MM-407: NANOSTRUCTURED MATERIALS

NANOTECHNOLOGY

Nanotechnology deals with small structures or small-

sized materials

Prefix of nanotechnology i.e. nanos

comes from the Greek word for dwarf

Nanometer (nm) is one billionth of a meter, or l0-9 m

One nanometer is approximately the length

equivalent to 10 hydrogen or 5 silicon atoms aligned
in a line
Small features permit more functionality
Physical Properties of Nanomaterials

Copper which is an opaque substance become

transparent.

Platinum which is an inert material become catalyst.

Aluminum which is a stable material turns

combustible.

Silicon insulators become conductors.

Gold which is solid, inert and yellow on room
temperature at micro scale becomes liquid and red in
color at nano scale on room temperature. It also gets
unusual catalytic properties not seen at macro scale.
 Nanotechnology Definitions

The development and use of devices that have a size

of only a few nanometres
www.physics.about.com

Research and technology development at the atomic,

molecular or macromolecular level in the length scale
of approximately 1 - 100 nm range, to provide a
fundamental understanding of phenomena and
materials at the nanoscale and to create and use
structures, devices and systems that have novel
properties and functions because of their small and/or
intermediate size.
www.nano.gov

Branch of engineering that deals with things smaller

than 100 nm (especially with the manipulation of
individual molecules).
www.hyperdictionary.com

The art of manipulating materials on an atomic or

molecular scale especially to build microscopic
devices.
Miriam Webster Dictionary
Nanotechnology, or, as it is sometimes called,
molecular manufacturing, is a branch of engineering
that deals with the design and manufacture of
extremely small electronic circuits and mechanical
devices built at the molecular level of matter.
www.whatis.com
OLD NANOTECHNOLOGY

Stained-glass windows

Silver-Halide Photography

AR-coated lenses
(anti-reflecting)

Viruses are nanomachines

NEW NANOTECHNOLOGY

Vastly improved catalysts enhance surface area

to volume ratios

Designer drugs

Cheap, sensitive medical diagnostics

Transparent Sunblock

Nanotube-strengthened cables

Difference:
Designing and manipulating at the molecular level whereas
before it was either evolution that did it for us or results
 happened which we never really understood and so
couldnt optimize
HISTORY OF SCIENTIFIC REVOLUTIONS

Discovery type Name Age Start date

2,200,000
Industrial Tools Stone
BC
Industrial Metallurgy Bronze 3500BC
Industrial Steam power Industrial 1764
Automation Mass production Consumer 1906
Automation Computing Information 1946
Genetic
Health Genetic 1953
Engineering
Industrial Nanotechnology Nano age 1991
Molecular Assembler
Automation 2020?
assemblers age?
Health, industrial,
Life assemblers Life age 2050?
automation

Wilson et al. 2002. Nanotechnology: basic science and emerging

technologies. Chapman & Hall/CRC. New York.
PERSPECTIVE OF SIZE

Water molecules 3 atoms

DNA molecules millions of atoms

Carbon nanotubes millions of atoms

Molecule of DNA

Carbon nanotubes
Examples of zero-dimensional nanostructures or nanomaterials
with their typical ranges of dimension
SURFACE VS. VOLUME
a

Diamond unit cell

Si has a diamond structure with a = 5.43

A Si nanocube 10 nm on a side is composed of:
~6250 unit cells
~50,000 atoms

Each nanocube face is composed of:

~340 unit cells per face
~680 surface atoms per face
Total surface area is:
~4080 atoms (~10% surface atoms)
A bulk Si film 1 m thick on a 10 cm square:
~6.3 X 1019 unit cells
~5 X 1020 atoms
~1.4 X 1017 surface atoms (~0.03% surface atoms)
MORE THAN SIZE.

Interesting phenomena:

Chemical
Take advantage of large surface to volume ratio,
interfacial and surface chemistry important, systems
too small for statistical analysis

Electronic
Quantum confinement, bandgap engineering, change
in density of states, electron tunneling

Magnetic
Giant magneto-resistance by nanoscale multilayers,
change in magnetic susceptibility

Mechanical
Improved strength hardness in light-weight
nanocomposites and nanomaterials, altered bending,
compression properties, nanomechanics of molecular
structures
Optical
Absorption and fluorescence of nanocrystals, single
photon phenomena, photonic band gap engineering
Fluidic
Enhanced flow properties with nanoparticles,
nanoscale adsorbed films important

Thermal
Increased thermoelectric performance of nanoscale
materials, interfacial thermal resistance important
 WHAT ARE NANOSTRUCTURES?

At least one dimension is between 1 - 100 nm

2-D structures (1-D confinement):

Thin films
Planar quantum wells
Superlattices

1-D structures (2-D confinement):

Nanowires
Quantum wires
Nanorods
Nanotubes

0-D structures (3-D confinement):

Nanoparticles
Quantum dots

Dimensionality, confinement depends on structure:

Bulk nanocrystalline films
Nanocomposites
THIN FILMS

Nanoscale Thin Film

Single two dimensional film, thickness < ~100

nm

Electrons can be confined in one dimension;

affects wavefunction, density of states

Phonons can confined in one dimension; affects

thermal transport

Boundaries, interfaces affect transport

FABRICATION OF NANOSTRUCTURES AND
NANOMATERIALS
Group according to the growth media:

(1) Vapor phase growth, including laser reaction

pyrolysis for nanoparticle synthesis and atomic
layer deposition (ALD) for thin film deposition.

(2) Liquid phase growth, including colloidal

processing for the formation of nanoparticles and
self assembly of monolayers.

(3) Solid phase formation, including phase

segregation to make metallic particles in glass
matrix and two-photon induced polymerization
for the fabrication of three-dimensional photonic
crystals
.
4) Hybrid growth, including vapor-liquid-solid
(VLS) growth of nanowires.
Group the techniques according to the form of
products:

(1) Nanoparticles by means of colloidal processing,

flame combustion and phase segregation.

(2) Nanorods or nanowires by template-based

electroplating, solution liquid solid growth(SLS),
and spontaneous anisotropic growth.

(3) Thin films by molecular beam epitaxy (MBE)

and atomic layer deposition (ALD).

(4) Nanostructured bulk materials, for example,

photonic bandgap crystals
 CHALLENGES IN NANOTECHNOLOGY

Integration of nanostructures/nanomaterials into

or with macroscopic systems that can interface
with people

Building & demonstration of novel tools to

study at the nanometer level what is being
manifested at the macro level

The small size and complexity of nanoscale

structures make the development of new
measurement technologies

New measurement techniques need to be

developed at the nanometer scale and may
require new innovations in metrological
technology.

Measurements of physical properties of

nanomaterials require extremely sensitive
instrumentation, while the noise level must be kept
very low.

FABRICATION AND PROCESSING OF

NANOMATERIALS THE FOLLOWING
CHALLENGES MUST BE MET:

(1) Overcome the huge surface energy, a result

of enormous surface area or large surface to
volume ratio.

(2) Nanomaterials with desired size, uniform

size distribution, morphology, crystallinity,
chemical composition, and microstructure

(3) Prevent nanomaterials and nanostructures

from coarsening through either Ostwald ripening
or agglomeration as time evolutes.

For the fabrication of nanoparticles, a small size

is not the only requirement.
 PRACTICAL APPLICATION
&
PROCESSING CONDITIONS FOR
NANOMATERIALS

(i) Identical size of all particles (also called

monosized or with uniform size
distribution)

(ii) Identical shape or morphology,

(iii) Identical chemical composition and

crystal structure that are desired among
different particles and within individual
particles, such as core and surface
composition must be the same
 (iv) Individually dispersed or mono-
dispersed, i.e. no agglomeration.
If agglomeration does occur,
nanoparticles should be readily
redispersible.
EXCITING APPLICATIONS OF
NANOTECHNOLOGY INCLUDE:
Nanopowders
the unusual properties of particles less than 100 nm
allow a range of new and improved materials with a
breadth of applications, such as plastics that behave
like ceramics or metals; new catalysts for
environmental remediation; improved food shelf-life
and packaging; and novel drug delivery devices.

Carbon nanotubes graphite can be rolled into a

cylinder with a diameter of about 1 nm. These strong
but light carbon nanotubes are being developed for
a raft of uses, such as sensors, fuel cells, computers
nd televisions.

Nanomembrane filtration systems these have

the potential to address one of the most pressing
issues of the 21st Century safe, clean, affordable
water.
 Molecular electronic cross bar latches
Hewlett-Packard believes that silicon computer chips
will probably reach a technical dead end in about a
decade, to be replaced by tiny nanodevices described
as cross bar latches.

Quantum dots these are small devices that

contain a tiny droplet of free electrons essentially
artificial atoms. The potential applications are
enormous, such as counterfeit-resistant inks, new bio-
sensors, quantum electronics, photonics and the
possibility of tamper-proof data transmission.

New technologies for clean and efficient energy

generation.
 Nanostructures
Definition:

A nanostructure is an object of intermediate size

between molecular and microscopic (micrometer-
sized) structures.

Number of dimensions on the nanoscale

Nanotextured surfaces one dimension on nanoscale

i.e., only the thickness of the surface of an object is
between 0.1 and 100 nm.

Nanotubes have two dimensions on the nanoscale,

i.e., the diameter of the tube is between 0.1 and 100
nm; its length could be much greater.

Spherical nanoparticles have three dimensions on

the nanoscale,
i.e., the particle is between 0.1 and 100 nm in each
spatial dimension.
The terms nanoparticles and ultrafine particles (UFP)
often are used synonymously although UFP can reach
into the micrometer range.

Two approaches to the synthesis of

nanomaterials and the fabrication of
nanostructures:

1) Top-down

2) Bottom-up

Attrition or milling is a typical top-down method

in making nanoparticles.

Colloidal dispersion is a good example of bottom-up

approach in the synthesis of nanoparticles.

Lithography may be considered as a hybrid approach,

since the growth of thin films is bottom-up whereas
etching is top-down, while nanolithography and
nanomanipulation are commonly a bottom-up
approach.

BOTTOM-UP APPROACH

Build-up of a material from the bottom:

atom-by-atom molecule-by-molecule

In organic chemistry and/or polymer science, we

know polymers are synthesized by connecting
individual monomers together.

In crystal growth, growth species, such as atoms, ions

and molecules, after impinging onto the growth
surface, assemble into crystal structure one after
another.

Advantages
Less defects,
Homogeneous chemical composition,
Better short and long range ordering
 Reason
Driven mainly by the reduction of Gibbs
free energy,, therefore closer to a
thermodynamic equilibrium state

Examples:

Production of salt and nitrate in chemical industry,

Growth of single crystals and deposition of films in
electronic industry.

For most materials, there is no difference in physical

properties of materials regardless of the synthesis
routes, provided that chemical composition,
crystallinity, and microstructure of the material in
question are identical.

Top-down Approach

Disadvantages
Introduces internal stress,
Surface defects (i.e. imperfections)
Contaminations
SOLID SURFACES PHYSICAL CHEMISTRY

Nanomaterials possess a large fraction of surface

atoms per unit volume.

The ratio of surface atoms to interior atoms changes

on dividing macroscopic object into smaller parts.

The total surface energy increases with the overall

surface area.

Large surface energy therefore thermodynamically

unstable or metastable
The percentage of surface atoms changes with the palladium cluster
diameter.
 SURFACE ENERGY REDUCTION

(i) Surface Relaxation

The surface atoms or ions shift inward

(ii) Surface Restructuring

Combining surface dangling bonds into new bonds
 Original Restructured

(iii) Surface adsorption

Chemical or physical adsorption of terminal
chemical species onto the surface by forming
chemical bonds or weak attraction forces such as
electrostatic or van der Waals forces

(iv) Composition segregation or impurity enrichment

Through solid-state diffusion.

AGGLOMERATION OF INDIVIDUAL
NANOSTRUCTURES

(1) Sintering
Individual structures merge together
Polycrystalline material

(2) Ostwald ripening

Large structures grow at the cost of
smaller ones
Appreciable solubility in a solvent
 Single uniform structure

(a) Sintering (b) Ostwald ripening

Sintering
Solid-state diffusion
(i) Surface diffusion
Requires the smallest activation energy
Start at relatively low temperature

(ii) Volume diffusion

Require moderate temperatures,
Volume diffusion dominates

(iii) Cross grain-boundary diffusion

Requires highest activation energy
Significant only at high temperatures
Evaporation-condensation
Nanomaterials have an appreciable vapor pressure at
the processing temperature.

Dissolution-precipitation
Solid is dispersed in a liquid in which the solid is
partially soluble
Vapor pressure of a number of liquids as a function of droplet
radius
Variation in solubility of silica with radius of curvature of surface
 OSTWALD RIPENING

Can have either positive or negative influence on the

resulting materials, depends on process & application

Can either widen or narrow the size distribution,

depending on the control of the process conditions

Abnormal grain growth, leading to inhomogeneous

microstructure and inferior mechanical properties

Specifically, it has been used to narrow the size

distribution of nanoparticles by eliminating small one