Unit 5: Nanomaterials and Its Characterization techniques

Nanoscience deals with the study of production, properties and possible applications
of nanomaterials

Nanotechnology is the art and science of controlling and rearranging atoms or

molecules to produce new materials that have entirely new structure with novel
properties for a certain application.

Nanoscale means smaller than 100 nanometer in at least one dimension of an object.

Nanomaterials are the materials which show dramatic change in properties of bulk

material.

Classification of nanomaterials
1) Zero dimensional nanomaterials (0D): These are the material having all the
dimensions within the nanoscale (no dimensions are longer than 100 nm ).
e.g Quantum dot, Nanodot, fullerene
2) One dimensional nanomaterials (1D): These are the material having one
dimension outside the nanoscale (one dimension is longer than 100 nm ).
e.g Nanowire, Nanorod, Nanopiller, Nanotubes, CNT etc.
3) Two dimensional nanomaterials (2D): These are the material having two
dimensions outside the nanoscale (Two dimensions are longer than 100
nm ).e.g Graphene, nanofilms, nanocoatings, nanolayers etc.
4) Three dimensional nanomaterials (3D): These are the material having all the
dimensions outside the nanoscale (All dimensions are longer than 100 nm ).
e.g Bulk powder, diamonds, graphite, dispersion of nanoparticles etc.

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 Classification of Techniques for synthesis of Nanomaterials

There are two general approaches for the synthesis of nanomaterials as shown in
folowing Figure: a) Top- down approach b) Bottom–up approach.

(a) Top-down approach

Top-down approach involves the breaking down of the bulk material into nanosized
structures or particles.
Top-down synthesis techniques are extension of those that have been used for
producing micron sized particles.
Top-down approaches are inherently simpler and depend either on removal or on
division of bulk material or on miniaturization of bulk fabrication processes to
produce the desired structure with appropriate properties.
The biggest problem with the top-down approach is the imperfection of surface
structure.
For example, nanowires made by lithography are not smooth and may contain a lot of
impurities and structural defects on its surface. Examples of such techniques are high-
energy wet ball milling, electron beam lithography, atomic force manipulation, gas-
phase condensation, aerosol spray, etc.

(b) Bottom-up approach

The alternative approach, which has the potential of creating less waste and hence the
more economical, is the ‘bottom- up’.
Bottom-up approach refers to the build-up of a material from the bottom: atom-by-
atom, molecule-by-molecule, or cluster-by cluster.
Many of these techniques are still under development or are just beginning to be used
for commercial production of nanopowders.
Oraganometallic chemical route, revere-micelle route, sol-gel synthesis, colloidal
precipitation, hydrothermal synthesis, template assisted sol-gel, electrodeposition etc,

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are some of the well- known bottom–up techniques reported for the preparation of
luminescent nanoparticals.

Characterization techniques

1. X-ray diffraction (XRD):

X-ray diffraction (XRD) is a powerful non-destructive technique for characterizing

crystalline materials. It provides information on structures, phases, preferred crystal
orientations (texture), volume, unit cell, hkl planes and other structural parameters,
such as average grain size, crystallinity, strain, and crystal defects.
X-ray diffraction peaks are produced by constructive interference of a monochromatic
beam of X-rays scattered at specific angles from each set of lattice planes in a sample.
The peak intensities are determined by the distribution of atoms within the lattice.
Consequently, the X-ray diffraction pattern is the fingerprint of periodic atomic
arrangements in a given material. This review summarizes the scientific trends
associated with the rapid development of the technique of X-ray diffraction over the
past five years related to the field of pharmaceutical industry, forensic science,
geological applications, microelectronics and glass industry, as well as in corrosion

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analysis.

There are some strengths and some limitations of X-ray diffraction (XRD):
Strengths X-ray diffraction (XRD):

1. Powerful and rapid (<20 min) for identification of an unknown mineral.

2. Provides unambiguous mineral determination in most cases.
3. Requires minimal sample preparation.
4. Wide availability of XRD units.
5. Relatively straightforward data interpretation.
Limitations X-ray diffraction (XRD):

1. Homogeneous and single-phase material is best for identification of an

unknown.
2. Access to a standard reference file of inorganic compounds is required.
3. Material, in tenths of a gram quantity, must be ground into a powder.
4. For mixed materials, detection limit is » 2% of sample.
5. For unit cell determinations, indexing of patterns for nonisometric crystal
systems is complicated.
6. Peak overlay may occur and worsens for high angle “reflections”

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 Applications of X-ray diffraction

Determination of unknown solids is critical to studies in Geology, Environmental

Science, Material Science, Engineering and Biology.

1. Microelectronics Industry:
The microelectronics industry uses silicon and gallium arsenide single-crystal
substrates in integrated circuit production; there is a need to fully characterize these
materials using XRD. XRD topography can easily detect and image the presence of
defects within a crystal, making it a powerful non-destructive evaluation tool for
characterizing industrially important single-crystal specimens.
The engineering of strained semiconductor materials represents an important aspect of
the enhancement of complementary metal-oxide semiconductor (CMOS) device
performance required for current and future generations of microelectronic
technology. An understanding of the mechanical response of the silicon (Si) channel
regions and their environment is key to the prediction and design of device operation.
Because of the complexity of the composite geometries associated with
microelectronic circuitry, in situ characterization at a submicron resolution is
necessary to verify the predicted strain distributions. Of the measurement techniques
commonly used for strain characterization, synchrotron-based X-ray micro beam
diffraction represents the best non-destructive method to provide spatially resolved
information.
2. Corrosion Analysis: XRD is the only analytical method that readily provides
information about the phase composition of solid materials. The most important,
versatile, and widely used method for corrosion protection of steelwork is by paint or
organic coatings. Information on the microscopic level for a protective coating is
essential to understand the basic determinants of its attributes and improvement
requirements.
3. Pharmaceutical Industry: In the drug design, discovery, development, and
formulation process, X-ray powder diffraction can help to establish a formulation by
discovering the morphology and the degree of crystallinity, providing unique
polymorph identification, and determining the quantity of each in mixture. With XRD,
nonambient analysis can also be performed to study moisture influence on physical
properties of drugs.
4. Forensic Science: Chemical analysis of forensic “specimens” usually means
identification and/or comparison. However, the specimens differ from most of those
encountered in other situations in that they constitute evidence, and as such should be
preserved. Powder diffraction is a non-destructive process, and is therefore well suited
to forensic analysis. It is also versatile and can be used for analyzing organic,
inorganic, and metallic specimens, and, qualitatively and quantitatively, mixtures of
these materials.
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5. Glass Industry: The glass is X-ray amorphous and does not it give X-ray
diffraction patterns, there are still various uses of XRD in the glass industry. They
include identification of crystalline particles that cause tiny faults in bulk glass and
measurements of crystalline coatings for texture, crystallite size, and crystallinity.

Other applications include:

1. Thin-film analysis
2. Lattice parameter determination
3. Purity/quality control of materials
4. Determination of crystallinity of polycrystalline materials
5. Particle Size Determination

2. Scanning Electron Microscopy (SEM)

A scanning electron microscope (SEM) is an analytical testing method that captures

high-resolution images of objects as small as 15 nanometers.
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

The signals used by an SEM to produce an image result from interactions of the
electron beam with atoms at various depths within the sample. Various types of
signals are produced including secondary electrons (SE), reflected or back-scattered
electrons (BSE), characteristic X-rays and light (cathodoluminescence) (CL),
absorbed current (specimen current) and transmitted electrons. Secondary electron
detectors are standard equipment in all SEMs, but it is rare for a single machine to
have detectors for all other possible signals.

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The major components of the Scanning Electron Microscope include;
1. Electron Source – This is where electrons are produced under thermal heat at
a voltage of 1-40kV. the electrons condense into a beam that is used for the
creation of an image and analysis. There are three types of electron sources that
can be used i. e Tungsten filament, Lanthanum hexaboride, 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 – It’s 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. The display device (data output devices)
6. Power supply
7. Vacuum system

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Working

 The source of the electrons and the electromagnetic lenses are

from tungsten filament lamps that are placed at the top of the column and it is
similar to those of the transmission electron Microscope.
 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 activates the emission of primary scattered (Primary)
electrons at high energy levels and secondary electrons at low-energy levels from
the specimen surface. The beam of electrons interacts with the specimen to
produce signals that give information about the surface topography and
composition of the specimen.
 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 of heavy metal elements to
allow spatial scattering of electric charges on the surface of the specimen allowing
better image production, with high clarity.
 Scanning by this microscope is attained by tapering a beam of electrons back and
forth over a thin section of the microscope. When the electrons reach the
specimen, the surface releases a tiny staw 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 to 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.
Applications of the Scanning Electron Microscope (SEM)
It is used in a variety of fields including Industrial uses, nanoscience studies,
Biomedical studies, industries.

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1. SEM Applications in Semiconductor Inspection: Semiconductor technology
forms the backbone of the global digital infrastructure, with silicon wafers especially
contributing enormously to consumer electronics, telecommunications, photovoltaics,
and so on. Inspecting silicon wafers for morphological and topographical uniformity is
one of the primary SEM applications in modern engineering. Inspectors use what is
known as defect review SEM to magnify the surface of silicon wafers to detect and
characterize defects at specific localities and to subsequently determine what causes
the fault. This feeds back into a constant quality assurance loop with SEM data
providing rich insights for incoming materials screening, process control, and more.

2. Microchip Assembly with SEM: Microchips remain a crucial part of everyday life
the world over, forming the basis of every electronic subsystem at hand. The level of
finite detail and electronic density that manufacturers can achieve with new and
emerging microelectronic systems is incredible, with smaller, lower cost, and more
efficient chipsets spearheading the next generation of networked devices. This comes
with its own unique challenges.

The extremely high resolution of SEM imaging makes it uniquely suited as a

supplementary technique for microchip assembly, providing the three-dimensional
magnifications necessary for advanced SEM applications on the microelectronics
production line.

3.SEM Applications in QA/QC :Lastly, engineering SEM applications stem into

quality assurance and control (QA/QC) at large. The powerful resolution of industrial-
grade SEMs makes it the ideal solution for micro- and nanoscale screening of fibers,
particles, and pigments in high-value applications. Compositional analysis of paint,
for instance, to determine the presence of specific heavy metals, toxic elements, and
desirable pigments are one of a routine production-grade SEM application. This same
level of detail can be applied to synthetic fibers, polymers, and practically a limitless
range of intermediate goods.

4.EOI: More SEM Applications:At Electron Optics Instruments (EOI), we offer a

range of SEM systems for various fields of application.

5. Used for spot chemical analysis in energy-Dispersive X-ray Spectroscopy.

6. Used in the analysis of cosmetic components which are very tiny in size.

7. Used to study the filament structures of microorganisms

8. Used to study the topography of elements used in industries

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Advantages of Scanning Electron Microscope (SEM)
1. They are used in a variety of industrial applications to analyze surfaces of solid
objects
2. Some modern SEMs are able to generate digital data that can be portable
3. It is easy to acquire data from the SEM, within a short period of time of about 5
minutes
4. They are easy to operate and have user-friendly interfaces

3. Transmission electron microscope (TEM)

The transmission electron microscope is a very powerful tool for material science and
engineering. 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 analyse the quality, shape, size and density of quantum wells, wires and
dots.

Their working mechanism is enabled by the high-resolution power they produce

which allows it to be used in a wide variety of fields. It has three working parts which
include:
1. Electron gun
2. Image producing system
3. Image recording system
Electron gun
 This is the part of the Transmission Electron Microscope responsible for
producing electron beams.
 Electrons are produced by a cathode that is a tungsten filament that is V-shaped
and it is normally heated. The tungsten filament is covered by a control grid
known as a Wehnelt cylinder made up of a central hole which lies columnar to the
tube. The cathode lies on top of or below the cylindrical column hole. The cathode
and the control grid are negatively charged with an end of the anode which is
disk-shaped that also has an axial hole.
 When electrons are transmitted from the cathode, they pass through the columnar
aperture (hole) to the anode at high voltage with constant energy, which is
efficient for focusing the specimen to produce an accurately defined image. It also
has the condenser lens system which works to focus the electron beam on the
specimen by controlling the energy intensity and the column hole of the electron
gun.

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 The TEM uses two condenser lenses to converge the beam of electrons to the
specimen. The two condenser lens each function to produce an image i.e the first
lens which has strong magnification, produces a smaller image of the specimen, to
the second condenser lens, directing the image to the objectives.

 Image- Producing system

 Its made up of the objective lens, a movable stage or holding the specimen,
intermediate and projector lenses. They function by focusing the passing electrons
through the specimen forming a highly magnified image.
 The objective has a short focal length of about 1-5mm and it produces an
intermediate image from the condenser which are transmitted to the projector
lenses for magnification.
 The projector lenses are of two types, i.e the intermediate lens which allows great
magnification of the image and the projector lens which gives a generally greater
magnification over the intermediate lens.
 To produce efficient high standard images, the objectives and the projector lenses
need high power supplies with high stability for the highest standard of resolution.

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Image-Recording System
 Its made up of the fluorescent screen used to view and to focus on the image.
They also have a digital camera that permanently records the images captured
after viewing.
 They have a vacuum system that prevents the bombardment or collision of
electrons with air molecules disrupting their movement and ability to focus. A
vacuumed system facilitates the straight movement of electrons to the image.
 The vacuumed system is made up of a pump, gauge, valves and a power supply.
 The image that is formed is called a monochromatic image, which is greyish or
black and white. The image must be visible to the human eye, and therefore, the
electrons are allowed to pass through a fluorescent screen fixed at the base of the
microscope.
 The image can also be captured digitally and displayed on a computer and stored
in a JPEG or TIFF format. During the storage, the image can be manipulated from
its monochromatic state to a colored image depending on the recording apparatus
eg use of pixel cameras can store the image in color.
 The presence of colored images allows easy visualization, identification, and
characterization of the images.
The parts of the TEM mentioned above. To mean:
 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 of 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 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.

Application of TEM

TEM is used in a wide variety of fields From Biology, Microbiology,

Nanotechnology, forensic studies, etc. Some of these applications include:
1. To visualize and study cell structures of bacteria, viruses, and fungi
2. To view bacteria flagella and plasmids
3. To view the shapes and sizes of microbial cell organelles
4. To study and differentiate between plant and animal cells.
5. It’s also used in nanotechnology to study nanoparticles such as ZnO nanoparticles

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6. It is used to detect and identify fractures, damaged microparticles that further
enable repair mechanisms of the particles.

Advantages of TEM

1. It has a very powerful magnification of about 2 million times that of the Light
microscope.
2. It can be used for a variety of applications ranging from basic Biology to
Nanotechnology, to education and industrial uses.
3. It can be used to acquire vast information on compounds and their structures.
4. It produces very efficient, high-quality images with high clarity.
5. It can produce permanent images.
6. It is easy to train and use the Transmission Electron Microscope

Limitations of TEM

1. Generally, the TEMs are very expensive to purchase

2. They are very big to handle.
3. The preparation of specimens to be viewed under the TEM is very tedious.
4. The use of chemical fixations, dehydrators, and embedments can cause the
dangers of artifacts.
5. They are laborious to maintain.
6. It requires a constant inflow of voltage to operate.
7. They are extremely sensitive to vibrations and electro-magnetic movements hence
they are used in isolated areas, where they are not exposed.
8. It produces monochromatic images, unless they use a fluorescent screen at the end
of visualization.
4. Atomic Force Microscope

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 Principle :It is based on measuring the interatomic force.
Construction and working: The AFM consists of a cantilever with a sharp tip (with
a radius of 20 nm) made of silicon or silicon nitride and it scans the sample surface. It
touches the sample with a force of one tenth of a millionth (10-7) of a gram. A laser is
obliquely incident at the end of cantilever. When the tip is brought close to the
surface, it is either repelled or attracted by the surface and the cantilever to which the
tip is attached, bends. The deflection of cantilever is measured using a laser beam
reflected from the top surface of the cantilever and gives topography of the surface.

Applications and Uses of AFM

Currently, AFM is one of the most effective imaging techniques being used at the
nanoscale and subnanoscale level. This technique has been applied to multiple
problems across the field of natural sciences and can record a range of material
surface properties in both liquid media and in air. Disciplines where AFM is used
include:

1. Semiconductor science and technology

2. Thin film and coatings
3. Tribology (surface and friction interactions)
4. Surface chemistry
5. Polymer chemistry and physics
6. Cell biology
7. Molecular biology
8. Energy storage (batter) and energy generation (photovoltaic) materials
9. Piezoelectric and ferroelectric materials

Carbon nanotubes (CNTs)

What are Carbon nanotubes ?
Carbon nanotubes (CNTs) are allotropes of carbon. These cylindrical carbon
molecules have interesting properties that make them potentially useful in many
applications in nanotechnology, electronics, optics and other fields of materials
science, as well as potential uses in architectural fields. They exhibit extraordinary
strength and unique electrical properties, and are efficient conductors of heat. Their
final usage, however, may be limited by their potential toxicity

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Synthesis of CNTs

1.Arc discharge CNTs Can be found in the carbon soot of graphite electrodes during
an arc discharge involving high current. This process yields CNTs with lengths up to
50 microns.

2. Laser Ablation In the laser ablation process, a pulsed laser vaporizes a graphite
target in a high-temperature reactor while an inert gas is inserted into the reactor.
Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon
condenses.

Properties of CNTs

1. Mechanical
2. Electrical
3. Thermal
4. Chemical
5. Mechanical
1. Mechanical (Strength Properties)

• Carbon nanotubes have the strongest tensile strength of any material known.
(50x steel)

• It also has the highest modulus of elasticity (5x steel).

2. Electrical Properties

• If the nanotube structure is armchair then the electrical properties are metallic

• If the nanotube structure is zigzag or chiral, then the electrical properties are
semiconducting with moderate or very small band gap.

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 • In theory, metallic nanotubes can carry an electrical current density of 4×109
A/cm2 which is more than 1,000 times greater than metals such as copper

a) Armchair- parallel to the axis b) Zigzag- oriented in a circle around the axis

c) Chiral- twist to the nanotube

3. Thermal Properties

• All nanotubes are expected to be very good thermal conductors along the tube,
but good insulators laterally to the tube axis.

• It is predicted that carbon nanotubes will be able to transmit up to 6000 watts

per meter per Kelvin at room temperature; compare this to copper, a metal
well-known for its good thermal conductivity, which transmits 385 watts per
meter per K.

• The temperature stability of carbon nanotubes is estimated to be up to 2800 oC

in vacuum and about 750oC in air.

4. Chemical Properties

• Reactivity Increases as most of the reactions takes place at surfaces. Smaller

the diameter of the tube higher is the reactivity.

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