Characterization of

Nanomaterials
Estareja, Rogel Lindolf B.

How did it all start?

Professor Richard Feynman presented the idea of manipulating
and controlling things on an extremely small scale by
building and shaping matter one atom at a time.
Feynman described how the 24 volumes of the Encyclopedia
Brittanica can be written on the head of a pin. He said that
letters could be represented by six to seven bits of
information for each letter. He also suggested using the
inside as well as the surface of a metal to store information.
Feynman allowed that if each bit was equal to 100 atoms, all
the information of all the books of the world could be written
in a cube of material 1/200 inch wide, about the size of a tiny
speck of dust.
THERE IS PLENTY OF ROOM AT THE BOTTOM!

Nanotechnology
In 1989, Don Eigler of IBM formed the
letters of the company from 35
xenon atoms by STM.

Optical Microscopes are not for

nanoscale analysis?
The smallest resolvable distance
between objects is about half the
wavelength of the light used
So, for visible light (500nm), resolving
power is about 250 nm only!
Nanomaterials (<100 nm) would
appear blurred or undistinguishable.
Only wavelengths from UV, X-ray, up
to Gamma are applicable for visual
characterization.

Using Electron beam

By de Broglie wave equation

(nm)

v (x 108 cm/sec)

50, 000

0.0055 nm

1.326

100, 000

0.0039

1.875

1, 000, 000

0.0012

5.930

Scanning Electron
Microscopy
SEM
Characterization
1. Topography
2. Composition
. Secondary Electrons
produced by Inelastic
collision
with
a
Core
electron, having energy
lower than the Primary
electrons. Responsible for
IMAGING
. Backscattered Electrons
produced
by
Elastic
scattering of Core electrons
and having the same
energy as the primary
electrons. Responsible for
CONTRAST.
. Auger Electrons Instead
of photon emission when
electron-hole decay, higher
orbital
electrons
would
instead be emitted.

Low voltage SEM

The extreme surface sensitivity of this
technique is a result of the reduced
interaction volume.
This allows the measurement of images with
nanometer scale resolution with under 1
kV acceleration.
At these low energies, charging is not an
issue and it is possible to measure
images without conductive coatings.
Analytical Electron Microscopy
SEMs can be equipped with other analytical
tools such as X-ray, Electron, and Ion
detectors which could be used for
qualitative and quantitative informations.

Transmission
Electron Microscopy
TEM
Characterization
a. Imaging Mode
1.

Topography

b. Scattering Mode
1.
2.

c.

Morphology
Composition

The high magnification

or resolution of all
TEM is a result of the
small
effective
electron wavelengths

Focused Mode
1.
2.

Thermal Properties
Mechanical Properties

. Elastic scattering no
energy loss and gives rise
to diffraction patterns.
. Inelastic interactions energy loss due to grain
boundaries,
dislocations,
second-phase
particles,
defects, density variations
leading to spatial variation
in intensity of transmitted
electrons.

Higher electron energy

causes
smaller
electron wavelengths.

SEM vs TEM
Scanning Electron Microscope

Samples must be
conductive or else it
will BURN!
Im in 3D!
Over 300k times
magnification

Transmission Electron
Microscope

Samples must be thin

enough or else it wont
project a recognizable
image!
Just 2D.
Up to 1million times
magnification

X-ray Diffraction
XRD
Characterizations
1. Lattice constant
2. d-spacing
3. Crystallinity
4. Thickness (films)
5. Particle Size (grains)
. X-ray
interactions
depends
on
the
number of atom on a
plane. This is why
only specific planes
would
cause
diffraction.

Smaller crystals
produce broader XRD
peaks
Scherrers Formula

t- thickness of crystallite
K- shape constant
- wavelength
B- FWHM
- Bragg Angle

Small Angle X-ray

Scattering
SAXS
Characterization
1. Particle Size
2. Specific Surface Area
3. Morphology
4. Porosity
. Fluctuations in electron
density over lengths on the
order of 10nm or larger can
be sufficient to produce an
appreciable scattered X-ray
densities at angles 2 < 50
. It is capable of delivering
structural information of
molecules between 5 and
25
nm.
Of
repeated
distances
in
partially
ordered systems of up to
150 nm.

SAXS is the scattering due

to the existence of
inhomogeneity regions of
sizes of several
nanometers to several
tens nanometers.

How Scanning Probe Microscopy

Works?

Scanning Tunneling
Microscopy
STM uses the a quantum physics phenomenon
called Tunneling to provide detailed images
of substances that can conduct electricity.
The probe is brought to within a few angstroms
of the surface of the material, and a small
voltage is applied between the surface and the
probe.
Because the probe is so close to the surface,
electron leaks, or tunnel, across the gap
between the probe and surface , generating
current.

 The strength of the tunneling current depends

on the distance between the surface and the
probe.
If the probe moves closer o the surface, the
tunneling current increases, and if the probe
moves away from the surface, the tunneling
current decreases.
As the scanning mechanism moves along the
surface, the mechanism constantly adjusts the
height of the probe to keep the tunneling
current constant.
By tracking these minute changes, a computer
can create a 3-D representation of the surface.

Atomic Force Microscopy

As the metal probe in an AFM moves
along the surface of a sample, the
electrons in the probe are repelled by
the electrons of the atoms in the sample
and the AFM adjusts to the height of the
probe to keep the force on it constant.
By the up-and-down movements of the
probe, a computer can track and make a
3-D image of the surface sample

Scanning Probe
Microscopy
SPM
Characterization
1. Topography
2. Magnetic
3. Thermal
4. Electrical
5. Mechanical
6. Chemical
. By modifying the tip
chemically allows various
properties of the sample
surface to be measured.
. Characterization depends
on the type of the
interactions between the
tip and the sample surface.
. Resolving power depends
on the geometry of the tip,
a sharper tip would be able
to scan a deeper surface

Types of SPM
1. Scanning Thermal Microscopy
2. Magnetic Force Microscopy
3. Dynamic Force Microscopy
4. Electrostatic Force Microscopy
5. Chemical Force Microscopy
6. Friction Force Microscopy
7. Magnetic Resonance Microscopy
8. Kelvin Force Microscopy
9. Scanning Capacitance Microscopy
10.Elasticity Modulus Microscopy
11.Ultrasonic Force Microscopy
12.Force Distance Microscopy

Scanning Probe Microscopy

The up-down movement of the tip of the probe are
measured by a laser beam that reflects off the top of the
cantilever, and its jiggling as the beam vibrates is
measured by a optical detector that maps the surface.

The Tiniest Wires

An image from a STM reveals wires on eight to ten atoms
wide. Researchers at Hewlett-Packard Company in Palo
Alto, California, developed the nanowires, the tiniest wires
yet created.

Gas Adsorption
Characterization
1. Particle Size
2. Specific Surface Area
3. Pore volume
. Adsorption maybe physical
or chemical
. Physical Adsorption is
particularly useful in the
determination of specific
surface area and pore
volume in mesopores
(2~50nm) or micropores
(<2nm).
. Chemical Adsorption is also
for the determination of
surface area; however it
takes place via specific
chemical forces and is thus
unique to the gas and solid
in question.

KELVIN EQUATION:

P Equilibrium vapor pressure

P0 Equilibrium pressure
r radius of pore
surface tension
V molar volume
Rg Gas constant
T Absolute Temperature

Gas Adsorption

Energy Dispersive
X-ray Spectrometry
Characterization
EDS/EDX
1. Composition

. The primary beam of an

SEM/TEM
collides
with
Core Electrons and ejects
them.
. The core hole thus created
may get filled by electron
de-excitation resulting in Xray.
. All photons (X-ray) emitted
by the sample are collected
and
measured
simultaneously by a solidstate X-ray detector
. The common EDS detector
is lithium drifted silicon
(Si/Li)

HOW DOES EDS WORKS?

When an X-ray photon falls on an intrinsic
semiconductor, charge carriers are
created, the electrons and holes.
The X-ray photon is slowed down by
colliding
inelastically
with
other
electrons in the semiconductor, and thus
creating many charge carriers.
The number of charges created will count
as pulses, this pulses then are converted
to voltage, representing the energy of
the X-ray photons.
Different atoms would emit different
energies of X-ray since every atom has
different atomic sizes and electron
configuration.

Energy Dispersive X-ray

Spectrometry

How does PL works?

Photoluminescence
(XPS, UPS)
Characterization:
1. Compositional
2. Concentration

. The emission of light can

result from a variety of
stimulations.
. When the emission is
resulted from electronic
stimulation, it is referred as
cathodoluminescence.
. When
a
high-energy
photon such as X-ray is
used to excite the sample,
it is called to as X-ray
fluorescence.

A material gains energy by absorbing

photon at some wavelength by
promoting an electron from a low to a
higher energy level.
The system then undergoes a nonradiative internal relaxation involving
interactions
with
crystalline
or
molecular vibration and rotational
modes, and the excited electron moves
to a more stable excited level such as
the bottom of the conduction band or
the lowest vibrational molecular state.
After a characteristic lifetime in the excited
state, electron will return to the ground
state. Some or all of the energy is
released during this final transition.

Infrared
Spectroscopy
FT-IR
(vibrational)
Characterization:
1. Compositional
2. Concentration
3. Atomic Structure
. The mechanical molecular
and crystal vibrations are at
very high frequencies ranging
from 1012 to 1014 Hz (3-300m
wavelength), which is in the
infrared (IR) regions of the
electromagnetic spectrum.
. The oscillations induced by
certain vibrational frequencies
provide a means for matter to
couple with an impinging
beam
of
infrared
electromagnetic radiation and
to exchange energy with it
when frequencies are in
resonance.

What is the principle behind IR

spectroscopy?
Firstly, molecules and crystals can be thought
of as systems of balls (atoms or ions)
connected by springs (chemical bonds).
These systems can be set into vibration, and
vibrate with frequencies determined by the
mass of the balls (atomic weight) and by
the stiffness of the springs (bond strength).
With these oscillations of the system, a
impinging beam of infrared EMR could
couple with it and be absorbed.
These
absorption
frequencies
represent
excitations of vibrations of the chemical
bonds and, thus, are specific to the type of
bond and the group of atoms involved in
the vibration.
In an infrared experiment, the intensity of a
beam of IR is measured before and after it
interacts with the sample as a function of
light frequency.

Raman
Spectroscopy
(vibrational)
Characterization:
1. Compositional
2. Concentration
3. Atomic Structure
. It differs from the IR
spectroscopy by an indirect
coupling of high-frequency
radiation, such as visible
light, with vibrations of
chemical bonds.
. Raman Spectroscopy is
very
sensitive
to
the
lengths,
strengths
and
arrangements of chemical
bonds, but less sensitive to
the chemical compositions

How Raman Spectroscopy works?

When an incident photon interacts with the
chemical bond, the chemical bond is excited
to a higher energy state.
Most of the energy would be re-radiated at the
same frequency as that of the incident
exciting light, which is known as Rayleigh
scattering.
A small portion of the energy is transferred and
results in exciting the vibrational modes,
and this Raman process is called Stokes
scattering.
The subsequent re-radiation has a frequency
lower than that of the incident exciting light.
The vibrational energy is deducted by
measuring the difference between the
frequency of the Raman Line and the
Rayleigh Line.

Chemical characterization
Techniques
Method

Element
Sensitivity

Detection
Limit (%)

Lateral
Effective
Resolution probe
depth

SEM-EDS

Na U

~0.1

~1m

~1m

AES

Li U

~0.1 - 1

50nm

~1.5nm

XPS

Li U

~0.1 1

~100m

~1.5nm

RBS

He-U

~1

1mm

~20nm

SIMS

H-U

~10-4

~1m

1.5nm

References
Nanotechnology Demystified
-Linda Williams & Wade Adams
NANO: The Essentials (Understanding
Nanoscience and Nanotechnology)
- T. Pradeep
Nanostructures and Nanomaterials
(Synthesis, properties & applications)
- Guozhong Cao