Frontier Chemistry

Chapter 6

Nanomaterials
Materials

having critical dimension

between 1-100nm
Solid material
Exhibits novel properties related to
this scale
Novel optical properties appear in
nanoparticle are being exploited for
Information
Biological
Sensing
Energy technologies
Example: semiconducting nanoparticle

and metallic nanoparticle

Nanomaterials - DNA
Ultimate

nanomaterial
Stores information as the sequence
of base pairs that are spaced about 3
nm apart.
Folded DNA molecules have an
information density of more than
about 1 Tb = 1012 which is much
greater than achieved in most
current data storage system.

Nanoscale
Sheet

of paper

100,000

nanometers thick
Human

Hair

80,000 100,000

nanometers wide
Fingernail
Grows one

nanometer per
second

http://www.nano.gov/nanotech101/what/nano-size

Applications

Tsuzuki International
Journal of Nanotechnology
2009

Applications
UV

Protection

Ultra fine grade TiO2 (Kobo Corporation)

Antibacterial
Nano silver Samsung washing machines
Wound Dressings Smith and Nephew Acticoat

Pilkington

Aktiv

Applications
Water

treatment

Nano4water cluster

Drug

Delivery

Liposomes

Catalysts
Hybrid Copper/ Gold

Nanoscience
Study

of the properties of matter

that have length scales between 1
and 100 nm
Study of the new effects that arise
only in materials that exist on the
nanoscale

Nanotechnology
Collection

of procedures for manipulating matter

on this scale in order to build nanosized entities
for useful purposes
Creates new functionalities
Photosynthesis example of biological
nanotechnology
Nanostructures are exploited to:
absorb light
Separate electric charge
Shuttle proton around
Convert solar energy into biologically useful chemical

energy

Nanotechnology
Human

have practiced nanotechnology for

centuries
Gold and silver salts have been used to colour
glass
Gold produce red stained glass
Silver produce yellow

Photosensitive

nanosized particle in silver halide

emulsions used in photography
Nanosized carbon granules in the carbon black
used for reinforcing tires and in printers ink
Biomedical technology metallic nanopigment
Use to tag DNA and other nanoparticle

Nanotechnology
Began

to take shape in the latter half

of the twentieth century
Significant contribution
Gerd Binnig and Heinrich Rohrer

developed the scanning tunneling

microscope
Scanning probe tip was used to
rearrange atoms on a surface to spell
out words
Demonstrating and ability to manipulate

Characterization
Scanning

tunneling microscopy

Atomically sharp conductive tip is scanned at about 0.3

10 nm above the surface

Uses tunneling current from a sharp tip to image and
characterize a surface
Atomic

force microscopy

Atoms at the tip of the probe interact with the surface

atoms of the sample through intermolecular forces such

as van der waals interactions.
The cantilever holding the probe bends up and down in
response to the forces and the extent of deflection is
monitored with a reflected beam

Characterization
Atomic

force microscopy

Variations on AFM include

Frictional force microscope measures variations in the lateral
forces on the tip based on chemical variations on the surface
Magnetic force microscope uses magnetic tip to image
magnetic structures
Electrostatic force microscope - uses tips that can sense
electric fields
Scanning capacitance microscope - tip is used as an electrode
in a capacitor
Scanning near field optical microscopy (SNFOM)
Combines the local interactions of a scanning probe and a
specimen with well established methods of optical
spectroscopy

AFM
2D image

Membrane sample

3D image

Characterization Electron
microscopy techniques
Electron

beams are accelerated through 1

200kv and electric and magnetic field are used to
focus the electron
In transmission electron microscopy (TEM) the
electron beam passes through the thin sample
being examined and is imaged on a
phosphorescent screen
Used for imaging electron-transparent biological

samples

Characterization Electron
microscopy techniques
In

scanning electron miscroscopy

(SEM) the beam is scanned over
the object and the reflected
(scattered) beam is then imaged by
the detector

SEM at UKM

SEM
Membrane sample

Surface of a membrane

Cross section of a membrane

Top-down and bottom-up

fabrication
Top-down

approaches

A macroscale (or microscale) object and to carve out

nanoscale patterns
Patterns are first designed on a large scale, their
lateral dimensions are reduced, then used to transfer
the nanoscaled features into or onto the bulk material
Physical interaction
Lithography
Mechanical stamping
nanoscale printing

Most common approach is photolithography, the

technique used to fabricate very large scale integrated

circuits having feature dimension on the 100 nm scale

Top - down

1m

1 nm

100 pm

Bulk material
Thin films
Heterostructures
Litographic wires
Quantum dots

Nanocrystals
Molecular wires
Proteins
Molecules
Atoms

Bottom - up

Top-down and bottom-up

fabrication
Bottom

up

Build larger objects by controlling the

arrangements of their component smallerscale objects

Start with control over the arrangements of
atoms and molecules
Bottom up approach to nanoscale fabrication
because of its focus on the interactions of
atoms and molecules and their arrangement
into larger functional structures

Top-down and bottom-up

fabrication
TOP DOWN

BOTTOM UP

Simple, cheaper
Conceptually simpler
Easy to control
Difficult to achieve
true nano and size
monodispersity
Require more energy
and time

More complex and

expensive
Conceptually more
difficult
Difficult to control
Easier to achive true
nano and size
monodispersity
Require less energy
and time

Synthesis
Solution

based synthesis of nanoparticles

Main techniques for nanoparticle synthesis because

they have atomically mixed and highly mobile

reagents
allow for the incorporation of stabilizing molecule
Widely successful in practice
Two stages of crystallization from solution are nucleation
and growth

Vapour phase synthesis of nanoparticle

Alternative techniques for nanoparticle synthesis because
they have atomically mixed and highly mobile reagents

Synthesis
Synthesis

using frameworks, supports and

substrates
Nanosized reaction vessel
By carrying out reactions in nanoscale reaction vessels, the
ultimate dimensions of solid products are confined to the
vessel size; a reverse micelle has an aqueous core in which
reactions can occur
Physical vapour deposition
A vapour of atoms, ions or clusters physically adsorb to the
surface and combine with other species to create a solid
molecular beam epitaxy is a technique where evaporated
species from elemental charges are directed as a beam at
a substrate where growth occurs

Synthesis
Chemical

vapour deposition

A vapour of molecules chemically

interact or decompose at or near the

substrate, where they adsorb to the
surface and combine with other species
to create a solid an residual gaseous
product