Unit-2

Synthesis and characterization of Nanomaterials

Synthesis of nanomaterials: Bottom-up and Top-down Approach: Co-Precipitation, solution

combustion, hydrothermal, chemical vapour deposition and mechanical milling.
Characterization of nanomaterials: Principle and applications of Powder X-ray diffraction, UV-
Vis spectroscopy, Scanning electron microscopy, transmission electron microscopy and BET-
analysis.

Synthesis of Nanomaterials
Synthesis of nanomaterials and nanostructures are the important aspect of nanoscience and

nanotechnology. New physical/chemical properties and applications of nanomaterials are only

possible when nanostructured materials are made available with desired size, shape,

morphology, crystal structure and chemical composition.

The interest in synthesis of nanomaterials has grown because of their distinct optical, magnetic,

electronic, mechanical, and chemical properties compared with those of the bulk materials.

There are plenty of methods to synthesise nano materials. These methods are grouped into two

categories namely:

(1) Top-Down and

(2) Bottom-Up techniques.

The techniques are classified based on the phase of the starting material.

In the Top-down class of techniques, the starting material is in solid state, whereas in Bottom-

Up techniques the starting material is either in gaseous state or in liquid state.

Top-down approach refers to a subtractive process in which a bulk starting material is divided

into smaller ones of nanosize.

Examples: 1) Mechanical grinding (Ball Milling) 2) Lithography 3) Etching

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Advantages: Bulk/mass production of nanomaterials is possible

Disadvantages:

• Methods require expensive apparatus

• Methods cause crystallographic damage and introduce surface defects
• The nanomaterials will have internal stress
• The nanomaterials will be generally contaminated

Bottom-up approach refers to an additive process that starts with precursor atoms (or)

molecules which combine to form nanosized structure. Here nanostructures are built atom-by-

atom or molecule-by-molecule.

Examples: 1) Sol gel method 2) Co-precipitation 2) Chemical Vapour Deposition 5)

Hydrothermal method

Advantages:

• Methods are simple, versatile and economically viable

• Methods offer better control over chemical composition, size, microstructure and aspect
ratio
• Resulting nanomaterials will have less defects and are of high purity
Disadvantages:
• Agglomeration is a major challenge
• Product production rates are very less
• Controlling the nanoparticles sizes is tough
Depending on the requirement we have to select an appropriate method for preparation of nano

materials.

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(1) Co-precipitation
Co-precipitation method is the most simplistic and more convenient chemical method

for the synthesis of the metal oxides like Al2O3, ZrO2, TiO2, ZnO and so on. In this chemical

process the aqueous solution of the metal salt in the form of nitrates or sulphates or chlorides

are converted into respective metal hydroxides by the addition of the hydrolyzing agents like

aqueous ammonia, sodium hydroxide or potassium hydroxide at room temperature. These

metal hydroxides are subjected to heating at elevated temperature to obtain the respective metal

oxides. The structure, particle size and morphology of the oxide nanoparticles are greatly

dependent on the type and the nature of the precursor salts, hydrolyzing agent used, pH of the

medium and the temperature of the reaction. One can achieve the nanoparticles of uniform

size and morphology by the careful control of the above-mentioned reaction parameters.

Example: synthesis of ZnO nanoparticles through Co-Precipitation method

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Advantages of co-precipitation reactions

(i) homogeneity of component distribution

(ii) relatively low reaction temperature
(iii) fine and uniform particle size with weakly agglomerated particles
(iv) low cost.

Disadvantages of co-precipitation reactions

(i)These reactions are highly susceptible to the reaction conditions

(ii) because of incomplete precipitation of the metal ions, control over the
stoichiometry of the precursors is rather difficult to achieve

(2) Solution combustion synthesis

Solution combustion synthesis is a technique in which the main solid phase products

form during exothermic redox reactions between the precursors i.e., metal nitrates (oxidizer),

and organic fuel (reductant), mixed at a molecular level in a solution.

Solution combustion synthesis is one of the most alternative methods for the synthesis of pure

as well as doped metal oxide nanoparticles. Solution combustion synthesis is an adaptable,

simple and quick process which allows effective synthesis of a variety of nanosized materials.

Combustion synthesis of metal oxide nanoparticles is as follows:

The required amounts of the metal nitrates and fuel to be dissolved in a minimal volume

of distilled water. The solution is heated till excess water is evaporated and transparent gel is

obtained. Transfer the gel into a preheated (~600 °C) muffle furnace. The synthesis is

conducted under ambient air atmosphere. Initially the solution vigorously boils and undergoes

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dehydration followed by catching fire leading to the liberation of the enormous amount of the

gases like CO2, N2 and water vapours and finally lead to the formation of the highly swelled,

porous and voluminous metal oxide nanoparticles.

Example: synthesis of Aluminium oxide nanoparticle using Aluminium nitrate as an

oxidiser and urea as a fuel:

2 Al2(NO3)3 + 4 NH2CONH2 2Al2O3 +7N2 + 4CO2 + 8H2O

The flow chart for the synthesis of metal oxide nanoparticles is as follows:

Metal oxide NPs

The Advantages of the combustion synthesis are

i. Formation of highly porous products

ii. Simple equipment is enough for the synthesis
iii. Low cost synthesis approach
iv. Yield obtained is high

The disadvantages of the combustion synthesis are

i. Large and non-uniform agglomerations are formed in the prepared samples

ii. The presence of unintentional carbon impurities in large concentration

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(3) Hydrothermal synthesis of nanomaterials
Hydrothermal synthesis is generally defined as crystal synthesis or crystal growth under
high temperature and high pressure water conditions from substances which are insoluble in
ordinary temperature and pressure (<100 °C, <1 atm).

The word “hydro” means water and “thermal” means heat. Hydrothermal method
usually refers to any heterogeneous reaction in the presence of aqueous solvents at high
pressure and temperature conditions.

In hydrothermal synthesis, to the aqueous solution of metal salt, reagents like NaOH/
NH4OH/urea/thiourea in water are added dropwise under constant stirring till the desired
precursor solution is obtained. The solution is further stirred continuously for some time and
the resultant solution is transferred to Teflon-lined stainless steel autoclave and maintained at
certain temperature for required time in a furnace. After the hydrothermal reaction the
autoclave is naturally allowed to cool to room temperature. The product in the form of
precipitate is obtained and washed with distilled water and ethanol several times and dried at
hot air oven at 60 °C. The dried particles are annealed at required temperature and for required
time.

The formation mechanism of metal oxide particles from metal nitrate solution is as
follows:
(i) hydrated metal ions are hydrolysed to metal hydroxide.
(ii) metal hydroxides proceed to precipitate as metal oxides through dehydration

M(NO3) + H2O = M(OH) + HNO3

M(OH)2 = MO + H2O
The flow chart for the synthesis of nanoparticles by hydrothermal method is as follows:

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Disadvantages
1. Water is the solvent and is eco-friendly
2. Uniform particle size can be obtained
3. Simple procedure
Disadvantages
1. The important limitation is that, This method requires long time to complete the
reaction > 12 hours.
2. The greatest disadvantages of teflon lining is that beyond 300°C, it cannot be used
because teflon dissociates which affects the pH of neutral solutions.
3. Accidental explosion of the high pressure vessel cannot be avoided.

(4) Mechanical milling

It is used in making of nanoparticles of some metals and alloys in the form of powder. Usually
the mill contains one or more containers and are used at a time to make fine particles. Size of
container depends upon the quantity of interest. Hardened steel or tungsten carbide balls are
put in containers along with powder or flakes of a material of interest. Initial material can be
of arbitrary size and shape. Container is closed with tight lids. The containers are rotated at
high speed (a few hundreds of rpm) around their own axis. Additionally they may rotate around
some central axis and are therefore called as ‘planetary ball mill’. When the containers are
rotating around the central axis, the material is forced to the walls and is pressed against the
walls. But due to the motion of the containers around their own axis, the material is forced to

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other region of the container. By controlling the speed of rotation of the central axis and
container as well as duration of milling, it is possible to ground the material to fine powder
whose size can be quite uniform. Some of the materials like Co, Cr, W, Ni-Ti, AlFe, Ag-Fe
etc. are made nanocrystalline using ball mill.

Advantages

• low installation cost

• low cost of grinding medium

• suitability for both batch and continuous operation

Disadvantages:

Large balls, used for milling, produce smaller grain size and larger defects in the particles. The
process may add some impurities from balls. The container has to be filled with air or inert gas
as per the requirements. However, this can be an additional source of impurity. A temperature
rise in the range of 100 to 1100 ˚C is expected to take place during the collisions. Cryo-cooling
is used to dissipate the generated heat.

(5) Chemical Vapour deposition (CVD)

Chemical vapor deposition (CVD) is a well-known technology in the field of

nanomanufacturing. It is often used in large-scale integrated circuits, insulating materials,

magnetic materials, optoelectronic materials.

Principle of Chemical Vapor Deposition (CVD)

CVD belongs to the "bottom-up" technology. Its principle is to introduce the vapor of

gaseous or liquid reactant containing film elements and other gases needed to react into the

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reaction chamber. By increasing the temperature, plasma action, light radiation, or other

forms of energy, CVD can produce chemical reactions on the substrate surface and generate

new solid substances to be deposited on the surface.

CVD consists of four main stages:

① The reaction gas diffuses to the surface of the material.

② The reaction gas is adsorbed on the surface of the material.

③ Chemical reaction occurs on the surface of the material.

④ The gaseous by-products are separated from the material surface.

Because of the molecular level nucleation or growth, CVD is more suitable for forming

dense and uniform films on the irregular substrate surface. CVD deposition speed is fast, and

film quality is stable. Some notable films also have excellent optical, thermal, and electrical

properties, making it easy to achieve mass production.

The deposition temperature of CVD is usually very high, between 900 ℃ ~ 2000 ℃, it

is easy to cause the deformation of parts and the change of structure so as to reduce the

mechanical properties of the body material and weaken the binding force between the body

material and the coating, which limits the selection of substrate, the deposition layer or the

quality of the workpiece. Therefore, low temperature and high vacuum are the main

development direction of CVD.

Advantages

a) Versatile- CVD can deposit any element or compound.

b) CVD produces high dense films.

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c) Economical in production since many products can be coated at a time.

d) Used for coatings or freestanding structures

e) Fabricates net or near-net complex shapes

f) Self-cleaning—extremely high purity deposits (>99.995% purity)

g) Conforms homogeneously to contours of substrate surface

h) Controllable thickness and morphology

Disadvantages:

Precursors used are volatile, which are usually hazardous and highly toxic. The by-products of

these precursors are also very toxic.

Applications

a) CVD can be used for the synthesis of nanotubes and nanowires.

b) CVD can be used for hard coatings and metal films which are used in microelectronics.

c) CVD can also be used for preparing semiconducting devices, dielectrics, energy conversion

devices etc.

Characterization of Nanomaterials

Advanced nanomaterials characterization is a very important field that leads to the

establishment of their structure-properties relationship and determines their potential

applications in the modern nano technology. Various techniques have been developed to

characterize the size, shape, crystal structure, chemical composition, optical, magnetic, and

mechanical properties of nanomaterials.

Among these techniques, X-ray diffraction (XRD), Scanning Electron Microscopy

(SEM) Transmission Electron Microscopy (TEM), UV-Visible spectroscopy and BET surface

analyser have been widely used to investigate the properties of nanomaterials.

(1) X-ray Diffraction(XRD) Analysis

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Principle:

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

are generated by a cathode ray tube, filtered to produce monochromatic radiation, collimated

to concentrate, and directed toward the sample. The interaction of the incident rays with the

sample produces constructive interference (and a diffracted ray) when conditions

satisfy Bragg's Law

(nλ=2d sin θ) where n = 1,2,3,4,……

This law relates the wavelength of electromagnetic radiation to the diffraction angle and the

lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed and

counted.

The powder X-ray diffraction is an analytical method used to identify the crystal phase

of material. XRD technique is a unique and non-destructive and can obtain the multiple results

including crystal phase and lattice parameters. In addition to these the line widths i.e. Full

width at half maxima (FWHM) was be used to estimate the average crystal size in the sample

by using Debye-Scherrer equation.

D = Kλ / βcosθ

Where, shape factor, K = 0.94, the wavelength of Cu-Kα radiation λ = 1.5418Å, β is the half

width of each diffraction peak and represents the half angle of the diffraction peak.

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How to interpret the data

The result of X-ray diffraction plots the intensity of the signal for various angles of

diffraction at their respective two theta positions. The two theta positions correspond to a

certain spacing between the crystals or atoms in the samples. The intensity of the peaks is

related to the amount of atoms in that phase or with that spacing. The greater the intensity of

the peak, the greater the amount of crystals or molecules with that distinct spacing.

The width of the peaks is inversely proportional to the crystal size. A thinner peak

corresponds to a bigger crystal. A broader peak means that there may be a smaller crystal,

defect in the crystalline structure, or that the sample might be amorphous in nature, a solid

lacking perfect crystallinity. From the following Figure (a) Crystalline and (b) amorphous phase

of the nanomaterials.

Application of XRD

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 1. measurement of sample purity
2. crystal phase identification
3. Determine atomic arrangement
4. Calculation of crystallite size
5. Defect studies
Advantages
1. Less expensive
2. Best method for phase analysis
3. Widely used method for crystal structure determination
Disadvantages
1. Time consuming process
2. It requires large volume of sample
3. X-rays do not interact strongly with lighter elements
(2) Scanning Electron Microscopy (SEM)
Scanning electron microscopy (SEM) is an important electron microscopy technique

that is capable of achieving a detailed visual image of a particle with high-quality and spatial

resolution. SEM is a multipurpose state-of-the-art instrument which is largely employed to

observe the surface phenomena of the materials. The sample is exposed in SEM to the high-

energy electron beam and gives information about topography, morphology, composition,

chemistry, orientation of grains, crystallographic information, etc. of a material, and therefore

SEM is a useful tool to be used for the characterization of materials.

Morphology indicates the shape and size, while topography indicates the surface

features of an object or “how it looks”, its texture, smoothness or roughness. Likewise,

composition means elements and compounds that constitute the material, while crystallography

means the arrangement of atoms in the materials.

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Principle

The electrons are emitted from a filament and collimated into a beam in the electron

source. The beam is then focused on the sample surface by a set of lenses in the electron column

and are accelerated. Accelerated electrons carry significant amounts of kinetic energy, and this

energy is dissipated as a variety of signals produced by electron-sample interactions when the

incident electrons are decelerated in the solid sample. These signals include secondary

electrons (that produce SEM images), backscattered electrons (BSE), diffracted backscattered

electrons (EBSD that are used to determine crystal structures and orientations of minerals),

photons (characteristic X-rays that are used for elemental analysis and continuum X-rays),

visible light (cathodoluminescence--CL), and heat. Secondary electrons and backscattered

electrons are commonly used for imaging samples: secondary electrons are most valuable for

showing morphology and topography on samples and backscattered electrons are most valuable

for illustrating contrasts in composition in multiphase samples (i.e. for rapid phase

discrimination). Xray generation is produced by inelastic collisions of the incident electrons

with electrons

Applications of SEM
1. Used for chemical analysis in energy-Dispersive X-ray Spectroscopy.
2. Used to study the topography of elements
3. Used to study the morphology of materials
Advantages
1. It is easy to acquire data from the SEM

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2. They are used in a variety of industrial applications to analyze surfaces of solid objects
3. It is easy to acquire data from the SEM

Disadvantages
1. They are very expensive
2. They must be maintained with a consistent voltage

(3) Transmission Electron Microscopy (TEM)

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

high energy beam of electrons is passed through a very thin sample, and the interactions

between the electrons and the atoms can be used to observe features such as the crystal structure

and features in the structure like dislocations and grain boundaries. Chemical analysis can also

be performed.

TEM can be used to study the growth of layers, their composition and defects in

semiconductors. High resolution can be used to analyze the quality, shape, size and density of

quantum wells, wires and dots.

Principle: The TEM operates on the same basic principles as the light microscope but uses

electrons instead of light. Because the wavelength of electrons is much smaller than that of

light, the optimal resolution attainable for TEM images is many orders of magnitude better than

that from a light microscope. Thus, TEMs can reveal the finest details of internal structure - in

some cases as small as individual atoms.

The beam of electrons from the electron gun is focused into a small, thin, coherent beam by

the use of the condenser lens. The beam of electrons then strikes the specimen and parts of it

are transmitted depending upon the thickness and electron transparency of the specimen. This

transmitted portion is focused by the objective lens into an image on phosphor screen or charge

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coupled device (CCD) camera.. The image then passed down the column through the

intermediate and projector lenses, is enlarged.

Applications

1. It used to study the crystallize size of the material

2. Crystal structure can be determines

3. Used for compositional analysis

Advantages

1. It has a very powerful magnification of about 2 million times that of the Light microscope.
2. It can be used to acquire vast information on compounds and their structures.
3. It produces very efficient, high-quality images with high clarity.
Disadvantages

1. Generally, the TEMs are very expensive

2. Difficult sample preparation to create extremely thin specimens

3. They are laborious to maintain.

(4) BET Analysis

surface area analysis is one of the most widely used methods in material characterization. BET

(Brunauer-Emmett-Teller) Specific Surface Area is the most widely recognized technique for

determining the surface area of solids and powders. BET surface area analysis is the

measurement of an analyte’s specific surface area (m2/g) through gas adsorption analysis,

where an inert gas such as nitrogen is continuously flowed over a solid sample, or the solid

sample is suspended in a defined gaseous volume. This theory is used to measure the surface

area of solid or porous materials.

Principle: Samples are first prepared by drying, with a flow of inert gas or vacuum atmosphere,

to clear the surface of any contaminants. The sample is introduced to cryogenic temperature to

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allow a probe gas to physically adsorb to the surface of the sample. The volume of probe gas

adsorbed is measured to determine the quantity of gas required to cover the surface of the

sample. The Brunauer, Emmett and Teller (BET) theory is then applied to the adsorption data

to generate a specific surface area, reported in units of area per mass of sample (m2/g).

BET equation to calculate the surface area:

Where,

V = Adsorbed gas quantity

vm = Adsorbed gas quantity for monolayer

Po = saturated vapour pressure

P = equilibrium pressure

C = constant

The nature of the graph during the adsorption and desorption process is as follows:

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APPLICATIONS

• Surface area analysis of solid materials (such as carbon black, catalysts, batteries
and ceramics)

• Simultaneous acquisition of surface area and pore size data

Advantages

• Non-destructive method

Disadvantages

1. Volume of the sample required is more for analysis

2. Closed pores are not accessible via the material surface.

Optical methods
UV-Visible spectroscopy
UV-Visible spectroscopy(UV-Vis) measures the extinction (scatter + absorption) of light

passing through a sample. Nanoparticles have unique optical properties that are sensitive to the

size, shape, concentration, agglomeration state, and refractive index near the nanoparticle

surface, which makes UV-Vis a valuable tool for identifying, characterizing, and studying

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nanomaterials. Deuterium and tungsten lamps are used to provide illumination across the

ultraviolet, visible, and near-infrared electromagnetic spectrum.

UV-Vis-NIR spectroscopy monitors the interaction between materials and electromagnetic

radiation, but with a focus on the wavelengths either side of visible light. As its name suggests,

in practice these wavelengths can stretch from the ultraviolet (200–400nm) through the visible

light spectrum (400–800nm) to the NIR (800–2500nm).

All non-transparent materials will absorb, scatter and reflect specific visible wavelengths, as

this determines their colour, as well as certain UV and NIR wavelengths.

Principle of the Uv-Vis spectroscopy

The statement of the Beer-Lambert law can be written as follows: When a beam of

monochromatic light is made incident on a solution that contains a substance that absorbs the

monochromatic light, the rate at which the intensity of the beam decreases along the thickness

of the solution is directly proportional to the concentration of the absorbing substance in the

solution and is also directly proportional to the intensity of the incident monochromatic

radiation.

As per the Beer-Lambert law, the greater the number of absorbing molecules (that have the

ability to absorb light of a specific wavelength), the greater the extent of absorption of the

radiation.

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Where
C = concentration of the sample Io = Intensity of incident light
A = absorbance I = Intensity of light transmitted through the sample
ε = molar absorptivity T = Transmittance
L = path length

Applications

1. It is used to calculate the band-gap of semiconductor materials

2. Used to check the purity of the materials

3. Used to study the optical properties of quantum dots

Advantages

1. The technique is non-destructive

2. Easy to use the instrument

3. It is inexpensive technique

Disadvantages

1. For colloidal solutions scattering of light takes place and leads to error.

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