Introduction

The term nano originated from the Greek ‘nanos’ which means ‘dwarf’. It is one
billionth of a meter. Therefore, whenever we think about nanoscience or
nanotechnology, very small objects come to the mind. Nanomaterials are
cornerstones of nanoscience and nanotechnology. Nanostructure science and
technology is a broad and interdisciplinary area of research and development
activity that has been growing explosively worldwide in the past few years. It has
the potential for revolutionizing the ways in which materials and products are
created and the range and nature of functionalities that can be accessed. It is
already having a significant commercial impact, which will assuredly increase in
the future.

Fig. 1: Evolution of science and technology and the future

What is Nanoscale? – An idea (size comparison)

Nanoscale materials are defined as a set of substances where at least one dimension
is less than approximately 100 nanometers. A nanometer is one millionth of a
millimeter - approximately 100,000 times smaller than the diameter of a human
hair. Nanomaterials are of interest because at this scale unique optical, magnetic,
electrical, and other properties emerge. These emergent properties have the
potential for great impacts in electronics, medicine, and other fields.

Fig. 2: Nanomaterial (For example: Carbon nanotube)

The size of a football or a soccer ball when compared with the size of the earth, it
is around 10 million times smaller. And now, if a nanomaterial like a C60 molecule,
which is also called a fullerene is compared, then the C60 molecule is nearly 1
billion times smaller than the size of a football. So, we can now imagine that how
small is a nanoparticle, if we know, how small is the football with respect to the
size of the earth. And the fullerene molecule which is a nanoparticle is much
smaller than the ratio of the earth size to the football as compared to the size of the
football to the nanoparticle.
History and Evolution of Nanotechnology

The history of nanomaterials began immediately after the big bang when
Nanostructures were formed in the early meteorites. Nature later evolved many
other Nanostructures like seashells, skeletons etc. Nanoscaled smoke particles were
formed during the use of fire by early humans.

The Lycurgus cup, 4th century (A.D.) nano wonder which is kept at the British
Museum is a familiar example of the early artistic use of the metal nanoparticles.
Fig. 3: Lycurgus cup (a) in the reflected light (green), (b) in the transmitted light
(red).

The scientific story of nanomaterials however began much later. One of the first
scientific report is the colloidal gold particles synthesized by Michael Faraday as
early as 1857. From the paper in Philosophical Transactions entitled ‘Experimental
relations of gold (and other metals) to light’, based on his Bakerian lecture to the
Royal Society in London on 5 February 1857, it is clear that Michael Faraday was
fascinated by the ruby colour of colloidal gold. The objective of his investigations
was to examine the interaction of light with metal particles, but much of this paper
focused on various aspects of the formation, nature and properties of ruby gold,
and these systematic studies and perceptive interpretations did in fact mark the
birth of modern colloidal chemistry.

Although Faraday described work with a number of metals, the ruby colour
produced in ‘solution’ by fine particles of gold which are “very minute in their
dimensions”, and prepared via various practical approaches, was the main topic of
his lecture. A typical preparation used an aqueous solution of a gold compound,
e.g. NaAuCl4, and treated this with a reducing solution such as phosphorus in
carbon disulfide in a two phase system. The yellow colour of sodium chloroaurate
(NaAuCl4) changes within minutes to the deep ruby colour of colloidal gold.
Faraday concluded that the ruby fluid was gold dispersed in the liquid in a very
finely divided metallic form not visible in any of the microscopes available in his
day. Nearly 100 years later Turkevich used electron microscopic investigations to
reveal that the ruby-coloured colloids made by Faraday’s preparative routes
produce particles of gold with average sizes in the 6 ± 2 nm range.

(a) (b)

Fig. 4: (a) Faraday’s microscopic slide coated with gold colloid, (b) Faraday’s
colloidal ruby gold, reproduced by courtesy of The Royal istitution of Great Britain

Nanostructured catalysts have also been investigated for over 70 years. By the
early 1940’s, precipitated and fumed silica nanoparticles were being manufactured
and sold in USA and Germany as substitutes for ultrafine carbon black for rubber
reinforcements.
 Richard P. Feynman (Nobel Laureate in Physics, 1965) is often credited for
introducing the concept of nanotechnology about 50 years ago. In the annual
meeting of the American Physical Society at California Institute of Technology on
26 December 1959, he delivered a famous lecture entitled “There’s Plenty of
Room at the Bottom”. In this lecture, he talked about writing twenty four volumes
of the Encyclopaedia Britannica on the head of a pin, and miniaturizing the
computer. He also stated “The principles of physics, as far as I can see, do not
speak against the possibility of maneuvering things atom by atom” and suggested
that it would be possible to arrange the atoms the way we want.
The lecture of Feynman had inspired many scientists in various ways. The term
nanotechnology was first used by Norio Taniguchi in 1974. Later, K. Eric Drexler
developed the concept of nanotechnology by writing a book (in 1986) entitled
“Engines of Creation: The Coming Era of Nanotechnology”. Drexler envisioned a
world completely transformed by nano-scale robot assemblers.

Importance of size reduction

The smaller something is, the larger its surface area is compared to its volume.
This high surface-to-volume ratio is a very important characteristic of
nanoparticles. For example, imagine that you have a big block of ice with one-
meter sides (see Figure3). This block has a surface area of 6 square meters (1
square meter on a side x 6 sides) and a volume of 1 cubic meter. In this case, the
surface area to volume ratio for the ice block is 6/1 or 6. Suppose that cut the ice
into 8 pieces that are one-half of a meter per side. The surface area of each piece of
ice would be 1.5 square meters (0.5 m x 0.5 m x 6 sides). So the total surface area
of all the pieces would be 12 square meters. However, the total volume of ice
would stay the same: we haven’t added or removed any ice. So in this case, the
surface area to volume ratio is 12/1, or 12––twice the surface area to volume ratio
of the block before it was cut. If you cut the ice into 27 pieces, the surface area
increases to 18 square meters, and the surface area to volume ratio is 18/1 or three
times that of the uncut block. If you keep going, and cut the ice into 1000 small
pieces, the surface area to volume ratio is 60/1 or ten times that of the uncut block!

Fig. 5: Total surface area increases as the block is cut into smaller pieces. (the total
volume stays constant)
Imagine how big the surface area to volume ratio would be for something as small
as a bunch of nanoscale particles. The vastly increased ratio of surface area to
volume makes interactions between the surfaces of particles very important. If
something has more surface area, there are more places for other chemicals to bind
or react with it. For example, fine powders offer greater reaction speed because of
the increased surface area. Think about how much faster you can cool a glass of
water if you put
crushed ice in it rather than ice cubes. Nanoscale particles maximize surface area,
and therefore maximize possible reactivity. The large surface area to volume ratio
of nanoparticles opens many possibilities for creating new materials and
facilitating chemical processes. In conventional materials, most of the atoms are
not at a surface; they form the bulk of the material. In nanomaterials, this bulk does
not exist. Indeed, nanotechnology is often concerned with single layers of atoms on
surfaces. Materials with this property are unique. For example, they can serve as
very potent catalysts or be applied in thin films to serve as thermal barriers or to
improve wear resistance of materials.

Manipulation of Atoms
Assembly atom-by-atom is similar to bricklaying in that atoms are moved into
place one at a time using tools like the STM and AFM. Using this technique,
scientists have, for example, positioned xenon atoms on nickel and buckyballs on
copper to create nanoscale structures like the IBM logo and nanoscale abacus
shown below. As you might guess, building structures one atom at a time is very
time consuming. Examples of this type of assembly have typically been “proof of
concept” to show that it can be done but don’t necessarily have practical
application because the process is expensive and slow.

(a) (b)
Fig. 6: (a) IBM logo assembled from individual xenon atoms arranged on a nickel
surface, (b) Nanoscale buckyball “beads” placed on a copper surface.

Nomenclature and classification of Nanomaterials

Nomenclature of various ultrafine materials is given below.
Cluster – A collection of up to 50 units, e.g. atoms, molecules
Colloidal Particle – 1-1000 nm sized particle in a stable colloidal phase.
Nanomaterial – Any one of the dimensions is in 1-100 nm size.
Nanoparticle – All three dimensions should be in 1-100 nm in size.
Nanocrystal – A single crystal in nano range.
Quantum dot – A nanomaterial with quantum confinement effect.
Nanocomposite – A multiphase solid material where one of the phases
has one, two or three dimensions of less than 100 nm.

Nanomaterials can be nanoscale in one dimension (eg. surface films), two

dimensions (eg. strands or fibres), or three dimensions (eg. particles). They can
exist in single, fused, aggregated or agglomerated forms with spherical, tubular,
and irregular shapes. Common types of nanomaterials include nanotubes,
dendrimers, quantum dots and fullerenes. Nanomaterials have applications in
the field of nano technology, and displays different physical chemical
characteristics from normal chemicals (i.e., silver nano, carbon nanotube,
fullerene, photocatalyst, carbon nano, silica).
According to Siegel, Nanostructured materials are classified as Zero
dimensional, one dimensional, two dimensional, three dimensional
nanostructures.
Fig. 7: Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D
nanofibers, wires, and rods, (c) 2D films, plates, and networks, (d) 3D
nanomaterials.

Self-assembly of nanoparticles may lead to the formation of different

nanomaterials, as shown in Fig. 8.

Fig. 8: Schematic representation of 1D, 2D, and 3D self-assembly of

nanoparticles.