MTOE48

Nanomaterials
and Applications

Dr. V. Karthik

Assistant Professor, Department of MME, NITT

 Properties of a Material

– A property describes how a material acts under certain

conditions
– Types of properties
– Optical (e.g. color, transparency)
– Electrical (e.g. conductivity)
– Physical (e.g. hardness, melting point)
– Chemical (e.g. reactivity, reaction rates)
– Properties are usually measured by looking at large (~1023)
aggregations of atoms or molecules

Sources: http://www.bc.pitt.edu/prism/prism-logo.gif
http://www.physics.umd.edu/lecdem/outreach/QOTW/pics/k3-06.gif
Unique attributes of the
nano-scale
 Here is a Listing of Some of the Unique
Attributes of the Nano-scale
– Very small size—obvious yet the impact is tremendous!
– High surface to volume ratio ─ resulting in many, if not most, of the
atoms being on the surface
– High surface to volume ratio ─ resulting in a unique surface environment
for most of the atoms
– Surface forces dominate over bulk forces ─ for example, gravity (a bulk
force) is not important
– Quantum mechanical effects are important
– Wave properties of light are important
 Some of the Unique Attributes of the
Nano-scale (continued)

– Sizes corresponding to basic biological structures

– Unique chemical bonding configurations possible
– Size range in which molecules can self-assemble
– New epistemologies (Working at the nano-scale has
caused us to learn new ways of “seeing” our world)
Size-Dependent Properties

How do properties change at the

nanoscale?

Some examples of the impact of these

unique attributes
 Very Small Size

• Can fit many “nano-sized things”

together with little space in between
R (radius)
• Can get large number of “nano-
sized things” per volume

• Or, can get large number per area

An example of an impact of this
attribute: Huge Areal Densities
The huge number of nano-scale transistors possible per area
means today’s state-of-the-art microelectronics circuits with
their nano-scale transistors can give more speed and more
functionality.

Copyright Matco Services Inc.

www.materialsforum.com Mick Feuerbacher, December
2005.
High surface to volume ratio

4πR2_
Ratio =
4/3πR 3

R Ratio = 3/R

This ratio is very big

when R is very small
 Impact of the Huge Surface to Volume
Ratio
This figure shows the inverse relationship between particle size and number of
Percent Surface Atoms

surface atoms.

As a particle gets smaller, a larger and larger percentage of the atoms that make
up the particle are surface atoms.

Because the number of atoms or molecules on the surface of a particle influences

the particle’s chemical and physical interactions with its environment, this
Diameter (nm)
percentage in the figure is key to defining the chemical and biological properties
of nanoparticles.

Figure 1 from Andre Nel, Tian Xia, Lutz Mädler and Ning Li., SCIENCE Vol.311. p. 622 (2006).
 Physical Properties Change:
Melting Point of a Substance
– Melting Point (Microscopic Definition)
– Temperature at which the atoms, ions, or molecules in a
substance have enough energy to overcome the intermolecular
forces that hold the them in a “fixed” position in a solid

– Surface atoms require less energy to

move because they are in contact
with fewer atoms of the substance

In contact with 3 atoms

Sources: http://puffernet.tripod.com/thermometer.jpg and

In contact with 7 atoms
image adapted from http://serc.carleton.edu/usingdata/nasaimages/index4.html
 An example of an impact of this
attribute: Melting Temperature

The melting temperature gets lower as a

nanoparticle gets smaller because higher
This data percentage of atoms are on the surface.
is for Gold This makes sense since surface atoms are
not bound to each other the same way
bulk atoms are.

Particle diameter in Angstroms

Reprinted figure with permission from Buffat and Borel, “Phys Rev. A” Volume 13, p 2287
(1976). Copyright 1976 by the American Physical Society.
Physical Properties Example:
Melting Point of a Substance

At the macroscale At the nanoscale

The majority of …almost all on the inside of …split between the inside
the atoms are… the object and the surface of the object

Changing an …has a very small effect on …has a big effect on the

object’s size… the percentage of atoms on percentage of atoms on the
the surface surface

The melting …doesn’t depend on size … is lower for smaller

point… particles
Surface Forces Dominate
over Bulk Forces

– Bulk force importance

decreases with decreasing
volume

– Surface force importance

increases with decreasing
volume
 Surface Forces Dominate
over Gravity

– Gravity’s importance
decreases with decreasing
Surface volume
forces

– Surface force importance

increases with decreasing
volume
gravity gravity
 An example of an impact of this attribute:
Colloidal Solutions

“Electronic Imaging & Signal Processing: Improving biomedical imaging

with gold nanocages” by Younan Xia and Sara E. Skrabalak. 12 May 2008,
SPIE Newsroom. DOI: 10.1117/2.1200705.1135

The nano-scale colloidal particles in the solutions seen above

will never settle out. (so long as surface forces are not present
to cause them to agglomerate. If they agglomerated, this would
increase particle volume and give gravity a chance to become
important)
Emergence of Quantum Mechanical
Effects

– Electrons can only have certain

energies in atoms due to quantum
mechanics.

R – Semiconductor nanoparticles can

behave like man-made atoms and
have only certain energies allowed
for electrons.
– The energy difference between
these allowed energies in
nanoparticles gets bigger as R gets
smaller
 Optical Properties Example: Gold

– Bulk gold appears yellow in color

– Nanosized gold appears red in color
– The particles are so small that electrons are not free to move about as in bulk gold
– Because this movement is restricted, the particles react differently with light

“Bulk” gold looks yellow

12 nanometer gold particles look red
Sources: http://www.sharps-jewellers.co.uk/rings/images/bien-hccncsq5.jpg
http://www.foresight.org/Conferences/MNT7/Abstracts/Levi/
 Optical Properties Example:
Zinc Oxide (ZnO)
– Large ZnO particles
– Block UV light
– Scatter visible light
– Appear white
Nanoscale ZnO
– Nanosized ZnO particles sunscreen is clear
“Traditional” ZnO
– Block UV light sunscreen is white
– So small compared to the wavelength of visible
light that they don’t scatter it
– Appear clear

Sources: http://www.apt powders.com/images/zno/im_zinc_oxide_particles.jpg

http://www.abc.net.au/science/news/stories/s1165709.htm
http://www.4girls.gov/body/sunscreen.jpg Zinc oxide nanoparticles
An example of an impact of this attribute: Semiconductor Quantum Dots

When excited by light, quantum dots fluoresce (re-emit light). The size and material composition
of nano-scale quantum dots dictates the color they re-emit.

Evidenttech.com
Importance of the Wave Properties of
Light

– The wavelength  of visible light is much larger than the

sizes R of nano-scale structures.

– Because of this, light scatters and diffracts when it

interacts with nanostructures
An example of an impact of this attribute: Photonic Crystals
Man-made nano-structures can cause light to turn sharp 90 degree corners, as seen below

Reproduced with permission of the MRS Bulletin. www.mrs.org/bulletin

 Another example of an impact of this

attribute
Nanostructures can cause light of different colors to scatter and
diffract differently. This effect is used by nature to give the colors
seen in butterfly wings.

1x magnification 220x magnification 5000x magnification 20,000 x magnification

of wing
Butterfly Scales
Militaries Study Animals for Cutting-Edge Camouflage. James Owen in England for National Geographic News March 12, 2003, Proc. R. Soc. Lond. B (1999) 266, 1403-1411
 Sizes Corresponding to Basic Biological Structures

– We can now easily make structures in the 1nm to ~100nm size range.

– This is the size range of many of the key structures in biological systems
 An example of an impact of this
attribute:

Public Library of Science, “The Intersection of Biology and Materials Science” by

George M. Whitesides and Amy P. Wong Vol. 31, p. 23.

The cell is a complex structure with many compartments and organelles possessing individual and
interdependent functions. Many of a cell`s features (e.g., pores) and, of course, DNA and RNA are all in
the nano-scale. We can now make structures like these smallest of features in a cell.
 Another Example:
Structures that can “read” DNA
DNA
Can now make We can now use
structures so small electrical signal
that they, for changes to “read” the
example, can force DNA as it passes
DNA to line-up through
single file in order
to pass through

Golovchenko, Branton, et. al. (Harvard Nanopore Group)

Sequencing DNA using nanopore ionic conductance.
Unique chemical bonding configurations possible
Carbon nanotubes

Odom et al, J. Phys. Chem. B104, 2794 (2000).

Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
Reproduced with permission.
An example of an impact of this attribute
Superior strength concrete for construction made with CNTs

S Bulletin, Vol. 31. P. 23, January 2006 Makar, J. M Beaudoin, J.J/NRCC-46618 http://irc.nrc-cnrc.gc.ca/ircpubs.
Reproduced with the permission of the Minister of Public Works and Government Services Canada, 2009.

Carbon nanotubes distributed on small cement grains

 Electrical Properties Example:
Conductivity of Nanotubes
– Nanotubes are long, thin cylinders of carbon
– They are 100 times stronger than steel, very flexible, and have unique electrical
properties
– Their electrical properties change with diameter, “twist”, and number of
walls
– They can be either conducting or semi-conducting in their electrical behavior

Electric current
varies by tube
structure

Multi-walled
Source: http://www.weizmann.ac.il/chemphys/kral/nano2.jpg
 New Ways of Seeing things

Actual
Atoms!

IBM Research Division

M.F. Crommie, C.P. Lutz, D.M. Eigler. Confinement of electrons to quantum corrals
on a metal surface. Science 262, 218-220 (1993).

The nano-scale tips on scanning probe

microscopes (SPMs) allow us to even “see” atoms
 Examples of the impact of this attribute:
New tools for “seeing”

– Electron beam-based techniques

TEM (Transmission Electron Microscopy)
SEM (Scanning Electron Microscopy)

– Nano-scale-sized probe-based scanning techniques

AFM (Atomic Force Microscopy)
STM (Scanning Tunneling Microscopy)
NSOM (Near Field Scanning Optical Microscopy)

Courtesy of Evans Analytical Group®

Size-Dependant Properties

Why do properties change?

Scale Changes Everything

– There are enormous scale differences in our universe!

– At different scales
– Different forces dominate
– Different models better explain phenomena
Scale Changes Everything II

– Four important ways in which nanoscale materials may differ from macroscale
materials
– Gravitational forces become negligible and electromagnetic forces dominate
– Quantum mechanics is the model used to describe motion and energy instead
of the classical mechanics model
– Greater surface area to volume ratios
– Random molecular motion becomes more important
 Dominance of Electromagnetic Forces

– Because the mass of nanoscale objects is so small, gravity becomes negligible

– Gravitational force is a function of mass and distance

and is weak between (low-mass) nanosized particles
– Electromagnetic force is a function of charge and
distance is not affected by mass, so it can be very
strong even when we have nanosized particles
– The electromagnetic force between two protons is 1036
times stronger than the gravitational force!

Sources: http://www.physics.hku.hk/~nature/CD/regular_e/lectures/images/chap04/newtonlaw.jpg
 Quantum Effects

– Classical mechanical models that we use to understand matter at the

Macrogold macroscale break down for…
– The very small (nanoscale)
Nanogold – The very fast (near the speed of light)
– Quantum mechanics better describes phenomena that classical
physics cannot, like…
– The colors of nanogold
– The probability (instead of certainty) of where an electron will be
found
Sources: http://www.phys.ufl.edu/~tschoy/photos/CherryBlossom/CherryBlossom.html
http://www.nbi.dk/~pmhansen/gold_trap.ht; http://www.sharps-jewellers.co.uk/rings/images/bien-hccncsq5.jpg;
 Surface Area to Volume Ratio
Increases
– As surface area to volume ratio increases
– A greater amount of a substance comes in contact with surrounding material
– This results in better catalysts, since a greater proportion of the material is exposed
for potential reaction
 Random Molecular Motion is Significant

– Tiny particles (like dust) move about randomly

– At the macroscale, we barely see movement, or why
it moves
– At the nanoscale, the particle is moving wildly,
batted about by smaller particles
• Analogy
– Imagine a huge (10 meter) balloon being batted about
by the crowd in a stadium. From an airplane, you barely
see movement or people hitting it; close up you see the
balloon moving wildly.
Source: http://www.ap.stmarys.ca/demos/content/thermodynamics/brownian_motion/rand_path.gif
What Does This All Mean?

– The following factors are key for understanding nanoscale-related

properties
– Dominance of electromagnetic forces
– Importance of quantum mechanical models
– Higher surface area to volume ratio
– Random (Brownian) motion
– It is important to understand these four factors when researching
new materials and properties