4.

MATERIAL CHARACTERIZATION TESTING

SYLLABUS

Macroscopic and Microscopic observations

Principles, Types, Advantages and Limitations, Applications of
1. Optical and Electron microscopy (SEM and TEM)
2. Diffraction techniques
3. Spectroscopic Techniques
4. Electrical and Magnetic Techniques

Material characterization is the process of measuring and determining physical,

chemical, mechanical and micro-structural properties of materials.

Macroscopic Observation

 The first step in any characterization of a material.

 Looking at the material with the naked eye.
 This simple process can yield a large amount of information about the
material such as the colour of the material, its lustre (does it display a
metallic lustre), its shape.
 This investigation clues as to what other tests could be performed to fully
identify the material.

Microscopic Observation

 Microscopy is a technique that, combined with other scientific techniques and

chemical processes, allows the determination of both the composition and
the structure of a material.
 It is essentially the process of viewing the structure on a much finer scale
than is possible with the naked eye.
 It is necessary because many of the properties of materials are dependent on
extremely fine features and defects that are only possible to observe using
one of the following techniques.

1.1 OPTICAL MICROSCOPE

 An optical microscope uses visible light reflected from a specimen through

a single or multiple lenses to form a magnified image of the specimen.

 Construction
 Condenser Lens
 Objective Lens
 Eyepiece Lens
 Light Source
Working

Specimen is placed perpendicular to optic axis of the microscope and illuminated

through objective lens using a white light source (wavelengths ranging from roughly
400 and 700 nanometres).

Light from a source is focussed by a condenser lens & half silvered mirror into a beam
nearly parallel to the optical axis.

Light reflecting from features of the specimen surface;

 That are close to the optical axis enters the objective lens.
 That is inclined to the optical axis moves away from the objective lens.
Final image formed on the eyepiece is bright for features normal to optic axis &
dark for inclined features like pits and grain boundaries.

The eyepiece can be removed and replaced with a camera lens, viewing of the
specimen is then through the camera viewfinder or if the camera can be tethered to a
computer, via the computer monitor.

Limitations

1. The first is that the maximum resolving power is limited by diffraction effects
to approximately 0.2 micrometres.

2.  Limited depth of field.

This limitation means that surfaces with features at different heights such as the
rough surfaces of a fractured specimen cannot be seen in sharp focus at the same time.
This means that flat or polished surfaces are preferred for this technique.

APPLICATIONS

1. To study the macro and microstructure of a material.

2.  To study grains, grain boundaries, phases and inclusions.
3. To analyze the failure of materials.
NOTE:

Bright field illumination is used for producing images with bright background and
dark non-flat structure features (pores, edges, etched grain boundaries).

Dark field illumination is used for producing images with dark background and
bright non-flat structure features (second phase particles & grain boundaries).
PROPERTIES OF MICROSCOPIC LENS

1. Magnification
= (Size of intermediate image formed / actual size of features in
the specimen)
= (V – f) / f

where V- dist. b/w image & lens.

f – focal length of lens.
2. NUMERICAL APERTURE

“RANGE OF USEFUL MAGNIFICATION FOR OBJECTIVE/EYEPIECE SYSTEM”

NA = μ sin θ

Where,
μ – refractive index of medium infront of lens
θ – semi cone angle

3. Resolution

“ABILITY TO OPTICALLY SEPARATE THE FEATURES THAT ARE SO CLOSELY SPACED”

RESOLVING POWER = (0.61 λ) / (μ sin θ)

4. Depth of field

“HEIGHT VARIATION ON A SAMPLE THAT CAN BE ACCOMMODATED ON A COMMON

FOCUS”

Df = 1.22 λ / μ sin θ tan θ

5. Depth of focus

“RANGE OF IMAGE PLANE POSITIONS AT WHICH THE IMAGE CAN BE VIEWED

WITHOUT APPEARING OUT OF FOCUS”

6. Aberration 

“PROPERTY OF OPTICAL SYSTEMS SUCH AS LENSES THAT CAUSES LIGHT TO BE

SPREAD OUT OVER SOME REGION OF SPACE RATHER THAN FOCUSED TO A POINT”. 

ABERRATIONS CAUSE THE IMAGE FORMED BY A LENS TO BE BLURRED OR

DISTORTED, WITH THE NATURE OF THE DISTORTION DEPENDING ON THE TYPE OF
ABERRATION.

IMAGE CONTRAST = (I OBJECT – I BACKGROUND) / (I BACKGROUND )

Where
I – Intensity

IMAGE BRIGHTNESS = NA4 / M2 (REFLECTED LIGHT MICROSCOPE)

= NA2 / M2 (TRANSMISSION LIGHT MICROSCOPE)
Where, NA – Numerical Aperture
M - Magnification

1.2 ELECTRON MICROSCOPY

Electron microscopy refers to a group formed by techniques based on the

analysis of the energies of emitted Electrons

1.2.1 SCANNING ELECTRON MICROSCOPE (SEM)

A scanning electron microscope (SEM) is a type of electron microscope that

produces images of a sample by scanning the surface with a focused beam of electrons.
The electrons interact with atoms in the sample, producing various signals that contain
information about the surface topography and composition of the sample. 

Principle of SEM

The Scanning electron microscope works on the principle of applying kinetic

energy to produce signals on the interaction of the electrons. These electrons are
secondary electrons, backscattered electrons and diffracted backscattered electrons
which are used to view crystallized elements and photons.

Secondary and backscattered electrons are used to produce an image.

The secondary electrons emitted from the specimen detect the morphology &
topography of the specimen while backscattered electrons shows the composition
of the elements of the specimen.

COMPONENTS OF THE SCANNING ELECTRON MICROSCOPE

1. Electron Source – This is where electrons are produced under thermal heat at
a voltage of 1-40kV, the electrons the condense into a beam that is used for the
creation of image and analysis.

There are three types of electron sources that can be used i. e Tungsten
filament, Lanthanum hexa-boride, and Field emission gun (FEG)

2. Lenses – it has several condenser lenses that focus the beam of electrons
from the source through the column forming a narrow beam of electrons that form a
spot called a spot size.

3. Scanning Coil – they are used to deflect the beam over the specimen surface.

4. Detector – Its made up of several detectors that are able to differentiate the
secondary electrons, backscattered electrons, and diffracted backscattered
electrons.

The functioning of the detectors highly depends on the voltage speed, the density
of the specimen.
5. Display device (data output devices)
6. Power supply unit
7. Vacuum system
 WORKING

 The electrons are emitted after thermal energy is applied to the electron source
and allowed to move in a fast motion to the anode, which has a positive charge.

 The beam of electrons accelerated from anode on reaching the specimen, the
specimen surface releases a tiny stream of electrons known as secondary
electrons which are then trapped by a special detector apparatus.

 When the secondary electrons reach and enter the detector, they strike a
scintillator (a luminescence material that fluoresces when struck by a charged
particle or high-energy photon).

 This emits flashes of light which get converted into an electric current by a
photomultiplier, sending a signal to the cathode ray tube. This produces an
image that looks like a television picture that can be viewed and photographed.

 The quantity of secondary electrons that enter the detector is highly defined by
the nature of the specimen i.e raised surfaces receive high quantities of
electrons, entering the detector while depressed surfaces have fewer
electrons reaching the surface and hence fewer electrons enter the detector.

 Therefore raised surfaces will appear brighter on the screen while depressed
surfaces appear darker.

 SPECIMEN PREPARATION

 The specimen does not need special treatment for visualization under the
SEM, even air-dried samples can be examined directly.

 However, microbial specimens need fixation, dehydration, and drying in

order to maintain the structural features of the cells and to prevent collapsing of
the cells when exposed to the high vacuum of the microscope.

 The samples are mounted and coated with thin layer heavy metal elements
to allow spatial scattering of electric charges on the surface of the specimen
allowing better image production, with high clarity.
Applications of the Scanning Electron Microscope (SEM)

1. It is used in a variety of fields including Industrial uses, nano-science studies,

Biomedical studies, Microbiology.
2. Used for spot chemical analysis in energy-Dispersive X-ray Spectroscopy.
3. Used to study the filament structures of microorganisms.
4. Used to study the topography of elements used in industries.
ADVANTAGES

1. They are easy to operate and have user-friendly interfaces.

2. They are used in a variety of industrial applications to analyze surfaces of solid
objects.
3. Some modern SEMs are able to generate digital data that can be portable.
4. It is easy to acquire data from the SEM, within a short period of time of about 5
minutes.
LIMITATIONS

1. They are very expensive to purchase.

2. They are bulky to carry.
3. They must be used in rooms that are free of vibrations and free of
electromagnetic elements.
4. They must be maintained with a consistent voltage.
5. They should be maintained with access to cooling systems.

1.2.2 TRANSMISSION ELECTRON MICROSCOPE

A powerful electron microscope that uses a beam of electrons to focus on a

specimen producing a highly magnified and detailed image of the specimen.

The magnification power is over 2 million times better than that of the light
microscope & SEM, producing the image of the specimen which enables easy
characterization of the image in its morphological features, compositions and
crystallization information.

Among all microscopes both light and electron microscopes, TEM are the most
powerful microscopes used in laboratories. It can magnify a small particle of about
0.2nm, and therefore they have a resolution limit of 0.2nm.

PARTS OF TEM

(1) AN ELECTRON GUN, which produces the electron beam, and the condenser

system, which focuses the beam onto the object,

(2) AN IMAGE-PRODUCING SYSTEM, consisting of the objective lens, movable

specimen stage, and intermediate and projector lenses, which focus the electrons
passing through the specimen to form a real, highly magnified image,

(3) AN IMAGE-RECORDING SYSTEM, which converts the electron image into

some form perceptible to the human eye. The image-recording system usually consists
of a fluorescent screen for viewing and focusing the image and a digital camera for
permanent records.

(4) A VACUUM SYSTEM, consisting of pumps and their associated gauges

and valves, and power supplies are required.

THERMIONIC EMISSION FIELD EMISSION GUN

GUN

WORKING OF TEM

A heated tungsten filament in the electron gun produces electrons that get focus
on the specimen by the condenser lenses.

Magnetic lenses are used to focus the beam of electrons on the specimen. By the
assistance offered by the column tube of the condenser lens into the vacuum creating a
clear image, the vacuum allows electrons to produce a clear image without collision
with any air molecules which may deflect them.

On reaching the specimen, the specimen scatters/transmits the electrons

focusing them on the magnetic lenses forming a large clear image, and if it passes
through a fluorescent screen it forms a polychromatic image.

The denser the specimen, the more the electrons are scattered forming a
darker image because fewer electron reaches the screen for visualization while
thinner, more transparent specimens appear brighter.

If the screen is moved aside, a photographic image can be captured in pixels

forming a permanent image.
 SPECIMEN PREPARATION

Pre-thinning

Dimple grinder – 1mm to 0.1mm

Final –Thinning – a. Electrolytic thinning

b. Ion milling

c. Ultra microtomy

DIMPLE GRINDING ION MILLING

ELECTROLYTIC THINNING

Contrast is provided by heavy metal precipitation in one of three ways.

Positive staining: The object is chemically stained with a solution of the metal salt and
appears dark on a bright background.

Negative staining: The object remains unstained but is embedded in a dried film of the
heavy metal salt. The specimen appears light on a dark background.

Shadowing: For microbial Specimens, a thin layer of heavy metal atoms is deposited on
the specimen by evaporation in a vacuum chamber.
ELECTRON MATTER INTERACTION –TEM ELECTRON MATTER INTERACTION - SEM

TEM IMAGING MODES

APPLICATIONS OF TEM

 TEMs provide topographical, morphological, compositional and crystalline

information.

 The images allow researchers to view samples on a molecular level, making it

possible to analyze structure and texture.
  This information is useful in the study of crystals and metals, but also has
industrial applications.

 TEMs can be used in semiconductor analysis and production and the

manufacturing of computer and silicon chips.

 TEMs identify flaws, fractures and damages to micro-sized objects; this data can
help fix problems and/or help to make a more durable, efficient product.

ADVANTAGES OF TEM

 TEMs offer the most powerful magnification, potentially over one million times
or more.
 TEMs have a wide-range of applications and can be utilized in a variety of
different scientific, educational and industrial fields.
 TEMs provide information on element and compound structure.
 Images are high-quality and detailed.
 TEMs are able to yield information of surface features, shape, size and structure.
 They are easy to operate with proper training.
LIMITATIONS

 TEMs are large and very expensive.

 Laborious sample preparation.
 Samples are limited to those that are electron transparent, able to tolerate the
vacuum chamber and small enough to fit in the chamber.
 TEMs require special housing and maintenance.
 Images are black and white.
 Electron microscopes are sensitive to vibration and electromagnetic fields and
must be housed in an area that isolates them from possible exposure.
 A Transmission Electron Microscope requires constant upkeep including
maintaining voltage, currents to the electromagnetic coils and cooling water.

NOTE:

In SEM, the best resolution might be about 3–4 nm,

In TEM the best resolution is 0.2 nm.

Since SEM’s operate at a much lower accelerating voltage than TEM’s (up to 30kV as

compared to say 200kV in a TEM), the electron wavelength is larger and the aberration

coefficient is also usually larger, hence the resolution is smaller in SEM.

 Scanning Electron Transmission
Microscopes (SEM) Electron
Microscopes
(TEM)
Electron stream Fine, focused beam Broad beam

Image taken Topographical/ Internal structure

surface
Resolution Lower resolution Higher resolution

Magnification Up to 2,000,000 times  Up to 50,000,000

times
Image dimension 3-D 2-D

Sample thickness Thin and thick Ultrathin samples

samples okay only
Penetrates No Yes
sample
Sample Less restrictive More restrictive
restriction
Sample Less preparation More preparation
preparation required required
Cost Less expensive More expensive

Speed Faster Slower

Operation Easy to use More

complicated;
requires training

2.0 DIFFRACTION TECHNIQUES

Diffraction refers to various phenomena that occur when a wave encounters an
obstacle or a slit. It is defined as the bending of waves around the corners of an
obstacle or through an aperture into the region of geometrical shadow of the
obstacle/aperture. The diffracting object or aperture effectively becomes a secondary
source of the propagating wave.

DIFFRACTION GRATING
In optics, a diffraction grating is an optical component with a periodic structure that
splits and diffracts light into several beams travelling in different directions. The
emerging coloration is a form of structural coloration. 

The directions of these beams depend on the spacing of the grating and the
wavelength of the light so that the grating acts as the dispersive element.

Lattice planes are very important in that they can act as diffraction gratings to
radiation that has a wavelength comparable in size to the spacing between planes. Each
crystalline solid has its unique characteristic pattern which may be used as a
"fingerprint" for its identification by XRD method.
Material properties like elasticity, strength, hardness etc depend upon the plane on
which the force is acting.
So researchers are interested to know how atomic planes are oriented in a sample
inorder to test the sample in a particular plane.

BRAGG’S DIFFRACTION
Diffraction from a three-dimensional periodic structure such as atoms in a crystal is
called Bragg diffraction. It is similar to what occurs when waves are scattered from
a diffraction grating. Bragg diffraction is a consequence of interference between waves
reflecting from different crystal planes.
The condition of constructive interference is given by Bragg's law:
nλ = 2d sin θ
where,
λ is the wavelength,
d is the distance between crystal planes,
θ is the angle of the diffracted wave and 
n is an integer known as the order of the diffracted/reflected beam.

TYPES OF DIFFRACTION
1. X-ray Diffraction
2. Electron Diffraction
3. Neutron Diffraction

X RAY DIFFRACTION METHODS

 METHOD λ θ

LAUE METHOD VARIABLE FIXED

ROTATING CRYSTAL FIXED VARIABLE

POWDER METHOD FIXED VARIABLE

LAUE METHOD – PIN HOLE CAMERA METHOD

The Laue method is mainly used to determine the orientation of large single crystals.
White radiation is reflected from, or transmitted through, a fixed crystal.

The diffracted beams form arrays of spots that lie on curves on the film. The Bragg angle
is fixed for every set of planes in the crystal. Each set of planes picks out and diffracts
the particular wavelength from the white radiation that satisfies the Bragg law for the
values of d and q involved. Each curve therefore corresponds to a different wavelength.
The spots lying on any one curve are reflections from planes belonging to one zone.

Laue reflections from planes of the same zone all lie on the surface of an imaginary cone
whose axis is the zone axis. Crystal orientation is determined from the position of the
spots. Each spot can be indexed, i.e. attributed to a particular plane, using special charts.
The Greninger chart is used for back-reflection patterns and the Leonhardt chart for
transmission patterns.

The Laue technique can also be used to assess crystal perfection from the size and shape
of the spots. If the crystal has been bent or twisted in anyway, the spots become
distorted and smeared out.

Experimental

There are two practical variants of the Laue method, the back-reflection and the
transmission Laue method. 
Back-reflection Laue

In the back-reflection method, the film is

placed between the x-ray source and the crystal. The
beams which are diffracted in a backward direction are
recorded.

One side of the cone of Laue reflections is defined by

the transmitted beam. The film intersects the cone,
with the diffraction spots generally lying on an
hyperbola.

Transmission Laue

In the transmission Laue method, the film is

placed behind the crystal to record beams which are
transmitted through the crystal.

One side of the cone of Laue reflections is defined by

the transmitted beam. The film intersects the cone,
with the diffraction spots generally lying on an ellipse.

ROTATING CRYSTAL METHOD

In the rotating crystal method, a single crystal is mounted with an axis normal to a
monochromatic x-ray beam. A cylindrical film is placed around it and the crystal is
rotated about the chosen axis. As the crystal rotates, sets of lattice planes will at some
point make the correct Bragg angle for the monochromatic incident beam, and at that
point a diffracted beam will be formed. Lattice constant of the crystal can be determined
by means of this method; for a given wavelength if the angle at which a reflection
occurs, is known, can be determined.
The reflected beams are located on the surface of imaginary cones. By recording the
diffraction patterns (both angles and intensities) for various crystal orientations, one
can determine the shape and size of unit cell as well as arrangement of atoms inside the
cell.
DEBYE SCHERRER POWDER METHOD

If a powdered specimen is used, instead of a single crystal, then there is no need to

rotate the specimen, because there will always be some crystals at an orientation for
which diffraction is permitted. Here a monochromatic X-ray beam is incident on a
powdered or polycrystalline sample. This method is useful for samples that are difficult
to obtain in single crystal form.
A very small amount of powdered material is sealed into a fine capillary tube made from
glass that does not diffract x-rays. The specimen is placed in the Debye Scherrer camera
and is accurately aligned to be in the centre of the camera. X-rays enter the camera
through a collimator.
The powder diffracts the x-rays in accordance with Braggs law to produce cones of
diffracted beams. When the film is removed from the camera, flattened and processed, it
shows the diffraction lines and the holes for the incident and transmitted beams.
DIFFRACTOMETER
A diffractometer is a measuring instrument for analyzing the structure of a material
from the scattering pattern produced when a beam of radiation or particles (such as X-
rays or neutrons) interacts with it.

X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder,
and an X-ray detector. 
X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the
target material with electrons. When electrons have sufficient energy to dislodge inner
shell electrons of the target material, characteristic X-ray spectra are produced. These
spectra consist of several components, the most common being Kα and Kβ. Kα consists,
in part, of Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as
Kα2. The specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr).
Filtering, by foils or crystal monochrometers, is required to produce monochromatic X-
rays needed for diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a
weighted average of the two is used. Copper is the most common target material for
single-crystal diffraction, with CuKα radiation = 1.5418Å . These X-rays are collimated
and directed onto the sample. As the sample and detector are rotated, the intensity of
the reflected X-rays is recorded. When the geometry of the incident X-rays impinging
the sample satisfies the Bragg Equation, constructive interference occurs and a peak in
intensity occurs. A detector records and processes this X-ray signal and converts the
signal to a count rate which is then output to a device such as a printer or computer
monitor.

The geometry of an X-ray diffractometer is such that the sample rotates in the path of
the collimated X-ray beam at an angle θ while the X-ray detector is mounted on an arm
to collect the diffracted X-rays and rotates at an angle of 2θ. The instrument used to
maintain the angle and rotate the sample is termed a goniometer. For typical powder
patterns, data is collected at 2θ from ~5° to 70°, angles that are preset in the X-ray scan.

3.0 SPECTROSCOPIC TECHNIQUES

Electron spectroscopy refers to a group formed by techniques based on the

analysis of the energies of emitted electrons such
as photoelectrons and Auger electrons.

This group includes XPS or ESCA, EELS, UPS and AES.

These analytical techniques are used to determine the elements and their
electronic structures from the surface of a test sample. Samples can be
solids, gases or liquids.
Chemical information is obtained only from the uppermost atomic layers of
the sample (depth 10 nm or less) because the energies of Auger electrons
and photoelectrons are quite low, typically 20 - 2000 eV.

For this reason, electron spectroscopy is a technique for surface

chemical analysis.

X-ray Photoelectron Spectroscopy (XPS) / Electron Spectroscopy for

Chemical Analysis (ESCA)
X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for
Chemical Analysis (ESCA), is used to determine quantitative atomic composition and
chemistry. A sample is irradiated with monochromatic x-rays, resulting in the emission
of photoelectrons whose energies are characteristic of the elements within the sampling
volume. An XPS spectra is created by plotting the number of electrons verses their
binding energy.

X-ray photoelectron spectroscopy (XPS), also known as electron spectroscopy for

chemical analysis (ESCA), is a technique for analyzing the surface chemistry of a
material. XPS can measure the elemental composition, empirical formula, chemical state
and electronic state of the elements within a material. XPS spectra are obtained by
irradiating a solid surface with a beam of X-rays while simultaneously measuring the
kinetic energy of electrons that are emitted from the top 1-10 nm of the material being
analyzed. A photoelectron spectrum is recorded by counting ejected electrons over a
range of electron kinetic energies. Peaks appear in the spectrum from atoms emitting
electrons of a particular characteristic energy. The energies and intensities of the
photoelectron peaks enable identification and quantification of all surface elements
(except hydrogen).
 XPS SPECTRUM FROM BARIUM OXIDE SHOWING VARIOUS BARIUM AND OXYGEN PEAKS AND A CARBON PEAK

ELECTRON ENERGY LOSS SPECTROSCOPY (EELS)

In electron energy loss spectroscopy (EELS) a material is exposed to a beam

of electrons with a known, narrow range of kinetic energies. Some of the electrons will
undergo inelastic scattering, which means that they lose energy and have their paths
slightly and randomly deflected.

The amount of energy loss can be measured via an electron spectrometer and

interpreted in terms of what caused the energy loss.

Inelastic interactions include phonon excitations, inter- and intra-band

transitions, plasmon excitations, inner shell ionization, and cherenkov radiation.

Electron Energy Loss Spectrometry (EELS) is used for the characterization of inelastic
scattering processes over a wide energy range.
In fact, a TEM offers optimal conditions for performing inelastic scattering experiments:
the beam of electrons can be focussed down to very small probe sizes and the scattering
properties can be investigated at very high spatial resolution while at the same time,
information about the geometric structure of the sample is provided by the imaging
capabilities of a TEM.

In addition, the electron gun provides a source of close to mono energetic electrons. One
therefore simply needs to analyze the amount of energy the probing electron has lost
during its passage through the sample. 

The energy loss spectrum is then generated by recording the number of electrons that
have lost a certain amount of energy and plotting this over the energy lost. As such, the
recorded spectrum resembles the probability of an inelastic interaction as a function of
the transferred energy.

The main advantages of EELS are the much better energy resolution and a higher
sensitivity for light elements.

In general, an EELS spectrum can be divided into:

Zero loss,
Low loss and
Core loss region.
The zero loss is the most intense feature and represents electrons that passed the
sample without loosing energy plus those which have excited phonon modes for which
the energy loss is less than the experimental resolution.

Phonons are lattice vibrations that mean heating of the specimen.

Plasmon and valence band excitations appear at low energy losses up to about 50 eV
while core shell excitations appear at atom characteristic ionization energies at higher
energy loss.

Plasmon are longitudinal oscillations of free electrons which decay either in photons or
phonons. Lifetime of plasmon is only 10-15s.

The whole range therefore contains valuable information not only about the elemental
composition, but also about the electronic, optical and mechanical properties of a
material.
AUGER ELECTRON SPECTROSCOPY (AES)

Auger Spectroscopy identifies chemical elements by measuring KE of

Auger electrons

Auger electron spectroscopy (AES) is one of the most commonly employed surface
analysis techniques. It uses the energy of emitted electrons to identify the elements
present in a sample, similar to X-ray photoelectron spectroscopy (XPS). The main
difference is that XPS uses an X-ray beam to eject an electron while AES uses an electron
beam to eject an electron. In AES, the sample depth is dependent on the escape energy
of the electrons. It is not a function of the excitation source as in XPS. In AES, the
collection depth is limited to 1-5 nm due to the small escape depth of electrons, which
permits analysis of the first 2 - 10 atomic layers. In addition, a typical analysis spot size
is roughly 10 nm.

Like XPS, AES measures the kinetic energy (Ek) of an electron to determine its binding
energy (Eb). The binding energy is inversely proportional to the kinetic energy.

Limitations
1. While AES is a very valuable surface analysis technique, there are limitations. Because
AES is a three-electron process, elements with less than three electrons cannot be
analyzed. Therefore, hydrogen and helium cannot be detected. Nonetheless,
detection is better for lighter elements with fewer transitions. The numerous transition
peaks in heavier elements can cause peak overlap, as can the increased peak width of
higher energy transitions.

2. Another limitation is sample destruction. Although focusing of the electron beam can
improve resolution; the high-energy electrons can destroy the sample.

Applications
1. AES is widely used for depth profiling. Depth profiling allows the elemental
distributions of layered samples 0.2 – 1 μm thick to be characterized beyond the escape
depth limit of an electron.

2. AES is commonly employed to study film growth and surface-chemical composition,

as well as grain boundaries in metals and ceramics.

3. It is also used for quality control surface analyses in integrated circuit production
lines due to short acquisition times. 

AES survey spectrum (red) and differentiated spectrum (black) of an oxidized Fe-Cr-Nb alloy

ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY (UPS)

Ultraviolet photoelectron spectroscopy (UPS) refers to the measurement of

kinetic energy spectra of photoelectron emitted by molecules which have
absorbed ultraviolet photons, in order to determine molecular
orbital energies (DOS) in the valence region.

UV- Spectroscopy is deals with the study of absorption of UV radiations

ranges from 200nm to 400nm.
Electrical and Magnetic Techniques

This includes electrical and magnetic methods for characterizing materials

SCANNING TUNNELING MICROSCOPY - Electrical Technique

ATOMIC FORCE MICROSCOPY - Magnetic Technique

SCANNING TUNNELING MICROSCOPY

The Scanning tunnelling microscopy is an extremely sensitive method for imaging
surfaces at the atomic level. It is based on the principle of the quantum tunnelling.

Principle
When a conducting tip is brought near the surface of the specimen, a voltage difference
is applied which would allow the passage of electrons (tunnelling) through the vacuum
between them. This would result in the tunnelling current.
The tunnelling current is the function of tip position, applied voltage and local density
state of the specimen.

It = V. e- c d

EXPERIMENTAL SETUP
It utilizes a tiny probe that has a sharp conducting tip made up of Platinum-Iridium (Pt-
Ir) or tungsten. It can move in three dimensions over the surface of the specimen. The
two dimensions, i.e., x and y represent the area of the specimen, and thus it would give
the idea of scanning the surface of the specimen. The z-dimension would represent the
distance between the tip and the surface ie. Stand-off distance.

A small tunneling current flows between the tip and the surface of the specimen when
the tip and the sample are connected to a voltage source. If the tip of the probe and the
surface is close enough and the surface is electrically conductive, then the electrons
would tunnel from the probe to the sample. This current can be measured. The
magnitude of the current would depend on the distance between the tip and surface ie.,
The tunneling depends on the distance. The distance is very small nearly few
Angstroms. So, even small irregularities in the surface/size will affect the rate of
electron tunneling.
In order to keep the current constant, the instrument is so designed that the tip can
move in the z-dimension. Therefore, the movement of the tip in the z-dimension can be
recorded which would give the idea about the surface of the specimen. The movement
of the tip is a function of the tunneling current and is highlighted on the video screen.

APPLICATION
A scanning tunneling microscope(STM) can provide atomic‐resolution images of
samples in ultra‐high vacuum, moderate vacuum, gases including air at atmospheric
pressure, and liquids including oil, water, liquid nitrogen, and even conductive
solutions.

Advantages

STMs give 3D profile of a surface, which allows examining a multitude of characteristics,

including roughness, surface defects and determining things about the molecules such
as size and conformation.

Capable of capturing much more detail than lesser microscopes. This helps better
understand the subject of their research on a molecular level. 

Disadvantages
The two major downsides to using STMs are:

STMs can be difficult to use effectively. There is a very specific technique that requires a
lot of skill and precision. STMs require very stable and clean surfaces, excellent
vibration control and sharp tips.

STMs use highly specialized equipment that is fragile and expensive.

 ATOMIC FORCE MICROSCOPY

- FOR TOPOGRAPHY MEASURMENT

- ie FOR SHORT FIELD INTERACTION
AFM is quite similar to the scanning tunnelling microscopy. Here also, It can image the
surface at the atomic-scale resolution.

However, unlike the scanning tunnelling microscopy, we do not require a conducting

material near the surface. The tip feels a chemical attraction (or repulsion) when
brought near the surface. The force between the surface and the tip is made constant
such that it would not harm the surface of the specimen.

WHAT PRODUCES THE FORCE?

It is because of the electrostatic, magnetic and Van der waals interactions between the
tip and the sample produces the force. To keep this force constant, the cantilever
holding the crystal would move up and down in the Z-axis.

Thus, when there is an elevation or depression in the surface, the cantilever would
automatically move up or down. While scanning the surface, the Cantilever also move
across the plane (i.e. X and Y axis). Hence we get the three-dimensional image of the
surface of the specimen.

The surface can be visualised on the screen. The deflection in the cantilever is tracked
by the laser light. The laser light is imposed on the cantilever and if cantilever moves up
or down, the laser would also deflect due to its movement. Thus, the elevation and
depression of the surface at the atomic level can be studied by this method. 
There are three imaging modes:

1. Contact mode

In the contact mode, the force between the tip and the surface is kept constant.
When the tip encounters obstacles, the cantilever would deflect upwards and
downwards and the probe will spot in anyone quadrant instead of detector
centre.

SOFT SAMPLES WILL BE DAMAGED ALSO THE PROBE TIP.

2. Non-contact mode

SHIFT IN FREQUENCY DUE TO DEPTH VARIATION INDICATES TOPOGRAPHY

3. Oscillating mode/tapping mode (produces cushioning effect)

NO DAMAGE TO SOFT SAMPLES

COMBINATION OF ABOVE TWO METHODS

PHASE CHANGE IN SIGNALS WILL INDICATE TOPOGRAPHY.

IN MAGNETIC AFM THE MAGNETIC PROBE/CANTILEVER TIP IS COATED WITH THIN

FERROMAGNETIC FILM.

THE INTERACTIVE FORCE BETWEEN MAGNETIZED TIP AND MAGNETIC PROPERTIES

OF THE SPECIMEN REVEALS THE SURFACE TOPOGRAPHY.

Magnetism is due to moving charges (current). If an atom has an even number of

electrons, the electrons cancel each other out. If it has an odd number there's one
electron whose motion isn't cancelled, and that's what gives the metal magnetic
properties.
 Advantages
 Easy to prepare samples for observation
 It can be used in vacuums, air, and liquids.
 Measurement of sample sizes is accurate
 It has a 3D imaging
 It can be used to study living and nonliving elements
 It can be used to quantify the roughness of surfaces
 It is used in dynamic environments.

Disadvantages 
 It can only scan a single nano-sized image at a time of about 150x150nm.
 They have a low scanning time which might cause thermal drift on the sample.
 The tip and the sample can be damaged during detection.
 It has a limited magnification and vertical range.

Applications
 Identifying atoms from samples
 Evaluating force interactions between atoms
 Studying the physical changing properties of atoms
 Studying the structural and mechanical properties of protein complexes and assembly,
such as microtubules.
 Differentiate cancer cells and normal cells.

******