resistivity of the specimen having the wide variety
of shapes but with uniform cross-section.

The soldering contacts proposed in two-probe method are replaced by pressure contacts to
eliminFour-probe method:

In this method, four probes are utilized to measure the resistance of the samples. For example,
two of the outer probes are used to send the current from the source meter and other two inner
probes are used to measure the voltage drop across the sample.

The typical set up of the four-probe method is shown in Figure 24.03. There are four equally
spaced tungsten metal tips supported by springs at one end to mount the sample surface without
any damage.

Effect of magnetic field on the electrical properties:

As shown in Figure 27.03, the resistance is low when the magnetizations of all the ferromagnetic
layers are parallel and the resistance becomes larger when the magnetizations of the neighboring
ferromagnetic layers are ordered antiparallel.
Figure 27.03: Magnetic multilayers with (a) parallel and (b) antiparallel configurations.

GMR is defined as

where R↑↑ and R↑↓ are the resistance of the films under parallel and antiparallel configurations.

Magnetic techniques

Magnetic property is one of the most important properties, which helps to classify different types
of magnetic materials. For instance, magnetic materials may be classified by their response to
externally applied magnetic fields as diamagnetism, paramagnetism, ferromagnetism,
antiferromagnetism and ferrimagnetism.

• Although the phenomenon of magnetism was known to many ancient civilizations, the first
recorded description is from the Greek Thales of Miletus, who shared the attraction of loadstone
to iron.

• Magnetism arises from charge in motion, whether at the microscopic level through the motion
of electrons in atomic orbitals or at macroscopic level by passing current through a wire. The
magnetization of a material is expressed in terms of density of net magnetic dipole moments,
i.e., M=μtotal  /V. The total magnetic field B in the materials is therefore given
as B=B0 + μ0 M where μ0 is the magnetic permeability of space and B0 is the externally applied
magnetic field.

• If one calculates the magnetic field inside materials using Ampere's law or the Biot-Savart law,
then the term μ0 is replaced by μ with the definition that μ=μ0μr, where μr is called relative
permeability.

• If any materials do not respond to the applied field by showing any magnetization, then the
value of relative permeability is considered to be 1. In such case, another magnetic parameter
called magnetic susceptibility is used to specify how much the relative permeability differs from
1→χ+1= μ.

he magnetic property, an intrinsic property that quantifies how strongly a given material respond
to the applied field, can be measured using several ways depending on the magnitude of the
moment in the materials.

Measurement methods:

The measurement devices can be divided into two general categories:

(i) Vector instruments

(ii) Scalar instruments

Vector Instruments:

Instruments that measure the magnetic-field vector magnitude and direction using one of the
following methods:

(a) Force

(b) Induction coil

(c) Flux gate

(d) Hall effect

(e) Magnetoresistance

(f) SQUID

Scalar Instruments:

Instruments that measure the magnitude of the magnetic-field only

(a) Nuclear Magnetic Resonance (NMR)

(b) Electron Spin Resonance (ESR) or Electron Paramagnetic Resonance (EPR)

In the following lectures, we shall focus on the principle and technical details of various
measurements for understanding the magnetic properties of magnetic materials using above two
category instruments.

Measuring Magnetization by Force:

By taking different types of magnetic materials in the solid form, we can relatively measure the
change in the force resulting from its magnetization.

Consider the magnetic materials having negative and positive susceptibility. As shown in Figure
28.02, taking the materials having negative susceptibility give a repulsive force away from
increasing field, pushing the sample up, while the materials having positive susceptibility give an
attractive force, drawing the material towards the field maximum.

Figure 28.02: Schematic of measuring magnetization by force for magnetic materials having
negative and positive susceptibility.

Measuring Magnetization by Induction Method:

This method depends on the Faraday's law of electromagnetic induction, i.e., the electro motive
force (e.m.f.) induced in a circuit is equal to the rate of change of flux linking the circuit

Φ is the magnetic flux passing through the coil, N is the number of turns in coil

The induced e.m.f. can be enhanced by,

(i) changing the magnetic field strength

(ii) moving a magnet towards or away from the coil,

(iii) moving the coil into or out of the magnetic field,

(iv) rotating the coil relative to the magnet, etc.

The above equation can be rewritten as 

Magnetometers:

Magnetometers are measurement instruments used to measure the magnetization of a magnetic

materials, measure the strength and the direction of the magnetic field at a point in space.

Magnetometers are generally used for measuring the Earth's magnetic field to detect magnetic
anomalies of various types, and also used in military to detect submarines.

In recent days, the magnetometers are used as compasses in consumer devices such as tablet
computers and mobile phones.

Laboratory type magnetometers are used to measure the magnetization (magnetic moment) of a
sample placed inside the magnetometers. We shall cover different types of magnetometers used
for detecting magnetic moment of the samples and see how to obtain various factors by
performing magnetic measurements as a function of applied field, temperature, time.