CHARACTERIZATION TECHNIQUES OF

NANOMATERIALS
Dr. Sajini Vadukumpully
1
COURSE STRUCTURE
Week 1 Jan 21 - 26 Week 14 April 22 - 27
Week 2 Jan 28 Feb 2 Week 15 April 29 May 4
Week 3 Feb 4 - 9
Week 4 Feb 11 - 15
Week 5 Feb 18 - 23 Total hours 30 h
Week 6 Feb 25 March 2 Weeks 1 - 3 SEM, TEM
Week 7 March 4 - 9 Weeks 4 -8 Chemical
characterization
techniques
Week 8 March 11 - 16 Weeks 9 - 12 Structural
characterization - XRD
Week 9 March 18 - 23 Weeks 12 - 15 SPM
Week 10 March 25 30
Week 11 April 1 - 6
Week 12 April 8 - 13
Week 13 April 15 - 20
3/3/2013
3
Characterization level o as a function of known properties.
The characterization of nanomaterials -
bottleneck
CHARACTERIZATION OF NANOMATERIALS
3/3/2013
4
Electron microscopy is generally used But it is not capable of providing insights
into non-crystalline surface matter or ligands
Scanning Electron Microscope (SEM): scattering of electrons,
secondary and backscattered electrons, electron gun, lenses and apertures, and
imaging modes in SEM.
One type of electron microscopic techniques makes use of electron
beams
5
SCANNING ELECTRON MICROSCOPE (SEM)
What is SEM?
Basic working principle.
Major components and functions
Electron beam specimen interactions
Different imaging modes in SEM
Energy Dispersive X-ray spectroscopy (EDS)

6
http://virtual.itg.uiuc.edu/training/EM_tutorial/
SCANNING ELECTRON MICROSCOPE
Gives information about topography, chemical composition,
grain size and thickness.
Uses electron beam (not light) to form an image.
SEM have a magnifications ranging from 10 - 500000x and
high resolution (~ 2 nm).
7
Cost: $0.8-2.4M
Magnification Depth of field Resolution
Optical microscope 4 - 1000x 60 0.2 m

0.2 m
SEM 10 - 500000x 4 mm 400 nm. 1 10 nm
OM
SEM
http://www.mse.iastate.edu/microscopy/
MAGNIFICATION vs RESOLUTION
8
Magnification Simple enlargement of an object.
Resolution Capability of making the individual parts of an
object, distinguishable.
J Nanopart Res (2010) 12:17771786
9
MAGNIFICATION vs RESOLUTION
Depth of field
10
SCANNING ELECTRON MICROSCOPE
Column
11
Source: L. Reimer,
Scanning Electron
Microscope, 2
nd
Ed.,
Springer-Verlag, 1998, p.2
Electron Gun
A more closer look!!
MAJOR COMPONENTS OF SEM
12
o Electron optical column
o Electron gun to produce electrons (thermionic/field
emission)
o Magnetic lenses de-magnifies the beam
o Magnetic coils modify/control the beam
o Apertures
o Vacuum system
o Chamber which holds vacuum (pumps to produce
vacuum)
o Valves and gauges to control and monitor vacuum
o Signal detection & display
o Detectors which collect the signal
o Electronics which produce an image from the signal
ELECTRON BEAM SOURCE
13
Source type : Thermionic, Schottky field emission and cold field emission
http://www.ammrf.org.au/myscope/sem/practice/principles/gun.php

Source Brightness Stability(%) Size Energy spread(eV) Vacuum

W 3X10
5
~1 50mm 3.0(eV) 10
-5

LaB
6
3x10
6
~2 5mm 1.5 10
-6
C-FEG 10
9
~5 5nm 0.3 10
-10
T-FEG 10
9
<1 20nm 0.7 10
-9

THERMIONIC ELECTRON GUN
14
o The electrons boil off (thermionic
emission) the sharply bent tip of
the filament and are attracted to
the anode.
o The filament is either W or LaB
6

o The anode is maintained at a
positive voltage (~ 5 30 kV).
o Vacuum is required to prevent the
oxidation of the filament.
o The Wehnelt cylinder is biased
negatively relative to the filament. It
acts as a grid that repels the
emitted electrons and focuses
them into a spot of diameter d and
divergence half angle, .
FIELD EMISSION GUN
15
http://fel.web.psi.ch/public/gun/index.html
Electrons are drawn from the filament
tip by an intense potential field set up
by an anode that lies beneath the tip
of the filament.
Ultra-high vacuum (better than 10-6
Pa) is needed to avoid ion
bombardment to the tip from the
residual gas.
Because of the smaller initial spot size
(< 2 nm), and lower accelerating
voltage (2-5 kV) a much smaller
primary excitation zone is produced.
Ultimately this results in much greater
resolution than is capable with a
conventional SEM using a tungsten
filament or LaB
6
crystal.
LENSES
16
Condenser lens focusing
determines the beam current which impinges on the sample.
Objective lens final probe forming
determines the final spot size of the electron beam, i.e., the
resolution of a SEM.
Note: When the instrument is operational, the electron
optical column and sample chamber must be under
vacuum.

If the column is filled with any gas, electrons will be scattered by
gas molecules, which will reduce beam intensity and stability.
Other gas molecules (may be from sample or microscope) might
condense on the sample. This will lower the contrast and clarity
of the image.
17
HOW THE ELECTRON BEAM IS FOCUSED
A magnetic lens is a solenoid
designed to produce a specific
magnetic flux distribution.
Lens formula: 1/f = 1/p + 1/q
f B
o
2
Demagnification:
M = q/p
f can be adjusted by changing B
o
, i.e., changing
the current through coil.
Condenser lenses are added to
demagnify or to reduce spot size
Objective lens controls the focus of the electron beam by
changing the magnetic field strength.
If the aperture is wider, electrons may not be focused to the
same plane to form a sharp spot. Hence lences with narrow
aperture is preferred.
The stigmator, which consist of two pairs
of pole-pieces arranged in the X and Y
directions, is added to correct the minor
imperfections in the objective lens.
ELECTRON BEAM SPECIMEN INTERACTIONS
19
TYPES OF DETECTORS
A detector placed within the column is known as an in-lens
detector and produces a very different image compared to a
conventionally located detector.

20
SE detectors
SECONDARY ELECTRONS

They are produced by the inelastic scattering of high
energy electrons from the conduction/valence electrons in
the atom of the specimen.
This causes ejection of electrons from the surface. The
energy of emitted electrons is very less and hence, only
SEs from the surface exit the sample and can be
examined.

21
Bright
Dark
TYPES OF DETECTORS /IMAGING MODES
22
Everhart-Thornley SE Detector
http://emalwww.engin.umich.edu/newemal/courses/SEM_lectureCW/SEM_se2.html
The incident electrons do not go along
a straight line in the specimen, but a zig-
zag path instead.
The penetration or, more precisely, the
interaction volume depends on the
acceleration voltage (energy of
electron) and the atomic number of the
specimen.
23
BACKSCATTERED ELECTRONS (BSE)
BSE are produced by elastic interactions of beam electrons with
nuclei of atoms in the specimen and they have high energy and large
escape depth.
BSE yield: h=n
BS
/n
B
~ function of atomic number, Z

BSE images show characteristics of atomic number contrast, i.e.,
high average Z appear brighter than those of low average Z. h increases
with tilt.
The image shows the different minerals within the
thin section as variations in greyscale contrast
(brightest to darkest: zircon, garnet, biotite, K-
feldspar, palgioclase and sillimanite).
24
BSE DETECTORS
BSE Robinson detector Semiconductor detector
A large scintillator collects the BSE
and guides the beam to a
photomultiplier

Large collection angle
Works at TV frequency
A silicon diode with a p-n junction
close to the surface collects the
BSE.

Large collection angle
Slow (poor at TV frequency)
25
If the diameter of primary
electron beam is ~5nm
- Dimensions of escape zone
of
ESCAPE VOLUMES OF VARIOUS SIGNALS
Secondary electron:
diameter ~10nm; depth~10nm
Backscattered electron:
diameter~1m; depth~1m
X-ray: from the whole
interaction volume, i.e., ~5m
in diameter and depth
This escape volume limits the resolution in images produced with
BSE and x-ray (element mapping) to a value that is of the order of
size of the escape volume.
IMAGE FORMATION IN SEM
26
SCAN COIL AND RASTER PATTERN
26
Two sets of coils are
used for scanning
the electron beam
across the specimen
surface in a raster
pattern similar to
that on a TV screen.
This effectively
samples the
specimen surface
point by point over
the scanned area.

Blanking means
interrupting the
electron beam
briefly and
periodically
o Beam is scanned over specimen in a raster pattern in
synchronization with beam in CRT.
o Intensity at A on CRT is proportional to signal detected
from A on specimen and signal is modulated by amplifier.
beam
e
-
A
A
Detector
Amplifier
10cm
10cm
M=

= 10cm/x
C = length of the
scan on CRT

x = length of the
scan on
specimen
HOW FINE WE CAN SEE WITH SEM
Need small electron beam probe to
achieve high magnification.
Changing magnification does not
involve changing any lens current,
only changing the current in the scan
coils, and so:
focus does not change as
magnification is changed
the image does not rotate with
magnification change (as in TEM)
28
Low M
Large x
40m
2500x
1.2m
e
-
High M
small x
7m
x
15000x
RESOLUTION IN SEM
29
o Ultimate resolution depends on the
electron-optical specifications.

o Electron Optical limitations
o Specimen Contrast Limitations
o Sampling Volume Limitations

o If we can scan an area with width 10
nm (10,000,000) we are supposed
to see atoms in SEM!! But, can we?

o Image on the CRT consists of spots
called pixels which are the basic
units in the image.

You cannot have details finer than
one pixel!
http://emalwww.engin.umich.edu/newemal/courses/SEM_lectureCW/SEM_SpotSize2.html
30
RESOLUTION IN SEM
Small beam size is needed for high resolution. Decrease the
beam size by:
1.Increasing the current on condenser lens
2.Decreasing the working distance

Decreasing the beam size also decreases the beam current
and therefore the signal to noise ratio gets worse.
P=D/Mag = 100m/Mag
P - pixel diameter on specimen surface
D - diameter of an image point on
the CRT
Resolution is the
pixel diameter on
specimen surface.
Mag P(m) Mag P(nm)
10x 10 10kx 10
1kx 0.1 100kx 1
31
RESOLUTION IN SEM
The optimum condition for
imaging is when the
escape volume of the
signal concerned equals
to the pixel size.
Signal will be weak if
escape volume, is smaller
than pixel size, but the
resolution is still
achieved.(Image is noisy)
Signal from different pixel will
overlap if escape volume is
larger than the pixel size.
The image will appeared out
of focus (Resolution
decreased)
IMAGE CONTRAST
32
Image contrast, C
is defined by

S
A
-S
B
A
S

C=
________
=
____
S
A
S
A



S
A
, S
B
Represent
signals generated
from two points,
e.g., A and B, in the
scanned area.









In order to detect objects of small size and low contrast in an SEM it
is necessary to use a high beam current and a slow scan speed (i.e.,
improve signal to noise ratio).
SE-topographic and BSE-atomic number contrast
33
SEI vs BSI
Atomic
number
contrast
Topographic
contrast
Field contrast
Voltage Charging effect

34
ENERGY DISPERSIVE SPECTROSCOPY (EDS)
EDS systems include a sensitive x-ray
detector, a liquid nitrogen dewar for cooling, and
software to collect and analyze energy spectra.
The most common detectors are made of Si(Li)
crystals that operate at low voltages to improve
sensitivity (latest - silicon drift detectors).
An EDS detector contains a crystal that
absorbs the energy of incoming x-rays by
ionization, yielding free electrons in the crystal
that become conductive and produce an
electrical charge bias. The x-ray absorption thus
converts the energy of individual x-rays into
electrical voltages of proportional size; the
electrical pulses correspond to the characteristic
x-rays of the element.

35
EDS DETECTOR COMPONENTS
36
FET field effect transistor
STEPS INVOLVED IN EDS
X-ray generation
Pre amplification by FET
Pulse processing
37
FET pre-amplification
Pulse processor
X-RAYS GENERATION
Two basic types of X-rays are produced on inelastic
interaction of the electron beam with the specimen atoms
in the SEM:
Characteristic X-rays result when the beam electrons eject inner shell
electrons of the specimen atoms.
Continuum (Bremsstrahlung) X-rays result when the beam electrons
interact with the nucleus of the specimen atoms.

38
39
Characteristic X-ray Nomenclature
MORE ABOUT X-RAYS IN EDS
The most probable transition, when a K-shell vacancy is created
is the L to K transition.
Therefore K

radiation will always be more intense than K

radiation.
It also follows that K

radiation will be of higher energy than K

radiation.
For a given atom, M

radiation will be of lower energy than L

radiation, which in turn will be of lower energy than K

radiation.
To ionize an atom, the incoming electron or ionizing radiation
must possess a minimum amount of energy. That energy is the
binding energy of the particular inner shell electron, which is a
specific, characteristic energy for each electron in the atom.
40
MOSELEYS LAW
The energy of the characteristic radiation within a given
series of lines varies monotonically with atomic number.
This is Moseleys Law:
E = C
1

(Z- C
2
)
2
where:
E = energy of the emission line for a given X-ray
series (e.g. K

)
Z = atomic number of the emitter
C
1

and C
2

are constants
41
Moseleys Law is the basis for elemental analysis
with EDS.
CRITICAL PARAMETERS FOR EDS
For higher resolution analyses requires high acceleration voltage
Current Typical EDS beam currents will be in nA range
Working distance Use a working distance ~ 9 mm (depends on the instrument)
Productivity depends on the rate of counts measured, called the output count
(acquisition) rate, rather than the input count rate into the detector
As the input rate increases so will the acquisition rate, but an increasing number of
events are rejected because they arrive in a shorter time period than the TP. This
phenomenon is termed pulse pileup. The way to avoid/minimize this is to ensure a
certain percentage of dead time time during which pulses are not measured.
Deadtime = (1 Output rate/Input rate) x 100.
42
43
Spot 2
Spot 1
Adapted from Characterization Facility, University of MinnesotaTwin Cities
Spacial Resolution : Low atomic number (Z): 1-5 um
3
; High Z: 0.2 1 um
3

Acceleration voltage : Should be high as compared to normal imaging.
ELEMENTAL MAPPING IN EDS
44
45
(A) SEM image of a single Au/Ni MF. (B,C)
Corresponding Au MR- and Ni KR-based
EDAX images collected from the sample
shown in panel A. (D) Single particle SEM
image of Au/Co MF. A Au Mo- and Co Ko-
based EDAX image of Au/Co MF (D) is
shown in panels E,F, respectively
(A, B) FESEM and EDAX images, respectively,
of a single Au/Ag bimetallic MF. (C) Magnified
FESEM image of the
stems of the Au/Ag MF and (D) corresponding
EDAX image. Inset of (C) shows the line profile
of the elements taken along the direction shown
by the arrow. The elemental profiles are shown
in different colors.
46
EDS analysis to prove the
biphasic nature of the dumbbell
shaped nanowires. (A) TEM
image of the dumbbell shaped
nanowire chosen for EDS
analysis. (B) Combined
intensity maps for Ag and Te for
the nanowire. (C) Te La
intensity map across the length
of the dumbbell shaped
nanowire. Note that the
intensity in the middle region is
higher than from the tips. (D)
Ag La intensity map showing
that silver is limited only to both
the ends. (E) EDS spectrum
collected from area 1 in A
showing the presence of both
Ag and Te in the atomic ratio of
2 : 1. (F) EDS spectrum from
area 2 in A, showing the
presence of only Te in the
middle section
CONDITIONS FOR SEM SAMPLE PREPARATION
Must be made
conducting to prevent
charging (normally, Pt or
Au is sputter coated).
Must be vacuum
compatible.
Hard/soft materials can
be tested.
47
If the particle size is
small (< 100 nm),
ultrasonicate to diperse a
small amount of powder
in a suitable solvent and
place a drop on a flat
surface and coat using
Au or Pt.
If the particle size is
large, sprinkle powder on
carbon table, blow off
excess sample and then
coat


Dispersion
TRANSMISSION ELECTRON MICROSCOPE
Interaction of electrons with matter, elastic and
inelastic scattering.
Electron sources, lenses, apertures and resolution.
TEM instrument.
Forming diffraction patterns and images,
Selected area and convergent beam electron
diffraction patterns,
Kikuchi diffraction
Imaging and contrast in TEM, HRTEM
48
HISTORY OF TEM
49
The electron microscope built
by Ruska and Knoll in early
1930s
http://www.iopb.res.in/~tem_iopb/temuse.html
JEOL 2010, 200 keV
In 1920s Louis de Broglie
discovered wave like nature of
electrons.
In 1926, H. Busch proved that e-
beams can be focused by
magnetic field (similar to that of
light in optical lens)
Ernst Ruska (Nobel Price in
1986!!), developed a lens system
to magnify the specimen by 16
times and first used the term
electron microscope in 1931.
In 1939, the first TEM was
manufactured by Siemens
(Ruedernberg).
50
Difference between optical and
TE Microscope

Do not observe the image
directly in TEM.
The inside of TEM is under
vacuum.
Instrument weight, sample
preparation, cost, resolution
etc are all different.
WHY DO WE NEED VACUUM IN TEM
51
The electron microscope is built like a series of vessels
connected by pipes and valves separate all the vessels from each
other.

The vacuum around the specimen is around 10
-7
Torr. The
vacuum in the gun depends on the type of gun, either around 10
-7

Torr (the tungsten or LaB
6
gun) or 10
-9
Torr (for the Field
Emission Gun).

The pressure in the projection chamber is usually only 10
-5
Torr
(and often worse).
The electrons will be hit with other molecules in the air and after
a certain distance there will not be any electrons in the beam.

Several hundred kilovolts are being applied across a small
distance between the cathode and anode. It would result in
enormous series of discharges (instead of a steady beam, it will
be like lighting)

Air contains contain large amount of hydrocarbons. They stick to
the specimens and fall apart when hit by electron beam. The
residual carbon as contamination.
ROLE OF SCATTERING IN TEM
52
Electron scattering is the underlying physics of TEM
Diffraction: elastic scattering
Imaging: elastic & inelastic scattering
Spectroscopy: inelastic scattering
Elastic - Direction of
electron beam changes,
but not magnitude.

Inelastic - Direction and
magnitude of electron
beam changes.
Inelastic scattering
Energy transferred to target atoms
Kinetic energy of electron beam decreases
Note: Lower electron energy will now increase the
probability of elastic scattering of that electron.
Secondary electron emission
X-ray generation
Plasmon excitation
Phonon excitation
Different processes
Beam Damage : High Voltage, high current density electron
beam can cause damage to the materials.
Radiolysis and knock-on are two different types
BEAM DAMAGE IN TEM
54
Beam heating is known to be a
problem in the TEM at high incident
currents, for example if a large (or
no) condenser-lens aperture is used.
Even at low current densities, heating
effects are worrisome for organic
materials such as polymers, where
thermal conductivity is quite low.
To produce atomic displacement
(loss of crystallinity or mass loss),
there must be some mechanism for
converting the energy acquired by
atomic electrons to kinetic energy
and momentum of atomic nuclei.
COMPONENTS OF TEM ELECTRON GUN
55
W hairpin
LaB
6
crystal
Heated tungsten A heated filament made
from tungsten. When high voltage is fed
through the filament, electrons are kicked
off from it. The amount of voltage required
is known as work function.
Lanthanum hexaboride (LaB
6
) - Thermal
filament. Work function is lower than W and
hence more efficient.
Tungsten field emission gun (FEG)
Electrons are expelled by applying a very
powerful electric field close to the filament
tip. The size and proximity of the electric
field to the electron reservoir in the filament
causes the electrons to tunnel out of the
reservoir.
56
57
Brightness : Current density per unit solid angle of the source
i
e
= Cathode emission current
d
0
= diameter of the electron beam
o
0
= angle at which electrons diverge from
the source
Current density
Brightness is directly proportional to the accelerating voltage
Other important properties of electron sources : Spatial coherency
Energy spread
Source size
Stability
Reasons for choosing the highest kV The gun is brightest
Shorter the wavelength, the better is
the resolution
Heating effect is smaller
58
COMPONENTS OF TEM LENSES
Objective lens : focus image.
Magnification lens : Determines
the magnification of the
microscope. Whenever the
magnification is changed, current
through the lens also changes
Condenser lenses : control how
strongly beam is focused
(condensed) onto specimen. At
low Mag. Spread beam to
illuminate a large area, at high
Mag. strongly condense beam.

C1 controls the spot size
C2 changes the convergence of the beam
Condenser-lens system
The condenser aperture must be centered
60
Magnification in TEM
Depending on the magnification, some lens may not be used
M
ob
M
int
M
proj
= Total Mag
61
EXTRACTING THE PHASE
In Focus
Under focus
Over focus
Sample




Objective Lens



Focal Plane
LENSES AND SOME OF THE PROBLEMS
62
1.Spherical aberration



r
s
= spherical abberation radius in the gaussian
image plane
C
s
= spherical aberration coefficient
| = collection semi angle

63
2. Chromatic aberration

In addition to the energy spread caused by the power source,
electrons with different wavelengths are generated during the
interaction of the electron beam with the sample. This leads
to a distortion in the image known as chromatic aberration
A
B
AE = Energy loss of the electrons

E
0
= Initial beam energy
64
3. Astigmatism

Occurs when electrons sense a non-uniform magnetic field
as they spiral around the optic axis. This imperfection is
caused by machining errors, inhomogeneities in the iron of
the lens, asymmetry in the windings, dirty apertures.

Af = difference in focus induced by
astigmatism
VIEWING SCREENS/DETECTORS IN TEM
Semiconductor detectors
Scintillator photomultiplier detectors

65
The viewing screen (lead glass) is
coated with modified ZnS, which emits
light with a wavelength of 450 nm,
Modified ZnS give off green light at
closer to 550 nm, hence screen will be
of different shades of green, which is
most relaxing to eyes.
Image recording:

1. Photographic emulsions
2. Computer and charge coupled devices


66
DETECTORS
Semiconductor detectors (p-n junction)
Pros & Cons

Cheap and easy to
replace
Easy to fabricate

Insensitive to low energy
electrons
Electron beam might
damage the detector
They have a large dark
current
Noise is inherent
67
Scintillator photomultiplier detectors
Pros & Cons

Gain is very high. Of the
order of 10
n
,
n is the
number of dynodes in PM
Noise level is low.

Susceptible to radiation
damage
More expensive and bulky
They have a large dark
current
Noise is inherent
SPECIMEN PREPARATION
68
Specimens are loaded on Grids
(3mm in diameter)
Dispersible samples
Disperse in suitable solvent
Drop cast a dilute solution on
grid
Allow it to dry
Solid samples
Ultramicrotome (soft
samples)
Ion milling
Electropolishing
Preferential chemical etching
Cleaving



69
IMAGING MODES IN TEM
o When we form images in TEM,
we either form an image using
the central spot or use the
scattered electrons.

o This can be achieved by
inserting an aperture into the
back focal plane of the
objective lens.

o This allows either the direct
beam or the scattered ones to
pass through.

o If the direct beam is chosen, it
is a BF image
70
BRIGHT FIELD AND DARK FIELD IMAGES
Centered dark field image
71
Carbon coated iron oxide nanoparticle
IMAGING MODES IN TEM
If you form an image without the aperture, the contrast will
be very poor because, then many atoms contribute to the
image
Choice of aperture size determines, which electrons to
contribute to the image and thus the contrast.
72
MASS THICKNESS CONTRAST (BF IMAGING)
Very important for biological / organic samples
Arises from incoherent inelastic scattering of electrons
73
Thicker areas of the specimen will
scatter more electrons off axis than
lower mass areas. Thus fewer
electrons from the darker region fall
on the area of the image plane, and
therefore appears darker in BF
images

The opposite will be true for DF
images
Lattice images (HRTEM)
74
IMAGING MODES IN TEM
The image is formed by the
interference of the
diffracted beams with the
direct beam (phase
contrast).

La
0.7
Sr
0.3
Mn0
3
(LSMO)-SrTiO
3

interface coherently grown by
pulsed laser deposition
CdSe
75
Dark Field Imaging Advantages and Disadvantages
Advantages Disadvantages
Provides high contrast for examining
molecules with very low contrast such
as DNA
More difficult to focus and correct for
astigmatism since phase contrast is not
present.
For crystalline objects, specific
diffraction spots can be selected in
the back focal plane of the objective
lens in order to form a dark field
image only from the electrons
scattered by a chosen set of crystal
planes.
Image brightness is low, since the
objective aperture transmits only a small
fraction of the scattered beam.
Longer exposure times needed to get
good images.

Specimens are subjected to more
radiation damage
DYNAMIC LIGHT SCATTERING (DLS)
76
Also known as Photon Correlation Spectroscopy.

Measures the Brownian motion of particles and connects it
with the particle size.

DLS is used for the measurement of particle size of
particles suspended in liquid.

When light impinges on matter, the electric field of the light
induces an oscillating polarization of electrons in the
molecules and causes scattering of light. The frequency
shifts, the angular distribution, the polarization, and the
intensity of the scatter light are determined by the size,
shape and molecular interactions in the scattering
material.
77
Brownian movement causes the particles to diffuse
through the medium. This diffusion depends on the particle
size and shape
Stoke Einstein Equation
d (H) = hydrodynamic radius
T = Temperature
q = viscosity
D = translational diffusion co-efficient
k = Boltzmanns constant
Factors that affect D

Ionic strength of the medium : Ionic concentration will affect the electrical
double layer, low conductivity medium produce an extended electrical double
layer and hence hydrodynamic radius will be more, where as high conductivity
medium will suppress the double layer thickness and hence lesser
hydrodynamic radius.
Surface structure and shape: Any change to the surface structure will affect the
diffusion speed.
78
The scattered light that is observed comes from a collection of scattering
elements within a scattering volume that is defined by the scattering angle and
detection apertures.
The observed intensity of the scattered light at any instant will be a result of the
interference of light scattered by each element; and thus, will depend on the
relative positions of the elements.
Because particles in Brownian motion move about randomly, the scattered
intensity fluctuations are random. The fluctuations will occur rapidly for smaller,
faster moving particles and more slowly for larger, slower moving particles.
Digital correlator
HOW DLS WORKS??
79
In DLS, the speed at which the particles are diffusing due
to Brownian motion is measured.
This is done by measuring the rate at which the intensity
of the scattered light fluctuates when detected using a
suitable optical arrangement.
The rate at which these intensity fluctuations occur will
depend on the size of the particles.
DIGITAL CORRELATOR IN DLS
80
software uses algorithms to
extract the decay rates for a
number of size classes to produce
a size distribution
Number, volume and intensity
distributions of 5 and 50 nm
particles (1:1) in a solution
ZETA POTENTIAL ANALYZER
81
On the assumption that DLVO theory, zeta potential, factors
affecting zeta potential is known
DLVO theory
V
T
= V
R
+ V
A
A = Hamaker constant
D = Particle separation
a = Particle radius,
t = solvent permeability,
= a function of the ionic composition a
= the zeta potential.
ZETA POTENTIAL
82
The liquid layer surrounding the
particle exists as two parts;
An inner region (Stern layer) where
the ions are strongly bound
An outer (diffuse) region where they
are less firmly associated.
Within the diffuse layer there is a
notional boundary inside which the
ions and particles form a stable
entity. When a particle moves (e.g.
due to gravity), ions within the
boundary move it. Those ions
beyond the boundary stay with the
bulk dispersant. The potential at this
boundary (surface of hydrodynamic
shear) is the zeta potential.
FACTORS AFFECTING ZETA POTENTIAL
83
pH






Conductivity
Concentration of a formulation component


CONFIGURATION OF A ZETA ANALYZER
84
U
E
= electrophoretic mobility,
Z = zeta potential,
= dielectric constant,
= viscosity and f(a)
=Henrys function
a = the ratio of the particle
radius to electrical double
layer thickness