Chapter 1

Introduction

1.1 Introduction to Nanoworld

Nanoscience is the study of phenomena on nanometer scale. Atoms are a few
tenths of a nanometer in diameter and molecules are typically a few nanometers
in size. The smallest structures humans have made; have dimensions of a few
nanometers and the smallest structures we will ever make will have the dimen-
sions of a few nanometers. This is because as soon as a few atoms are placed
next to each other, the resulting structure is a few nanometers in size. The
smallest transistors, memory elements, light sources, motors, sensors, lasers,
and pumps are all just a few nanometers in size.
Besides the technological relevance of nanoscience (or perhaps because of the
technological relevance) there is an enormous hype associated with it. Fantas-
tic claims have been made about faster computers, cheap production of goods,
and medical breakthroughs. Nanotechnology is expected to appear in prod-
ucts such as tennis rackets, self-cleaning cars, paint, food, cosmetics, solar cell,
bio-sensors, thermal underwear etc, out of which many of them are already in
market.
One of the first people to point out potential benefits of making devices at the
nanoscale was Richard Feynman. In a speech he gave in 1959 entitled, “There
is Plenty of Room at the Bottom” and estimated that it should be possible
to reduce the printing on a page by a factor of 25000 and if that were done, all
the books ever printed could be copied in a space of about 35 ordinary pages.
It has been said that a nanometer is “a magical point on the length scale”,
for this is the point where the smallest man-made devices meet the atoms and
molecules of the natural world.
Indeed, nanotechnology mania is sweeping through essentially all fields of
science and engineering, and the public is becoming aware of the quote of the
chemist and Nobel Laureate, Richard Smalley: “Just wait the next century
is going to be incredible. We are about to be able to build things that
work on the smallest possible length scales, atom by atom. These
little nanothings will revolutionize our industries and our lives.”
So what are these “nanothings” that are going to change our lives? Why are
they so special?
Nanotechnology creates and uses structures that have novel properties because

9
10 CHAPTER 1. INTRODUCTION

of their small size. The following two examples visually illustrate how nanosized
particles of a given substance exhibit different properties than larger sized par-
ticles of the same substance.
(a) GOLD SOL
Nanosized particles of gold, sometimes referred to as mesogold, exhibit differ-
ent properties than bulk gold. For example, mesogold has a different melting
point than bulk gold, and the color of mesogold can range from light red to
purple depending on the size (Fig.1.1), shape, and concentration of the gold
particles present. Gold nanoparticles are being investigated in medical research

Figure 1.1: Varitation of colors of gold sol with various sizes of the gold particles

for use in detecting and killing cancer cells, biosensors and a variety of other
applications.
(b) FERROFLUID
Ferrofluids contain nanoparticles of a magnetic solid, usually magnetite (Fe3 O4 ),
in a colloidal suspension. The nanoparticles are about 10 nm in diameter. Fer-
rofluids are interesting because they have the fluid properties of a liquid and
the magnetic properties of a solid. For example, a magnet placed just below a
dish or cell containing ferrofluid generates an array of spikes in the fluid that
correspond to the magnetic lines of force. When the magnet is removed, the
spikes disappear.

Figure 1.2: Optical image of ferrofluid in presence of magnetic field

Ferrofluids were discovered by NASA to control liquid in space. They have been
used in many applications, including computers disk drives, low friction seals,
loudspeakers etc. Medical researchers are even experimenting with using fer-
rofluids to deliver drugs to specific locations in the body by applying magnetic
fields.
1.2. A NEW REALM OF MATTER: NANOMATERIAL 11

1.2 A new realm of matter: Nanomaterial

Nanoscale materials frequently demonstrate a behavior which is intermediate
between that of a macroscopic solid (bulk matter) and that of an atomic or
molecular system. Chemistry is the study of atoms and molecules, a realm of
matter of dimensions generally less than one nanometer, while condensed mat-
ter physics deals with solids of essentially an infinite array of bound atoms or
molecules of dimensions greater than 100 nm. A significant gap exists between
these regimes.Table.1.1 illustrates this gap, which deals with particles of 1
to 100 nm, or about 100 to 105 atoms or molecules per particle.
In this nanoscale regime neither quantum chemistry nor classical laws of physics
hold. In materials where strong chemical bonding is present, delocalization of
valence electrons can be extensive, and the extent of delocalization can vary
with the size of the system. This effect, coupled with structural changes with
size variation, can lead to different chemical and physical properties, depending
on size. Indeed, it has now been demonstrated that a host of properties depend
on the size of such nanoscale particles, including magnetic properties, optical
properties, melting points, specific heats, and surface reactivity. Furthermore,
when such ultrafine particles are consolidated into macroscale solids, these bulk
materials sometimes exhibit new properties (e.g., enhanced plasticity). It is

Table 1.1: Comparision of Nanoscale matter with Atomic and Bulk matter.

System ⇒ Atomic/Molecular Nanoscale Bulk matter

# atom 1 ∼100 to ∼7x105 ∼106 to ∞
/molecule
size(nm) 0.1 ∼ 1 to 100 100 to ∞
To see Electron Microscope Electron Microscope Naked eye
Governing Quantum laws ??? Classical laws
law
Relevant Chemistry ??? Physics
subject

clear that a huge new field of science has been born. Each change in compo-
sition or size can lead to different physical and chemical properties. This new
field of nanoscale materials, lying between the traditional fields of chemistry
and solid-state physics, touches upon disciplines such as electronics, astronomy,
mathematics, and engineering. Therefore, interdisciplinary research is required
for progress to be made.The creative synthesis schemes, advanced characteriza-
tion tools and better understanding on their properties will master us to exploit
this new field to fulfill the societal needs.
At this stage we should define nanomaterial as
The material to be called as nanomaterial if the size of any of its three dimen-
sions (x, y, z) lies between 1-100nm with having unusual property with respect
to its bulk.
However, how a nanoparticle is viewed and is defined depends very much on
the specific application. In this regard, Table.1.2 summarizes the definition
of nanoparticles and nanomaterials by various organizations: International Or-
ganization for Standardization(ISO), American Society of Testing and Materi-
als (ASTM), National Institute of Occupational Safety and Health (NIOSH),
12 CHAPTER 1. INTRODUCTION

Scientific Committee on Consumer Products (SCCP), and British Standards

Institution (BSI).

Table 1.2: Definitions by various organizations

Organization Nanoparticles Nanomaterial

ISO A particle spanning 1-100 nm -
(diameter).
ASTM An ultrafine particle -
whose length
in 2 or 3 places is 1-100 nm.
NIOSH A particle with diameter -
between 1 and 100 nm,
or a fiber spanning
the range 1-100 nm.
SSCP At least one side is Material for which
in the nanoscale range. at least one side
or internal structure
is in the nanoscale.
BSI All the fields or diameters are -Same as above-
in the nanoscale range.
1.3. PERCEPTION ON SIZE 13

1.3 Perception on size

How Small is a Nanometer?
The meter (m) is the basic unit of length in the metric system, and a nanometer
is one billionth of a meter. It is easy for us to visualize a meter; that is about
3 feet. But a billionth of that? It is a scale so different from what we are used
to. It will be better for us to imagine if we consider the following Number-Scale
Table.1.3

Table 1.3: Number system: From Big to Small

Prefix Numerical Expression Name 10n

Peta 1000000000000000 Quadrillion 1015
Tera 1000000000000 Trillion 1012
Giga 1000000000 Billion 109
Mega 1000000 Million 106
Kilo 1000 Thousand 103
Hecto 100 Hundred 102
Deca 10 Ten 101
1 One 100
Deci 0.1 Tenth 10−1
Centi 0.01 Hundreth 10−2
Milli 0.001 Thosandth 10−3
Micro 0.000001 Millionth 10−6
Nano 0.000000001 Billionth 10−9
Pico 0.000000000001 Trillionth 10−12
Femto 0.000000000000001 Hundreth 10−15

After having idea on Number System, let us compare nanoparticles with other
objects as shown in Fig.1.3

Figure 1.3: Pictorial size comparision of nanomaterials with other objects

(a) The height of an adult lady (∼1.5m) is ∼109 times taller-

14 CHAPTER 1. INTRODUCTION

(b)The length of an ostrich egg (∼0.15m) is ∼108 times and a frog egg of size
∼1.5mm is ∼106 times lengthier-
(c)The size of human egg, ovum (∼0.15mm) is ∼105 times bigger-
than that of a nanoparticle and we can see these objects through our naked eye
but not the nanoparticles.
(d) An animal or plant cell of size 50 µm is ∼50x103 times and bacteria of size 5
µm is ∼5x103 bigger than a 1nm particle and we can’t see these object through
naked eye but can see thorough light microscope.
(e)The size of a flu virus (∼50nm) is just 50 times bigger. To see we need to
use electron microscope not optical microscope.
1
(f)And the size of a hydrogen atom (∼0.1nm) is 10 th of a 1 nm particles.

1.4 Classification of Nanomaterial

Existed Nanomaterials can broadly be classified based on the number of dimen-
sions, which are not confined to the nanoscale range (>100nm) as
(1)0-D (Zero Dimensional): All dimensions (x, y, z) are at nanoscale, d6100nm
and termed as Nanocluster(NC), Nanoparticles(NP),Quantum Dot(QD).
(2)1-D (One Dimensional): Two dimensions (x, y) are at nanoscale but not
the other dimension (z) and termed as Nanowire(NW), Nanorod(NR), Nan-
otube(NT).
(3)2-D (Two Dimensional): One dimension (x) is at nanoscale but no the
other tow dimensions (y) and termed as Nanofilm, Nanoribbon, Nanocoating.
(4)3-D (Three Dimensional): No dimensions are at the nanoscale but they
are with in few hundrens(<200nm) nanometer and termed also as Nanoparticles.

A schematic representation of classification of nanomaterilas is shown in Fig1.4.

Figure 1.4: Optical image of ferrofluid in presence of magnetic field

As the field of nanostructured materials has evolved, many names and labels
have been used. It is important that some definitionsof the terms be presented
here.
Cluster: A collection of units (atoms or reactive molecules) of up to about 50
units. Cluster compounds are such moieties surrounded by a ligand shell that
allows isolation of a molecular species (stable, isolable, soluble).
Colloids: A stable liquid phase containing particles in the 1-1000nm range. A
colloidal particle is one such 1-1000nm sized particle.
Nanoparticle: A solid particle in the 1-1000nm range that could be noncrys-
talline, an aggregate of crystallites, or a single crystallite.
1.5. BULK VS. INTERFACE 15

Nanocrystal: A solid particle that is a single crystal in the nanometer size range.
Quantum dot: A particle that exhibits a size quantization effect.
Table1.4 shows various man-made nanomaterials with their TEM (Transmis-
sion Electron Microscope) micrograph.

Table 1.4: Several examples of man-made nanomaterials

Class Type Example TEM mi-

crograph
0-D QD,NC,NP Au, Ag, Cu, CdSe etc

1-D NW,NR,NT Au-NR,C-NT etc

2-D Nanofilm, MoS2 , Graphene etc

Nanoribbon,
Nanocoating

3-D NP ZnO, CeO2 , SiO2 etc

1.5 Bulk Vs. Interface

A surface is the shell of a macroscopic object (the inside/ the Bulk ) in con-
tact with its environment (the outside world ). An interface is the boundary
between two phases (Fig.1.5). Phase boundaries are the locations of gradi-

Figure 1.5: Schematic representation of Bulk Vs. Surface (more precisely-

Interface)

ents, and gradients are a driving force for processes. If, for instance, we put a
16 CHAPTER 1. INTRODUCTION

piece of rock candy into a glass of tea, the sugar crystal and the water occupy
separate volumes, separated by a sharp phase boundary. With time, however,
water molecules attack the crystal (at the surface) and sugar molecules are de-
tached and diffuse into the liquid phase. We observe the process of dissolution,
which continues until the distribution of water and sugar molecules is uniform
throughout the glass, until there is no more phase boundary between sugar and
water. A similar decay process destroys our car despite all our care to maintain
and protect its surface as mentioned above. Thus, the gradients at interfaces
drive spontaneous processes, irrespective of whether we want them to occur or
not. The respective process, of course, depends on the nature of the two phases
on either side of the phase boundary. More precisely, the respective process de-
pends on the properties of both phases within their area of immediate contact.
These interface properties ultimately determine the mechanism, the speed, and
the final product of the process. It appears quite intuitive that the mere con-
tact between two unlike phases leads to an alteration of their properties at the
interface from their respective properties in the bulk. For instance, the interface
between a piece of pure iron and air will be enriched with oxygen compared to
the bulk of either adjacent phase. It is, however, much less intuitive that the
properties of the surface of a phase are different from the bulk properties if this
phase is in contact with nothing, that is, vacuum.
There are two good reasons to study and understand this intrinsic difference
between surface and bulk properties: (i) scientific curiosity and (ii) the
desire to gain control over the so important interface processes such as cor-
rosion, passivation, materials processing such as film growth and etching, and
heterogeneous catalysis, etc.
Why are surfaces so peculiar ? We start by drawing the attention to some ba-
sic deviations between the surface and the bulk of a condensed phase. These
obvious deviations will lead to the natural insight that surface and bulk prop-
erties must be different. Following this insight, we also draw the attention to
some fundamental as well as economic consequences of the peculiar physical and
chemical properties of surfaces and interfaces.
Let us take a crystal in vacuum as our test sample. The facets of a crystal are
planar surfaces as schematically depicted in Figure1.6a and b.

(a)
(b)

Figure 1.6: (a)Schematic crystal, (b)Cleavage breaks some bonds whereas sub-
limation breaks all bonds that previously held a crystal together.
1.6. SIZE EFFECT 17

These facets include characteristic angles. This simple geometric habitus of

crystals suggests that the basic building blocks, atoms, ions, and molecules are
also piled up in a regular way (as verified by diffraction techniques). Attrac-
tive interactions between these building blocks, for example, electrostatic forces
between the chloride anions and sodium cations in rock salt; metallic bonds in
metals such as iron, copper, platinum, or tungsten; or covalent bonds in silicon
or diamond, keep the building blocks together. These attractive forces can be
very strong, which becomes obvious if we try to cut up a crystal; it costs a
lot of work to cleave a piece of rock salt or to cut a piece of metal or even a
diamond. This energy is needed to sever, to cut the bonds between all atoms on
both sides of the section plane.As a result, two new surfaces have been created
(Figure1.6b), and all atoms at these two new surfaces have been bereaved of
their bonds to their former neighbors (which are now at the distant opposite
surface) (Figure1.6b).
The first consequence of this rupture is that all surface atoms find themselves
in an asymmetric environment. While the bulk atoms are symmetrically sur-
rounded by their nearest neighbors, the surface atoms have no neighbors on one
side, but only vacuum.
As a further, apparently trivial consequence of this asymmetry, surface atoms
are freely accessible from the vacuum side. On the one hand, they are freely
accessible by experimental probes, and, on the other hand, they would be the
first to be exposed to atoms or molecules of an adjacent (gaseous, liquid, or
solid) phase. Third, the applied energy needed to rupture the bonds must now
(to a large extent) be stored in the unsaturated bonds of all surface atoms
at the newly created surfaces (energy conservation).
As emphasized, surface atoms have neighbors only in and below the surface,
but not on the outside. This asymmetry causes an obvious imbalance of bond-
ing forces acting on the surface atoms perpendicular to the surface. As a
consequences the surface atoms are higly reactive and always have tendency
to interact or make bond with surrounding species to reduce the imabalanced
force/unsatisfied coordination and hence surface energy to gain the stability.
Let us conclude, what we have discussed so far-
(i)Actually atoms from its atomic size, form a particle, relatively bigger in size,
by satisfying its coordination number. Coordination number of an atom is the
nearest neighbour number of atoms with which it can make bond.
(ii) Surface atoms are unsaturatively coordinated. There is lot of dangling bonds
on the surface.
(iii) Surface atoms are different from the core atoms with respect to their
physico-chemical properties.
Hence, more number of surface atoms lead to more number of dangling bonds
leading to higher reactivity. In the next section we will discuss how the number
of surface atoms are related to size of the material (or particle).

1.6 Size effect

Dispersion
An important parameter for the description of size-dependent phenomena is the
dispersion, F , which designates the fraction of atoms in the surface shell with
18 CHAPTER 1. INTRODUCTION

respect to the total number of atoms of a material. For cubic clusters with n
atoms of radius r along the edge the total number of atoms is N = n3 , the
number of atoms at the surface is given by 6n2 for the six faces, corrected for
double counts of the 12 edges (12n) and reinstalling the 8 corners, so that the
dispersion becomes
6n2 −12n+8 6 2 8 6
F = n3
= 1 (1 − 1 + 2 )≈ 1
N3 N3 N3 N3

This behaviour is illustrated in Figure1.7.

Figure 1.7: Evolution of the dispersion, F as a function of n for cubic clusters

up to n = 100 (N = 106 ). The structure of the first four clusters is displayed.
1
Now, N 3 -term is nothing but n, the number of atoms along the edge of the
cube. So, if the size of the cube decreases then the number of atoms (of same
1
size, r) along the edge also decreases and hence in other word the term N 3 is
directly proportional to the size of the cubical material. The Figure1.7 shows
1
that as the value of N 3 (or in other word the size of the cube) decreases the
fraction of atoms at the surface, F shoot up exponentionally.
For large spherical clusters of radius R the dispersion is proportional to the
volume of a shell of thickness 2r divided by the total volume. Assuming the
same packing density, we can estimate the dispersion, F as follows -
Ns
F = N Where, N and Ns are the total number of atoms
and number of atoms on the shell respectively.
Vs
⇒F = V Where, V and Vs are the volume of the particle
and the shell of thickness 2r respectively. Ns ∝
Vs V
Vatom
, N ∝ Vatom , Vatom =Volume of an atom.
4 3 4 3
3 πR − 3 π(R−2r)
⇒F = 4
πR 3
3
3 3
⇒ F = R −(R−2r)
R3
⇒ F = 1 − (1 − 2rR)
3
6r
⇒ F ≈ 1 − (1 − R ) As rR, (1 − x)3 ≈ 1 − 3x
⇒ F ≈ 6r
R ≈
6
1
V
As N = Vatom = ( Rr )3
N3

The above expression is same like the expression of F for cubical cluster and is
1.6. SIZE EFFECT 19

applicable for N larger than about 100, for smaller clusters detailed structural
information is required.

Figure 1.8: Plot of % of fraction of atom on the surface (first layer), F with the
variation of particle size(R).

The Figure1.8 clearly shows that as the size of the particle decreases most of
the atoms are in the surface; especially in case of 1 − 5nm particle.

A
Effective surface area ( m ) or Surface-to-Volume ratio( VA )
A
Both the quantity, ( m ) and ( VA ) are one way or another of same type.Actually,
NPs have enormous surface area per unit mass as a result of their small size.

Figure 1.9: Leftside: Division of a bigger cube and Rightside: surface area
calculation with the division of the cube
20 CHAPTER 1. INTRODUCTION

Consider a cube with 1m side. It has a total surface area of 6m2 . If it is divided
equally into 8 cubes, the surface area would become 12m2 ; similarly when it
would have been divided equally into 36 cubes the surface area would have been
18m2 and finally if the same cube would have been divided into several cubes
such that the edge length of each cube would become 0.1mm then surface area
would have been increased to 104 m2 or 2.5 acres (Figure1.9). This enormous
surface area leads to some special properties of nanoparticles. Now, the expres-
6 2
sion of surface area for a cube of edge lenght L is L = 6L
L3
= VA which is nothing
−1
but Surface-to-Volume ratio of the cube. This length proportionality for ( VA )
holds good for spherical, cylindrical, ellipsoidal, tetrahedron, octahedron, do-
decahedron etc.
Due to this high F and/or ( VA ) the following properties become size dependent
(which we do not expect naturally)-
(a) Chemical properties−reactivity, catalysis
(b)Thermal properties−melting temperature
(c) Mechanical properties−adhesion, capillary forces
(d) Optical properties−absorption and scattering of light
(e) Electrical properties−tunneling current, conductivity
(f) Magnetic properties−superparamagnetic effect

We shall explaine why and how these above properties become size dependent
in the next chapter.