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Characterization of
Nanomaterials
UV-VISIBLE
UV-
•UV-visible
spectroscopy SPECTROSCOPY
•FTIRspectroscopy
•Raman spectroscopy
•XRD analysis

UV--Visible spectroscopy
UV Electronic excitations
 Absorption of light in the UV/Visible part
of the spectrum (200 – 800 nm).
 The transitions are between the
electronic energy
gy levels.
 Generally, the most probable transition is
from highest occupied molecular orbital
(HOMO) to lowest occupied molecular
orbital (LUMO)

Effect of substituents on the

The effect of conjugation of alkene
absorption spectra
 Bathochromic shift (red shift): a shift to
lower energy or longer wavelength.
 Hypsochromic shift (blue shift): a shift to
hi h energy or shorter
higher h wavelength.
l h
 Hyperchromic effect: an increase in
intensity.
 Hypochromic effect: a decrease in
intensity.

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UV/Vis analysis of Nanomaterials

 This technique quantifies the light that is
absorbed and scattered by a sample
 UV-vis technique hints about the optical
properties
NMs optical properties related to
◦ Size
Si
◦ Shape
◦ Concentration
◦ Agglomeration state
◦ Refractive index near the nanoparticle surface
 Therefore, the UV-vis analysis can hints these
properties of NMs

Interpreting UV/Vis/IR Spectroscopy

Data
1. Transmittance and Absorbance
The transmittance of a sample (T) is defined
In the near IR, where the
as the fraction of photons that pass through sample does not absorb
the sample over the incident number of strongly, the transmittance
is close to 100%
100%. In the UV
photons, i.e., T = I/I0 portion of the spectrum,
where the sample absorbs
 It is common to report the absorbance (A) strongly, the transmittance
of the sample, which is related to the drops to around 10% or less

transmittance by A = -log10(T).

Interpreting UV/Vis/IR Spectroscopy

Data contd..
2. Absorbance and Scattering
 The relative percentage of scatter or
absorption from the measured absorbance
spectrum depends on the size, shape,
composition and aggregation state of your
sample.
 Smaller particles will have a higher Even though the curves in
percentage of their extinction due to Figure 2 and 3 are very similar
absorption the mechanism for extinction
is different which is reflected in
 Larger particles will have a higher the strong differences in the
percentage of their extinction due to visible appearance of the
materials.
scattering of light

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Interpreting UV/Vis/IR Spectroscopy

 It is possible to calculate the contribution
of each effect
Data contd..
3. Effects of Aggregation
 Scattering contribution increases as the
particles aggregate to a greater extent.
 For example, the optical properties of Ag
NPs nanoparticles change when particles
aggregates
 The conduction electrons become delocalized
and are shared amongst neighbouring particles
and so the surface plasmon resonance shifts to
lower energies
 Therefore the scattering peaks red-shift to longer
wavelengths

Interpreting UV/Vis/IR Spectroscopy

Data contd..
4. Analyzing stability of NP dispersion
 As the particles destabilize, the original
extinction peak will decrease in intensity
p
 This is due to the depletion of stable
nanoparticles
 In general the peak will broaden or a
Figure 5. The absorption spectrum of silver nanoparticles changes
secondary peak will form at longer wavelengths as the particles transition from a well-dispersed state to an
(due to the formation of aggregates). aggregated state following the addition of a concentrated salt
solution; as aggregation proceeds, the plasmon peak at 420 nm
decreases, a secondary peak at 620 emerges.
The final aggregated state is readily seen by eye, as the original
dispersed particles form a yellow solution and the aggregated
particles become grey

Interpreting UV/Vis/IR Spectroscopy

Data contd..
 Correlation between size and band-gap in
semiconducting NPs
◦ When the particle size is decreasing the band-
gap energy is increasing
◦ This is explained on the basis of quantum
confinement theory

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 Gold nanoparticles possess a wine - red

colouration due to the oscillations of the
surface electrons of the particle on
interaction with light of suitable wavelength, FT-IR SPECTROSCOPY
called surface plasmon resonance.
 Surface plasmon band is greatly dependent
on the nanoparticle size and shape
 When the shape of gold nanoparticle
changes to the form of nanorods, the surface
plasmon resonance mode changes from 517
nm to 850 nm

FTIR Spectroscopy
 Molecules can be considered as ball and  When IR radiations passed through the sample
spring systems the oscillations induced by the vibrational
 Frequencies of vibrations are frequencies couple with an incident beam of IR
radiation when the are in resonance and this
proportional
p p to the l d to
lead t the
th formation
f ti off a peak
p k in
i the
th spectrum
p t
◦ mass of balls (atomic weight)  IR radiations lies between visible and
◦ stiffness of the springs (bond strength) microwave region of electromagnetic
 The vibration frequencies are in the range spectrum
of 1012 to 1014 Hz (3-300μm W.L) which  IR radiations have longer WL than visible and
is in the IR region of EM spectrum shorter WL than microwaves

 Absorption of IR radiation takes place

when,
Applied IR frequency = Natural frequency
of vibration
 Every bond/functional group requires
different frequency of absorption
 Thus characteristics peaks are observed
for every functional group of the
molecules

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 Condition for IR activity

◦ The dipole moment of the molecule must
change during the vibration
◦ H2, N2, O2 are IR inactive
 Stretching and bending vibrations
◦ Stretching vibrations are more intense than
b di vibrations
bending ib ti

 FTIR refers to the Fourier Transform Infrared

Spectroscopy, when the intensity-time output of the
interferometer is subjected to a Fourier transform
to convert it to a familiar FTIR spectrum.
 In practice, infrared radiation of
 Thus in FTIR spectroscopy, the detector collects all
successively increasing wavelength is
the information simultaneously and the computer passed through the sample and the
with the aid of Fourier transform programme percentage
p g of transmittance is measured
converts it into frequency domain spectrum. using an infrared spectrophotometer.
 So direct structural analysis of samples within
 The graph which shows the variation of
seconds is possible with the help of FTIR
spectroscopy. the percentage of transmittance with
wave number (cm-I) is called an infrared
spectrum

Informations gathered from IR

spectrum of nanomaterials
 Surface modification of the nanomaterial can
1. The IR spectrum of nanoparticles differs be identified via FTIR spectroscopy
considerably from that of the bulk counter
part
◦ The enhanced surface to volume ratio of the
nanoparticles is the reason for the distinguished
features exhibited by nanoparticles
2. An overall estimation of the particle size
and shape can also be made with the help
of IR spectroscopy (eg. Case of Au NPs  The presence of a nanfiller in the matrix can
be identified via FTIR spectroscopy
discussed in UV-Vis)

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 The confirmation of a nanomaterial

formation from a top-down method
◦ Eg. Formation of GO and rGO from graphite
can be confirmed by FTIR technique

RAMAN
SPECTROSCOPY

a) Graphite; b)Graphene oxide; c)reduced graphene oxide

Raman Spectroscopy
 Discovered by C.V Raman
 Spectroscopic technique used to study
vibrational, rotational modes in a system
 When a monochromatic radiation incident on
the material it mayy be reflected,, absorbed or
scattered
 Scattered radiation can give the idea abt the
structure of the molecule
 Raman is based on the scattering
◦ There can be elastic and inelastic scattering
◦ Elastic scattering: Rayleigh scattering
◦ Inelastic scattering: Raman scattering

 Raman spectroscopy is concerned with

radiation scattering from a sample.
 Scattering occurs when an incident photon
interacts with the electric dipole of a
molecule.
 A single frequency of radiation irradiates
the molecule and the radiation distorts
(polarizes) the cloud of electrons
surrounding the nuclei to form a short-
lived state called a “virtual state”. This state
is not stable, persist for the short timescale
of the scattering process and the photon is
Intensity order: Rayleigh>stokes>anti-stokes
quickly re-radiated. Frequency(energy)order: anti stokes>Rayleigh>stokes

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Stokes Scattering:
Stokes scattering result when molecules are in
their ground state where it interacts with the
beam of light. This causes the light to be absorbed
and then re-emitted at lower frequency.
Anti-stokes Scattering:
Anti stokes scattering occurs when molecules are
in a vibrationally excited state when it interact
with the radiations. The interaction can cause
molecules to drop to ground state and lose some
of it is vibrational energy to the light and is re-
emmited at higher frequency.
 Raman shift : a wavelength shift or a
vibration energy difference
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Conditions for Raman activity
 Rotation or vibration should cause change in
molecular polarizability.
◦ Change either in direction or magnitude of
polarizability
 This rule is contrasted with IR spectroscopy.
◦ IR activity requires the change in net dipole moment
in the molecule
◦ Eg. Homonuclear diatomic molecules are IR inactive
 Rule of mutual exclusion: If a molecule has a
center of symmetry, Raman active vibrations
are IR inactive and Raman inactive vibrations
are IR active
 The ratio of anti-Stokes to Stokes
intensities will increase with
temperature because a larger fraction of
the molecules will be in the first
vibrationally excited state under these
circumstances.
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Experimental setup for Raman

 Measure the amt of scattered radiation
 Fraction of scattered light is very low and thus we get
weak raman lines. Hence to detect these lines, powerful
sources like lasers are being used
 The laser beam (from, for example, an Nd : YAG laser
with l = 532 nm, or a rare gas laser) is passed through a
cell, usually a narrow glass or quartz tube filled with the
sample.
 Radiation scattered sideways from the sample is collected
by a lens and passed into a grating monochromator.
 The signal is measured by a sensitive photomultiplier and,
after amplification, is processed by a computer which
plots the Raman spectrum.

Applications Raman spectra of CNTs

 The D-band (between 1305 and 1345 cm-1 ) is
associated with vacancies, defects, and carbonic
impurities (amorphous carbon, glassy carbon,
etc) that destroy the symmetry of the graphene
sheets.
 The G-band (between 1500 and 1600 cm-1 )
corresponds to the graphitic bands,
bands 2D band
(between 2450–2675 cm-1 ) corresponds to the
second harmonic of the D-band and is
associated with the degree of crystallinity of the
graphitic layers.
 The ratio of the intensities of the G and D
bands (IG/ID ) in the Raman spectra of carbon
nanotubes is a measure of their crystallinity.
 A decrease in the D band intensity corresponds
to nanotubes with fewer wall defects and leads
to an increase in the IG/ID , ratio.

Raman spectra of graphene

 FWHM values of the 2D band < 32 cm-1
indicate single layer graphene, 33–55 cm-1
indicate bilayer graphene and >70 cm-1
indicate few layer-graphene.
 Also, when the ratio of intensity of the G X-RAY DIFFRACTION
and 2D bands (IG/I2D ratio) is less 0.5, then
it is an indication of single-layer graphene. (XRD)
 Similarly, IG/I2D ratio ~ 1 indicates bilayer
and IG/I2D ratio >1.5 indicates few layer
graphene •Technique used for phase identification of
 The IG/ID ratio indicates the crystalline a crystalline material
nature of graphene and a higher value •Provide information on unit cell
indicates a better quality material with low dimensions.
defects .

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What is X-
X-ray diffraction technique?  Wave Interacting with a Single Particle
◦ Incident beams scattered uniformly in all directions
 XRD is a non-destructive technique for
analyzing the structure of materials, primarily  Wave Interacting with a Solid/powder
at the atomic or molecular level. ◦ Scattered beams interfere constructively in some
directions, producing diffracted beams
 It works best for materials that are crystalline ◦ Random arrangements cause beams to interfere
or partially crystalline (i.e.,
(i e that have periodic destructively and no distinctive pattern is
structural order) but is also used to study produced
non-crystalline materials.  Crystalline Material
 The wavelength of X rays are comparable to ◦ Regular pattern of crystalline atoms produces
the distance between atoms and so the regular diffraction pattern.
interference pattern can results when a wave ◦ Diffraction pattern gives information on crystal
or a series of waves undergoes diffraction structure
when passed through the sample.

Crystallography basics:

 Crystalline materials are characterized by the orderly periodic

arrangements of atoms.  X Rays are also reflected, scattered
The (220) planes
of atoms in NaCl incoherently, absorbed, refracted, and
The (200) planes
of atoms in NaCl
transmitted when they interact with
matter

 The unit cell is the basic repeating unit that defines a crystal.
 Crystallographic planes are identified by Miller indices
 Diffraction from different planes of atoms produces a diffraction pattern,
which contains information about the atomic arrangement within the
crystal
 The dimensions of the unit cell is described by 3 axes and angle between
them.This can be analyzed by XRD

Working Principle
 XRD analysis is based on constructive
interference of monochromatic X-rays
 The X-rays are generated by a cathode ray
tube, filtered to produce monochromatic
 The incident angle, θ, is defined between the X-ray source
radiation collimated to concentrate,
radiation, concentrate and and the sample.
directed toward the sample.  The diffracted angle, 2, lies between the direction of an
 The diffracted rays undergoes constructive Incident beam and any resulting diffracted beam.
interference when conditions satisfy Bragg’s  The incident angle θ is always ½ of the diffracted angle 2
Law (nλ=2d sin θ).  The diffracted beams are in phase when the path
◦ This law relates the wavelength(λ) of length between the beams is an integral multiple of
the W.L.
electromagnetic radiation to the diffraction angle(θ) 
 This means the path length, xyz=nλ or 2d sin θ= nλ
and the lattice spacing (d) in a crystalline sample.

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 In a :2 instrument the tube is fixed, the

sample rotates at  °/min and the
detector rotates at 2 °/min.
 In a : instrument, the sample is fixed
andd the
h tube  °/min
b rotates at a rate - °/ i
and the detector rotates at a rate of  2

°/min.
At 20.6 °2, Bragg’s law fulfilled The (200) planes are parallel to the (100) planes.
Detector for the (100) planes, producing Therefore, they also diffract for this crystal
X- a diffraction peak.
ray
tub
   A single crystal specimen in a diffractometer would produce only
e one family of peaks in the diffraction pattern.

Applications of XRD technique

1. Identification of crystal present in the
given sample

2. Polymer characterization
A polycrystalline sample should contain thousands of crystallites. ◦ Identification of crystalline or amorphous
Therefore, all possible diffraction peaks should be observed. nature

3. Determination of unit cell dimensions -  The diffraction pattern of a mixture is a simple

measurement of sample purity sum of the scattering from each component
◦ Unit cell lattice parameters and Bravais lattice phase
symmetry –Lattice parameters can vary and therefore ◦ Eg. SiO2
give you information about, alloying, doping, solid
solutions, strains, etc.
4. Phase Composition of a sample
◦ Eg.
E Analysis
A l i off rutile/anatase/brookite
il / /b ki formf off TiO2

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5. Crystallite Size calculation

◦ The averaged crystallite size can be calculated by the
Scherrer equation can be written as:
ԏ =Kλ/βcosθ
where:
◦ ԏ is the mean size of the ordered (crystalline) domains,
which may be smaller or equal to the grain size;
◦ K is a dimensionless shape factor, with a value close to
unity. The shape factor has a typical value of about 0.9, but
varies with the actual shape of the crystallite;
◦ λ is the X-ray wavelength
◦ β is the line broadening at half the
maximum intensity (FWHM), after subtracting the
instrumental line broadening, in radians.
◦ θ is the Bragg angle.

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