Nanotechnology and

Characterization Techniques

Prof Azeez A. Barzinjy

(PhD, Materials Science, Leicester University, UK)
Soran University, Erbil, Iraq
azeez.azeez@soran.edu.iq
2023-2024
Course Contents:
Weeks Topics
Week 1 Introduction to Nanoscales, Nanoscience, and Nanotechnology √
Week 2 What Makes Nano Interesting? √
Week 3 Classification of Techniques to Produce Nanomaterials √
Week 4 Biosynthesis Method √
Week 5 Top-down approach √
Week 6 Students’ Presentations √
Week 7 Characterization Techniques for nanomaterials Part A
 Week 6

Characterization Techniques
for nanomaterials
Part A
(1)
Outline

• UV-Vis Spectroscopy
• FT-IR Spectroscopy
• XRD
• SEM
• FESEM
• EDX
• DLS

(2)
Characterization techniques for nanomaterials

Nanomaterial Characterization

Imaging methods Spectroscopic methods

TEM, SEM, AFM UV-VIS,FT-IR, DLS

(3)
Characterization techniques for nanomaterials

(4)
Characterization techniques for nanomaterials

Comparison of the time for measurements and instrumentation cost of

optical, AFM, and SEM/TEM microscopes.
(5)
Characterization techniques for nanomaterials

(6)
Characterization techniques for nanomaterials

Characterization of nanomaterials involve determining the:

• Optical properties
• Structural properties
• Electrical properties
• Magnetic properties
• Mechanical properties

(7)
UV-Vis Spectroscopic Characterization of
Nanomaterials

(8)
UV-Visible for nanomaterials

UV-Visible spectroscopy (UV-Vis) measures the extinction (scatter

+ absorption) of light passing through a sample.

(9)
UV-Vis spectroscopy
• UV-Vis spectroscopy (UV-Vis) is a relatively simplistic and low-cost
characterization method that is often used for the study of
nanoscale materials.
• It measures the intensity of light reflected from a sample and
compares it to the intensity of light reflected from a reference
material.
• NPs have optical properties that are sensitive to size, shape,
concentration, agglomeration state and refractive index near the
NP surface, which makes UV-Vis spectroscopy an important tool to
identify, characterize and investigate these materials, and evaluate
the stability of NP colloidal solutions
(10)
Spectroscopy
• Spectroscopy was originally the
study of the interaction between
radiation and matter as a function of
wavelength (λ).
• The sample is irradiated with an
electron probe.
• The incident electron beam causes
ionization of electrons belonging to
the inner shells of the atoms
composing the material.
(11)
The Electromagnetic Spectrum
The electromagnetic spectrum is divided into a number of
regions; these are artificial divisions in the sense that they
have been defined solely as a result of differences in the
instrumentation required for producing and detecting
radiation of a given frequency range.

(12)
What is Light?
• Light consists of
oscillating electric and
magnetic fields.
• Because nuclei and
electrons are charged
particles, their motions
in atoms and molecules
generate oscillating
electric fields.

(13)
Light-Matter Interaction
For most purposes, it is convenient to treat a molecule as if it
possesses several distinct reservoirs of energy. The total
energy is then given by:

Etotal = Etranslation + Erotation +

Evibration + Eelectronic +
Eelectron spin orientation +
Enuclear spin orientation

(14)
What happens when light interacts with a molecule?
A transition from a lower level to a higher level with transfer of
Absorption energy from the radiation field to an absorber, atom, molecule, or
solid.

A transition from a higher level to a lower level with transfer of

Emission energy from the emitter to the radiation field. If no radiation is
emitted, the transition from higher to lower energy levels is called
nonradiative decay.

Redirection of light due to its interaction with matter. Scattering

might or might not occur with a transfer of energy, i.e., the
Scattering scattered radiation might or might not have a slightly different
wavelength compared to the light incident on the sample.

(15)
Energy of Electromagnetic Radiation

(16)
Types of Spectroscopy

(1) Atomic Spectroscopy:

Here, the changes in
energy takes place at
atomic level.
e.g.: Atomic absorption
spectroscopy, Flame
photometry

(17)
Types of Spectroscopy

(2) Molecular
Spectroscopy :
Here, the changes in
energy takes place at
molecular level.
Eg.: UV spectroscopy,
colorimetry, infra red
spectroscopy

(18)
Absorption Spectrophotometry
• Absorption spectrophotometry
can be defined as the
measurement of absorption of
radiant energy by various
substances.
• It involves the measurement of
absorptive capacity for radiant
energy in the visible, UV and IR
regions of the spectrum.

(19)
Colorimetry
• λ- 400-800nm
• Colored substance absorbs light of different λ in different
manner and hence get an absorption curve.
• The λ at which maximum absorption takes place is called as
λmax.
• λmax is characteristic for every colored substance.
• On plotting a graph of concentration v/s absorbance, we
get a calibration curve that is useful in determining the
concentration or amount of a substance in the given
sample solution.
(20)
Colorimetry

(21)
UV-Visible for nanomaterials
• Gives quantitative measure of color.
• What wavelengths are absorbed?
• What wavelengths are transmitted?

(22)
(23)
UV Spectroscopy
• UV spectroscopy is concerned with the
study of absorption of UV-radiation which
ranges from 200-400 nm.
• Valence electrons absorb the energy
thereby molecules undergoes transition
from ground state to excited state.
• This absorption is characteristic and
depends on the nature of electrons present.
• Types of electrons:
σ :Methane(CH₄) has C-H bond (122nm),
σ electrons: in saturated compounds π Alkenes (170-205nm),
π electrons: in unsaturated compounds n Methyl chloride has a λmax of 173nm
n electrons: in non bonded electrons
(24)
UV Spectroscopy
Chromophore:
A chromophore is the part of a molecule
responsible for its color. The color that is
seen by our eyes is the one not absorbed
within a certain wavelength spectrum of
visible light.
Auxochromes:
An auxochrome is a group of atoms
attached to a chromophore which
modifies the ability of that chromophore
to absorb light.
(25)
UV Spectroscopy

(26)
Red-Shift
• When the absorption maxima
(λmax)of a compound shifts to
longer wavelength, it is known as
bathochromic shift or red shift.
• The effect is due to the presence
of auxochrome or by change of
solvent.
• Eg. An auxochrome group like –
OH, -OCH3 causes absorption of
compound at longer wavelength.
(27)
Blue-shift
• When the absorption maxima
(λmax) of a compound shifts to
a shorter wavelength, it is
known as hypsochromic shift
or blue shift.
• The effect is due to the
presence of a group causes
removal of conjugation or by
change of solvent.

(28)
Hyperchromic effect
• When absorption intensity (ε)
of a compound is increased, it
is known as hyperchromic shift.
• If auxochrome introduces to
the compound, the intensity of
absorption increases.
• When absorption intensity (ε)
of a compound is decreased, it
is known as hypochromic shift.

(29)
The Beer-Lambert Law
The Beer-Lambert The transmittance, T, of the solution
is defined as the ratio of the
Law (also called transmitted intensity, I, over the
Beer’s Law) is a incident intensity, I0:
relationship between and takes values between 0 and 1.
the attenuation of However, it is more commonly
light through a expressed as a percentage
transmittance:
substance and the
The absorbance, A, of the solution is
properties of that related to the transmittance and
substance. incident and transmitted intensities
through the following relations:
(30)
The Beer-Lambert Law

(31)
The Beer-Lambert Law

The Beer-Lambert law is a linear relationship

between the absorbance and the concentration,
molar absorption coefficient and optical August Beer
coefficient of a solution:

Johann Lambert

(32)
The Beer-Lambert Law
(a) Absorption spectra of
Rhodamine B solutions
with different
concentrations in water
measured using the
double beam UV-Vis
Spectrophotometer.
(b) Calibration curve of
Rhodamine B in the
water at measured at
λmax.
(33)
UV-Visible for nanomaterials
• UV-Vis technique is a required technique for the optical study of the
materials.
• Optical study helps the researcher for the application s of nanomaterials
for different uses.
• Different devices are fabricated on the basis of optical properties of the
materials especially solar cells.
• With this technique optical band gap can be calculated which helps to
choose the materials for the energy conversion purpose like light energy
to electrical energy in solar cell.
• Also, from this technique purity of the sample can be measured by
comparison with the reference solution.

(34)
Applications of the UV-Vis Spectroscopy
Detection of Chromophore functional group: To determine the functional
group in the material exclusively it confirms the presence and absence of
the Chromosphere in the sample which should be compound.
Chromophore is an atom or group which is responsible of the color of the
compound.

Determine the unknown compound: With the help of the UV-Vis

spectroscopy unknown compound can be determined in the sample. For
this purpose, required compound is compared to spectrum of the
reference compound if luckily both the spectrum is matched then
confirmation of unknown compound can be noted.

(35)
Applications of the UV-Vis Spectroscopy

Purity of the sample: The purity of the substance can be measured by this
unique technique for this purpose absorption of the reference and the
sample under observation is compared and via relative calculations of the
absorption intensity purity of the sample can be confirmed.

Band gap calculations: An interesting application of this technique is the

calculations of the band via different method there are different
software’s are available for this purpose.

(36)
UV-Visible for nanomaterials
The available phytochemicals in
plant extracts, such as phenolic
and flavonoids compounds are
important for nanoparticles
formation and stabilization. Thus,
UV-Vis spectra of the plant
extract confirm the existence of
phenolic, flavonoids and other
compounds that are participating
in nanoparticles formation

(37)
UV-Vis Spectroscopy for Plant Extract
Phenol

(38)
UV-Visible for nanomaterials
• After mixing the metal ion salt with the selected plant
extracts, the first and foremost indicator denotes to
the formation of the nanoparticles, is the color
change.
• This can be explained as the available phytochemicals
inside the plant extract reduces the metal ion to the
metal atom.
• UV-Vis spectroscopy monitors this reduction process.
• The absorption peak is predominated by surface
plasmon resonance (SPR) which displays a shift
towards the red-end or blue-end relies upon particle
size, shape, aggregation-state and the nearby
dielectric-medium.

(39)
UV-Visible for nanomaterials
• Moreover, it gives information
about the stability of the
nanoparticles through changing
the position of the absorption
peak.
• Furthermore, Plasmonic peak
and full width at half maximum
provides information about
mono-dispersity, poly-
dispersity and a wide range of
sizes, of the NPs

(40)
UV-Visible for nanomaterials

λ0 = 512, L1 =6.53, L2 = 0.0216

(41)
UV-Visible for nanomaterials

UV–Vis absorption spectra

of Ag NPs, Au NPs and
Ag@Au core–shell NPs

(42)
UV-Visible for nanomaterials

Absorption spectra of gold NPs of different sizes (5 to 400 nm) in water

(43)
UV-Vis Spectroscopy of The Leaf Extracts

The peak shifts lead to the formation of NPs with different size and morphology.

(44)
Tauc and Davis-Mott relation
𝛼ℎ𝑣 = 𝐵(ℎ𝑣 − 𝐸𝑔 )𝑛
This equation is known as Tauc and Davis-Mott relation Where 𝛼 is the
absorption coefficient, ℎ𝑣 is the energy of photon, 𝐸𝑔 is the straight
band-gap, B is the constant and the power n is an integer for direct
band gap 𝑛 = 1/2. So, in Tauc plot, The precise amount of the band-
gap is described through the extrapolation of the rectilinear part of
(𝛼ℎ𝑣)2 vs. ℎ𝑣 to the x-axis

(45)
UV-Visible for nanomaterials

(46)