Introduction to Nanotechnology

LECTURE- 17 and 18

Department of Physics & Nanotechnology

SRM Institute of Science & Nanotechnology, Kattakulathur
Tamil Nadu, India

Introduction to Nanotechnology
UNIT – IV CHARACTERIZATION OF NANOMATERIALS

 Scanning electron microscope (SEM)

Transmission electron microscope (TEM)
Scanning probe microscope (SPM)
Comparing SEM, TEM and SPM for different classes of
nanomaterials.
Coprecipitation reactions exhibit the following characteristics:

 Nucleation is a key step, and a large number of small particles will be formed.

 Secondary processes, such as Ostwald ripeing and aggregation, dramatically affect the
size, morphology, and properties of the products.

 The products are generally insoluble species formed under conditions of

high supersaturation.

 The super saturation conditions necessary to induce precipitation are usually the result of
a chemical reaction.
 Preparation of ZnO nanoparticles using wet chemical precipitation
method.

Procedure:

 Aqueous solution of 0.5M Zinc nitrate and 1M NaOH dissolved

in double distilled water

 Slowly add NaOH (in drops) to Zn (NO3)2 under vigeorous

string for 2 hours at 40 to 50 C

 After sometimes u can visibly see there is white precipitate at

the bottom of the reaction vessel.

 The white precipitate will be removed by filtering the reaction

solution

 Wash the precipitate with distilled water to remove residues

 Anneal the precipitate at 80 0c

MICROSCOPY

7
 Microscopy – introduction
 Microscopy techniques ‐ produce images at greater than life size.

 Magnification,
M = D/d
(D size of feature in the image and d the size of feature in object).

 Resolution:
The shortest distance between two points that can still be visually
distinguished as separate.
• Human eye – 0.1 ‐ 0.2 mm
• Optical (Light) microscope – 0.2mm
• SEM – 1‐2 nm
• TEM – 2 Å

This high resolution is achieved by TEM thanks to the use of a high energy
electron beam.
 Different Types of Microscope
Optical microscopy Scanning probe microscopy
The optical microscope is the most popular and Scanning probe microscopy maps interactions that
commonly seen type in use. In optical microscopy, occur between the probe and the sample. For this, the
visible light and transparent lenses are used to see method uses a very sharp needle, which scans the
objects down to a size of about half a micrometer. This specimen. During the process, it comes into contact or
makes it possible to examine, for example, tiny animals near-contact with the sample surface. On the basis of
such as insects and even single cells. interacting forces between tip and atoms on the surface,
this technique creates atomic scale resolution images.
Electron microscopy
In the 1920s, researchers found out that an electron beam in vacuum behaves much like light does: electrons
also exhibit wave-like properties—however, with a wavelength that is about 100,000 times shorter than that of
visible light. The discovery led to the invention of electron microscopy. Electrostatic lenses are used to
precisely focus either electrons or ions into a sharp beam, which scans the surface. An electron or ion
microscope allows for displaying features as small as 0.05 nanometers, which is 4,000 times better than a
typical light microscope.
 Why electrons?
Wave – Particle Duality
Wave behaviour
• Images and diffraction patterns.
• Wavelength can be tuned by energies.

Charged particle behaviour

• Strong electron‐specimen interactions in comparison to photons due to their charge.
• Chemical analysis is possible as wide range of secondary signal from the sample is produced.

Why not high energy photons?

• Visible light has wavelengths of 400–700 nanometres, larger than many objects of interest.
• Ultraviolet could be used, but soon runs into problems of absorption.
• Even shorter wavelengths, such as X‐rays, exhibit a lack of interaction: both in focusing (nothing interacts
strongly enough to act as a lens) and actually interacting with the sample.
 Why electrons?
• Using the de Broglie’s equation:
h
𝜆=
√ 2𝑚𝑒𝑉
Putting all the known values i.e. the values of h (Planck’s constant), m (mass of the electron)
and e (charge of the electron), the wavelength (nm) of the wave associated to the electron with
applied voltage V is:
1.22
𝜆=
√𝑉
For the electrons with energy 100 keV, l~ 0.003 nm !!
Can we ever achieve this resolution of 0.003 nm?
Why not?? Only if, our lenses are perfect. Which rarely happens!

The maximum resolution so far is 0.2 nm.

To improve the resolution, the electromagnetic lenses have to be perfect.
 Why electrons?
 Magnification range:
Electron microscopes offer a very high magnification range, typically in the range 10 - 500,000 times
for SEM, and 2000 to 1 million times for TEM. This enables characterization of microstructures at
many different length scales, from micro- to nanoscale, within an imaging session.

 High resolution:
The main advantage of electron microscopy is the high image resolution compared to light microscopy.

 Electron generated signals: A major advantage of using electrons rather than light is that because
electrons have negative charge they interact very strongly with atoms. Electron interactions with the
specimen lead to a wide range of phenomena which generate emission of signals from the specimen.

 Note that, magnification is making the image bigger, whereas resolution is the ability to distinguish the
features of the object in the image. High magnification is useless if the microscope operating conditions
have not been optimized to achieve high resolution.
 Interaction of electrons with matter
(Primary electrons)

Signals generated when

a high‐energy beam of
electrons interacts with
a thin specimen.

Secondary electrons: Electron-

Electrons with kinetic sample
energy produced by interaction
primary electron – volume
matter interactions. SE
emission occurs when
they escape from the
sample.

Fundamentals of Nanoscience & Nanotechnology/ March 29, 2021 / Dr. Bhaskar Ch. Behera 13
 Types of Electron Microscopes
SEM microscopes are designed primarily to examine material surfaces
(like reflection light microscopes), whereas TEM microscopes are
primarily designed to examine the internal structure of specimens (like
transmission light microscopes).
Scanning Electron Microscope Transmission Electron Microscope

Serial collection of data points in SEM Parallel image acquisition in TEM

SCANNING ELECTRON
MICROSCOPY (SEM)

15
 Scanning Electron Microscope (SEM)
 The scanning electron microscope (SEM) uses a focused beam of high-energy electrons to
generate a variety of signals at the surface of solid specimens.
 The signals that derive from electron-sample interactions reveal information about the sample
including external morphology (texture), chemical composition, and crystalline structure and
orientation of materials making up the sample.
 In most applications, data are collected over a selected area of the surface of the sample, and a
2-dimensional image is generated that displays spatial variations in these properties. Areas
ranging from approximately 1 cm to 5 microns in width can be imaged in a scanning mode
using conventional SEM techniques (magnification ranging from 20X to approximately
30,000X, spatial resolution of 50 to 100 nm).
 The SEM is also capable of performing analyses of selected point locations on the sample; this
approach is especially useful in qualitatively or semi-quantitatively determining chemical
compositions (using Energy Dispersive X-Ray Analysis (EDX)).
 Scanning Electron Microscope (SEM)
The detector
thermionic
signal is
emission gun synchronized
or field with known
emission gun. location of the
beam on the
specimen, and
The electron the signal
beam is intensity is used
focused to a to modulate the
spot, and is corresponding
image pixel.
scanned
The signals
sequentially collected in
across the series are
specimen. At combined to
each location, form an image
signals are
emitted from
the specimen Everhart-
and collected Thornley
by detectors. detector
Fundamentals of Nanoscience & Nanotechnology/ March 29, 2021 / Dr. Bhaskar Ch. Behera 17
 HOW THE SEM WORKS
 The SEM uses electrons instead of light to form an image.
A beam of electrons is produced at the top of the microscope by heating of a metallic
filament.
The electron beam follows a vertical path through the column of the microscope. It makes
its way through electromagnetic lenses which focus and direct the beam down towards the
sample.
 Once it hits the sample, other electrons ( backscattered or secondary ) are ejected from the
sample.
Detectors collect the secondary or backscattered electrons, and convert them to a signal
that is sent to a viewing screen similar to the one in an ordinary television, producing an
image.
CHARACTERISTIC INFORMATION: SEM
 Topography:
The surface features of an object or "how it looks", its texture; direct relation between these
features and materials properties
 Morphology:
The shape and size of the particles making up the object; direct relation between these
structures and materials properties
 Composition:
The elements and compounds that the object is composed of and the relative amounts of
them; direct relationship between composition and materials properties
 Crystallographic Information:
How the atoms are arranged in the object; direct relation between these arrangements and
material properties.
 HOW DOES IT LOOKS LIKE

AFM Cantilever Ant Blood Cells

Tip Head

Diamond Thin Microstructure of a plain carbon Calcium Phosphate

Film steel Crystal
 ELECTRON GUNS
 Electron guns are typically one of TWO types.
1) THERMIONIC GUNS
2) FIELD EMISSION GUNS

THERMIONIC GUNS:
 Which are the most common type, apply thermal
energy to a filament to coax electrons away from
the gun and toward the specimen under
examination.
 Usually made of tungsten, which has a high
melting point
 ELECTRON GUNS

FIELD EMISSION GUNS:

Create a strong electrical field to pull
electrons away from the atoms they are
associated with.
 Electron guns are located either at the very
top or at the very bottom of an SEM and
fire a beam of electrons at the object under
examination.
These electrons don't naturally go where
they need to, however, which gets us
to the next component of SEMs.
 CONDENSER LENSES
 Just like optical microscopes, SEMs use
Condenser lenses to produce clear and detailed
images.
The Condenser lenses in these devices,
however, work differently.
For one thing, they aren't made of glass.
Instead, the Condenser lenses are made of
magnets capable of bending the path of
electrons.
 By doing so, the Condenser lenses focus and
control the electron beam, ensuring that the
electrons end up precisely where they need to
go.
 OBJECTIVE APERTURE

The objective aperture arm fits above the

objective lens in the SEM.
It is a metal rod that holds a thin plate of metal
containing four holes.
By moving the arm in and out different sized
holes can be put into the beam path.
 An aperture holder: This arm holds a thin
metal strip with different sized holes that line
up with the larger holes.
The metal strip is called an Aperture strip.
 CHAMBER
 The sample chamber of an SEM is where
researchers place the specimen that they are
examining.
 Because the specimen must be kept extremely
still for the microscope to produce clear images,
the sample chamber must be very sturdy and
insulated from vibration.
 In fact, SEMs are so sensitive to vibrations that
they are often installed on the ground floor of a
building.
 They also manipulate the specimen, placing it at
different angles and moving it so that researchers
don't have to constantly remount the object to take
different images.
 SIGNALS FROM THE SAMPLE

Incoming electrons
Secondary electrons
Auger electrons
Backscattered Cathodo-
electrons luminescence (light)

X-rays

Sample
 SECONDARY ELECTRONS (SE)

 Generated from the collision between the incoming electrons and

the loosely bonded outer electrons

 Low energy electrons (~10-50 eV)

 Only SE generated close to surface escape (topographic

information is obtained)
 BACKSCATTERED ELECTRONS (BSE)

 A fraction of the incident electrons is

retarded by the electro- magnetic field of the

nucleus and if the scattering angle is greater
than 180° the electron can escape from the
surface
 High energy electrons

 Fewer BSE than SE

 DETECTORS
 Various types of detectors are there in SEM.

 These devices detect the various ways that the electron beam interacts with
the sample object.

 For instance, Everhart-Thornley detectors register secondary electrons,

which are electrons dislodged from the outer surface of a specimen. These
detectors are capable of producing the most detailed images of an object's
surface.

 Other detectors, such as backscattered electron detectors and X-ray detectors,

can tell researchers about the composition of a substance.
 VACUUM CHAMBER

 SEMs require a vacuum to operate.

 Without a vacuum, the electron beam generated by the electron
gun would encounter constant interference from air particles in
the atmosphere.
 Not only would these particles block the path of the electron
beam, they would also be knocked out of the air and onto the
specimen, which would distort the surface of the specimen.
 Key Features of SEM
 Electrons: The electron gun in an SEM typically accelerates electrons through 1 – 30 kV
accelerating voltage.

 Vacuum: The pressure inside the SEM chamber is usually low vacuum 0.1 – 10-4 Pa.

 Specimen: SEM can take specimens of up to 3 – 20 cm in diameter depending on the specimen

stage installed in the chamber. Attachment of the SEM specimen to the stage is flexible with a
wide range of specimen holders available, frequently in the form of flat metal disks called
specimen stubs.

 Control of the electron beam: Electromagnetic lenses are used to focus the electrons into a
beam, adjust beam astigmatism, move the beam across the specimen, and to scan the beam to
generate images.
 Working Principle of SEM

A Scanning Electron Microscope (SEM) uses focused beams of electrons to render high

resolution, three-dimensional images. These images provide information on:

 topography

 morphology

 composition
 The electron beam scans the sample in a
raster-pattern.
 electrons get reflected on the surface or even
ionize atoms within the sample by liberating
electrons.
 These so-called secondary electrons, as well
as the backscattered electrons, can serve as
signal to build up the final image.
 SEM images represent the morphology of a
sample and can also reconstruct quasi-three-
dimensional views of the sample surface.
 Therefore, the technique is basically used to
obtain a high-resolution picture of surface
features and allows conclusions about the
distribution of different chemical elements
within the sample.
 Scanning Electron Microscope (SEM)

x40,000

x5000

Scanning Electron Microscopy allows

direct observations of topography and
morphological features with high
resolution and depth of field than optical
microscope.
x100,000
Fundamentals of Nanoscience & Nanotechnology/ March 29, 2021 / Dr. Bhaskar Ch. Behera 34
SEM image of Fluorescent magnetic particles Optical image of Fluorescent magnetic particles

Polydisperse PLGA nanoparticle

 ADVANTAGES
 Advantages of a Scanning Electron Microscope include its wide-
array of applications, the detailed three-dimensional and
topographical imaging and the versatile information garnered from
different detectors.
 SEMs are also easy to operate with the proper training and
advances in computer technology and associated software make
operation user-friendly.
 Although all samples must be prepared before placed in the
vacuum chamber, most SEM samples require minimal preparation
actions.
 DISADVANTAGES
 The disadvantages of a Scanning Electron Microscope start with the size and
cost.

 SEMs are expensive, large and must be housed in an area free of any possible
electric, magnetic or vibration interference.

 Maintenance involves keeping a steady voltage, currents to electromagnetic

coils and circulation of cool water.

 SEMs are limited to solid, inorganic samples small enough to fit inside the
vacuum chamber that can handle moderate vacuum pressure.
 APPLICATIONS
 SEMs have a variety of applications in a number of scientific and industry-related
fields, especially where characterizations of solid materials is beneficial.
 In addition to topographical, morphological and compositional information, a
Scanning Electron Microscope can detect and analyze surface fractures, provide
information in microstructures, examine surface contaminations, reveal spatial
variations in chemical compositions, provide qualitative chemical analyses and
identify crystalline structures.
 In addition, SEMs have practical industrial and technological applications such as
semiconductor inspection, production line of miniscule products and assembly of
microchips for computers.
 SEMs can be as essential research tool in fields such as life science, biology,
gemology, medical and forensic science, metallurgy.
 EDX/EDAX
 Energy Dispersive X-Ray Analysis (EDX), referred to as EDS or
EDAX, is an x-ray technique used to identify the elemental composition
of materials.

 The Energy Dispersive X-ray (EDX) microanalysis is a technique of

elemental analysis associated to electron microscopy based on the
generation of characteristic X-rays that reveals the presence of elements
present in the specimens.

 The way EDX analysis works is that the electron beam hits the inner
shell of an atom, knocking off an electron from the shell, while leaving
a positively charged electron hole. When the electron is displaced, it
attracts another electron from an outer shell to fill the vacancy. As the
electron moves from the outer higher-energy to the inner lower-energy
shell of the atom, this energy difference can be released in the form of
an X-ray. The energy of this X-ray is unique to the specific element and
transition.
ZnO
nanoparticle

Fe Doped ZnO
nanoparticle
Characterization using SEM and EDS.

 Morphology SEM

 Average size of the particle

 Elemental composition using EDS

Thank you for your attention