Introduction to

Nanomaterials

Qaisar
Manzoor
UOL
What are nanomaterials?
The word ‘nano’ is a Greek prefix meaning dwarf
or something very small and depicts one billionth
(10-9) of a unit.

Nano-materials, therefore, refer to the class of

materials with at least one dimension between 1-100
nm.
Nano-materials can be metals, metal oxides,
ceramics, polymers or composites.
Table (1):- The world of small dimensions
Number Name Symbol
0.1 deci d
0.01 centi c
0.001 milli m
0.000 001 micro μ
0.000 000 001 nano n
0.000 000 000 001 pico p
0.000 000 000 000 001 femto f
0.000 000 000 000 000 001 atto a
0.000 000 000 000 000 000 001 zepto z
0.000 000 000 000 000 000 000 001 yocto y
Nanotechnology

“The creation of functional materials, devices and

systems through control of matter on the nanometer
length scale (1–100 nm), and exploitation of novel
phenomena and properties (physical, chemical,
biological) at that length scale”.
In the case of polycrystalline materials, the grain size is
typically of the order of 1–100 microns (1 micron = 10-6
m). Nano-crystalline materials have a grain size of the
order of 1−100 nm, and are therefore 100–1000 times
smaller than conventional grain dimensions, so, they can
no longer be treated as infinite systems and the resultant
boundary effects lead to fascinating and useful
properties, which can be explored and tailored for a
variety of structural and functional applications.
At this scale physical and chemical properties of materials differ
significantly from those at a larger scale
 Number of atoms
 Molecules, nanoparticles, and 1
Molecules
bulk materials can be 10

distinguished by the number

102
of atoms comprising each
type of material. 103
Nanoparticles
 Note: these are very 104
approximate numbers!
105

106
Bulk

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

Key Characteristics
Quantum size effect

The quantum size effect in nanomaterials refers to the

changes in electronic and optical properties that occur
when the size of the material becomes comparable to the
wavelength of electrons, typically at dimensions less than
10 nm. In these very small structures, the continuous
energy levels of bulk materials split into discrete energy
states due to confinement of electrons, similar to the
quantum behavior observed in atoms.
Energy Band Gap:
As the size of the nanomaterials decreases, the band gap widens,
meaning that more energy is required to excite an electron from the
valence band to the conduction band. This is particularly relevant for
semiconductor nanomaterials.
Optical Properties:
The size-dependent changes in the energy levels can alter the
absorption and emission spectra of the material. For example,
quantum dots exhibit different colors based on their size due to
this effect.
Electronic Properties:
In bulk materials, electrons move freely, but in
nanomaterials, electrons are confined, and their motion
becomes quantized. This can affect conductivity and
other electronic characteristics.

Surface-to-Volume Ratio:
Nanomaterials have an extremely high surface area
relative to their volume, which can make them more
chemically reactive or allow them to interact more
effectively with other substances.
The total surface area Atotal of a cube is given by: Atotal=6×a2
a = length of one side of the cube, a2 = area of one face of the cube (since
each face is a square), 6 = number of faces on a cube
Nano-size and Properties

When particles are the size that can be seen in a regular microscope,
their properties don't change much. But when they become super small,
around 1–100 nanometers (only visible with special microscopes), their
properties change a lot. At this tiny size, quantum effects control how
the particles behave. Things like melting point, fluorescence,
electrical conductivity, magnetic properties and chemical reactivity
all depend on how small the particles are.
 Classification of nanomaterials

Nanomaterials can be classified based on different criteria such as their

dimensionality, composition, morphology, and phase. Here is an
overview of the key classifications:
 Zero Dimensional (0D)
 One Dimensional (1D)
Two Dimensional (2D)
Three Dimensional (3D)
Zero-Dimensional (0D) Nanomaterials
Structure: All dimensions are confined to the nanoscale (x, y, and
z are all below 100 nm).
Examples: Nanoparticles, quantum dots, nanoclusters.
Properties: These materials have a spherical shape and no freedom
of movement in any direction beyond the nanoscale. Their unique
optical, electronic, and catalytic properties arise from quantum
confinement effects.
One-Dimensional (1D) Nanomaterials
Structure: One dimension (length) is outside the nanoscale,
while the other two dimensions (width and thickness) are
confined to the nanoscale.
Examples: Nanowires, nanorods, nanotubes.
Properties: These materials have elongated shapes and high
aspect ratios. They offer unique properties like enhanced
charge transport, making them ideal for electronic, photonic,
and energy applications.
Two-Dimensional (2D) Nanomaterials
Structure: Two dimensions (length and width) are outside the
nanoscale, while the third dimension (thickness) is confined to the
nanoscale.
Examples: Graphene, nanosheets, nanofilms, thin films.
Properties: These materials exhibit layered structures and offer large
surface area-to-volume ratios. They are used in applications like
sensing, catalysis, and energy storage due to their electronic and
mechanical properties.
Three-Dimensional (3D) Nanomaterials
Structure: All three dimensions (length, width, and thickness) are
outside the nanoscale, but they possess internal nanoscale structures.
Examples: Nanoporous materials, nanostructured bulk materials.
Properties: These materials may consist of nanoscale components
such as pores or grains, offering high surface areas and novel
mechanical or electronic characteristics. They are widely used in
catalysis, drug delivery, and filtration.
Based on Composition:

Carbon-based nanomaterials:
Composed primarily of carbon atoms.
Example: Carbon nanotubes (CNTs), fullerenes, graphene.
Metal-based nanomaterials:
Made up of metals or their compounds.
Example: Gold nanoparticles, silver nanoparticles, metal oxides (e.g., TiO₂,
ZnO).
Ceramic-based nanomaterials:
Composed of ceramic materials like oxides, nitrides, or carbides.
Example: Silica nanoparticles, alumina nanoparticles.
Polymeric nanomaterials:
Made from organic polymers.
Example: Dendrimers, polymer-based nanoparticles.
Composite nanomaterials:
Composed of a combination of different materials to achieve specific
properties.
Example: Nanocomposites (e.g., metal-polymer composites).
Based on Morphology:

Nanoparticles:
Spherical or quasi-spherical particles.
Nanotubes:
Tube-like structures with high aspect ratios.
Nanorods/Nanowires:
Rod- or wire-like structures that are longer in one
dimension.
Nanofibers:
Fibrous or filamentary nanomaterials.
Nanoporous materials:
Materials with nanopores for applications like
catalysis and drug delivery.
ZnO nanoparticles
ZnO nanoparticles
Synthesis of
Nanoparticles
Top-Down Methods are widely used in electronics (e.g., lithography for
semiconductor fabrication), nanofabrication of large-scale integrated systems,
and bulk material reduction to nanometer dimensions.
Bottom-Up Methods are preferred for applications requiring precise
nanostructures, such as catalysis, drug delivery, optoelectronics, and the
synthesis of nanoparticles for sensors or biotechnology.
The ball mill method is a mechanical technique widely used for the synthesis of
nanomaterials. It involves grinding materials into extremely fine particles using a rotating
cylindrical device filled with grinding media such as ceramic balls, metal balls, or other
hard materials.
Process of Ball Milling:
Material Loading: The starting material (bulk material or precursors) is placed in a
hollow cylindrical shell, which rotates around its axis.
Milling Action:
The rotation of the cylinder causes the grinding balls to rise and fall, which crushes
and grinds the material into fine powders due to impact and friction.
As the ball mill rotates, the balls tumble inside the cylinder and strike against the
material, causing fracturing and breaking down the particles.
Energy Transfer: The impact energy of the balls leads to breaking bonds and inducing
mechanical deformations, which produce nanoparticles or nanomaterials through:
Plastic deformation (stretching and bending of crystal structures).
Cold welding (joining small particles due to mechanical pressure).
Fracture (breaking down larger particles into smaller ones).
Nanoparticle Formation: Over time, as the milling continues, the material is reduced to
nanoscale dimensions (typically <100 nm). The process can be controlled by adjusting
factors such as milling time, rotation speed, ball size, and the ball-to-powder ratio.
Advantages of the Ball Milling Method:

Scalability: Can be used for large-scale synthesis.

Cost-effective: It’s a relatively inexpensive process.
Simple and versatile: Can be used for a variety of materials.
Low contamination: If inert materials are used as grinding media.

Disadvantages:
Time-consuming: It may take hours or days to achieve the desired size.
Agglomeration: Sometimes particles can stick together, forming agglomerates.
Control: It can be difficult to achieve precise control over particle size and distribution.

Applications:
The ball milling method is commonly used in the synthesis of:
Metal oxides
Alloy nanoparticles
Semiconductor materials
Magnetic materials
It is particularly valuable for producing materials for catalysis, sensors, and energy storage
applications.
The laser ablation method is a versatile and widely used physical technique for the
synthesis of nanoparticles. It involves using a high-energy laser beam to remove material from a
solid target in a liquid or gaseous environment, leading to the formation of nanoparticles.

Process of Laser Ablation:

Target Material: A solid target, usually made of the material from which nanoparticles are to
be synthesized (such as metals, oxides, or semiconductors), is placed in a vacuum, gas, or liquid
medium.
Laser Irradiation:
A pulsed or continuous high-power laser (commonly Nd (Neodymium)
or CO₂ lasers) is focused on the target surface.
The laser energy heats and vaporizes a small portion of the target, causing atoms or
clusters of atoms to be ejected in a process known as ablation.
Plasma Formation:
The ablated material forms a high-temperature, high-pressure plasma, containing
vaporized atoms and ions.
As the plasma expands, it cools rapidly, leading to nucleation and the condensation of
nanoparticles from the vapor phase.
Nanoparticle Growth:
The ejected atoms cluster together and form nanoparticles, which grow until they
reach a stable size.
The surrounding medium (gas or liquid) influences the cooling rate and the size
of the resulting nanoparticles. In a liquid, for example, the high cooling rate
typically leads to smaller nanoparticles.
Collection of Nanoparticles:
In a gas-phase laser ablation process, the nanoparticles are collected on a
substrate or in a chamber.
In a liquid medium, the nanoparticles are suspended directly in the liquid,
forming a colloidal solution.
Factors Affecting the Laser Ablation Process:

Laser Parameters: Laser wavelength, pulse duration, energy density, and

repetition rate impact the size and distribution of nanoparticles.
Target Material: The nature of the target material (its melting point, thermal
conductivity, etc.) influences the ablation rate.
Ambient Medium: The choice of liquid or gas medium controls the cooling rate
and agglomeration of nanoparticles.
Ablation Time: Longer ablation times lead to more material removal,
increasing nanoparticle concentration.
Advantages of Laser Ablation:
Purity: Since no chemical precursors are used, the resulting nanoparticles are often highly
pure.
Versatility: Can be used with a wide variety of materials (metals, ceramics, semiconductors).
Control: Provides good control over particle size and distribution by adjusting laser
parameters.
No Contamination: As a clean physical process, it minimizes contamination from chemicals
or reagents.
Disadvantages:
Cost: Requires expensive laser equipment.
Low Yield: May produce lower amounts of nanoparticles compared to chemical methods.
Energy Intensive: Laser systems can be energy-demanding, especially for large-scale
production.
Applications:
Nanoparticles Synthesis: Laser ablation is used to create nanoparticles of
metals (gold, silver), oxides (TiO₂, ZnO), and semiconductors (Si, Ge).
Biomedical: Nanoparticles produced through this method are used in drug
delivery, cancer treatment, and bioimaging due to their purity and controlled
size.
Optoelectronics: Nanoparticles made via laser ablation are used in sensors,
LEDs, and photo detectors.

Laser ablation is favored when high-purity nanoparticles are required, making

it an important tool for nanomaterials research and applications.
The Sol-Gel method is a chemical route used to produce nanoparticles or
nanomaterials with high purity and uniformity. It involves the transition from a
liquid solution to a solid gel phase.
The Sol-Gel method is a widely used process in nanotechnology for
synthesizing nanoparticles. It’s a versatile and simple approach that involves
transforming a solution (sol) into a solid (gel) phase to form nanoparticles.

Advantages of Sol-Gel Method:

Low temperature processing: The method can be performed at relatively low
temperatures, leading to energy savings.
Control over particle size and composition: You can adjust factors like pH, solvent
type, and precursor concentration to control the nanoparticle size and shape.
Purity and homogeneity: It produces highly pure and homogeneous nanoparticles,
ideal for many advanced applications.
Basic Steps of the Sol-Gel Method:
•Precursor Preparation:
Start with a chemical precursor, usually metal alkoxides or metal salts (e.g., zinc acetate for
ZnO).
This precursor is dissolved in a solvent (usually alcohol or water) to form a homogeneous
solution, known as a sol.
•Hydrolysis and Condensation:
Water is added to initiate hydrolysis, where the metal ions react with water molecules to
form hydroxides.
Condensation reactions then occur, where hydroxide groups bond to form a network of
metal-oxygen-metal (M-O-M) bonds.
These reactions gradually transform the sol into a gel – a three-dimensional solid network
with liquid inside.
•Aging:
The gel is allowed to age, where the network structure strengthens, and the liquid begins to
evaporate, shrinking the gel.
•Drying:
The remaining liquid is removed by controlled drying, leaving behind a porous solid
material (xerogel or aerogel, depending on drying conditions).
•Calcination:
Finally, the material is heated to high temperatures (400-800°C) in a process called
calcination.
This step removes any remaining organic substances and crystallizes the material,
producing nanoparticles with controlled size and morphology.
Applications of Sol-Gel Synthesized Nanoparticles:
Catalysis: Nanoparticles synthesized via Sol-Gel are widely used in
catalysis (e.g., photocatalysis).
Optical materials: Nanoparticles like TiO2 or ZnO for coatings or sensors.
Biomedical applications: Drug delivery systems, biosensors.

The Sol-Gel method is an efficient and flexible route for nanoparticles

synthesis. It allows control over the material properties, making it suitable
for a range of applications, from coatings to catalysis.
Hydrothermal method
The hydrothermal method is another popular technique for synthesizing
nanoparticles, especially for materials that require high pressure and
temperature conditions. This method uses water as the solvent in a sealed, high-
pressure environment to facilitate the growth of nanoparticles.

The Hydrothermal method is a process of synthesizing nanoparticles in a

water-based solution under controlled temperature and pressure. The method
mimics natural mineral formation processes that occur deep within the Earth
and allows the formation of nanoparticles with specific properties.
Basic Steps of the Hydrothermal Method:

1. Precursor Preparation:
A precursor, usually a metal salt (e.g., zinc nitrate or titanium tetrachloride for
ZnO or TiO2 nanoparticles), is dissolved in water to create an aqueous
solution.
2. Sealed Reaction Vessel (Autoclave):
The solution is transferred to a sealed autoclave or a Teflon-lined stainless
steel vessel.
The autoclave is crucial because it creates a high-pressure environment,
allowing reactions that might not occur under normal conditions.
3. Heating Under Controlled Conditions:
The autoclave is then heated to temperatures ranging from 100°C to 300°C,
depending on the desired material and particle properties.
The temperature increase causes water to act as a supercritical fluid, where it
exhibits both liquid- and gas-like properties, improving solubility and
reactivity of the precursors.
4. Nanoparticles Growth:
Under these conditions, the dissolved precursors undergo nucleation and
crystallization, forming nanoparticles.
The high temperature and pressure promote uniform growth, leading to highly
crystalline nanoparticles.
5. Cooling and Collection:
After the desired reaction time, the autoclave is allowed to cool naturally or
through controlled cooling.
The nanoparticles are collected by filtering or centrifugation, followed by washing
to remove any unreacted precursors or by-products.
6. Drying:
The synthesized nanoparticles are dried, often in an oven, to remove residual
moisture, resulting in the final product.
Key Features of the Hydrothermal Method:

High Pressure and Temperature Control: The method allows reactions at much
higher temperatures and pressures than are achievable in an open environment,
enabling the formation of materials with unique structures.

Solvent (Water) as Reaction Medium: Water, which acts both as a solvent and a
reaction medium, is eco-friendly and supports green chemistry principles.

Crystalline Nanoparticles: The method typically yields highly crystalline

nanoparticles with controlled size and morphology.
Advantages of the Hydrothermal Method:

Precise control over particle size and shape: By adjusting the reaction
parameters (temperature, time, and pressure), you can control the size and
morphology of the nanoparticles.

High purity and crystallinity: The high-temperature and pressure conditions

result in well-ordered, crystalline materials without the need for additional
calcination.

Environmentally friendly: The use of water as a solvent makes this method

relatively safe and environmentally benign.
Example: Synthesis of TiO2 Nanoparticles by Hydrothermal
Method
i. Dissolve titanium tetrachloride in water to form an aqueous precursor
solution.
ii. Place the solution into a Teflon-lined autoclave.
iii. Heat the autoclave to 180°C for 24 hours.
iv. Cool the autoclave, collect the white TiO2 nanoparticles, and wash them with
water.
v. Dry the nanoparticles to obtain the final TiO2 nanomaterial.
Characterization
of
Nanomaterials
X-ray Diffraction (XRD)

Purpose: Used to determine the crystalline structure and phase of nanomaterials.

The principle of XRD is based on Bragg's Law, which describes how X-rays
interact with the crystal lattice of a material. When a beam of X-rays hits a
crystalline sample, the X-rays are scattered by the atoms in the crystal. If the
conditions are right, constructive interference occurs, producing distinct
diffraction patterns that can be used to determine the material's crystal structure.

Bragg's Law:

nλ=2dsin⁡
θ

Where:
n is an integer (the order of diffraction),
λ is the wavelength of the X-ray,
d is the distance between planes of atoms in the crystal (interplanar spacing),
θ is the angle of incidence at which constructive interference occurs.
The X-rays are diffracted when they reflect off planes of atoms in the
crystal at angles where the difference in the path length of the waves is an
integer multiple of the X-ray wavelength. This causes constructive
interference, resulting in a detectable peak at a specific angle.