CHAPTER-I

NANOTECHNOLOGY: INTRODUCTION
Nanotechnology is the study of manipulating matter on an atomic
and molecular scale. Generally, nanotechnology deals with developing
materials, devices, or other structures possessing at least one dimension
sized from 1 to 100 nanometres. Quantum mechanical effects are
important at this quantum-realm scale.

Nanotechnology is very diverse, ranging from extensions of

conventional device physics to completely new approaches based upon
molecular self-assembly, from developing new materials with dimensions
on the nanoscale to investigating whether we can directly control matter
on the atomic scale.' Nanotechnology entails the application of fields of
science as diverse as surface science, organic chemistry, molecular
biology, semiconductor physics, microfabrication, etc.
On one hand, Nanotechnology may be able to create many new
materials and devices with a vast range of applications, such as in
medicine, electronics, biomaterials and energy production. On the other
hand, nanotechnology raises many of the same issues as any new
technology, including concerns about the toxicity and environmental
impact of nanomaterials [18], and their potential effects on global
economics, as well as speculation about various doomsday scenarios.
These concerns have led to a debate among advocacy groups and
governments on whether special regulation of nanotechnology is
warranted.
1.1 HISTORY AND ORIGIN

Fig. l.I: Buckminster fuUerene Ceo, also known as the buckyball

Buckminster flillerene Ceo, also known as the buckyball, or the

carbon mega-molecule, is a representative member of the carbon
structures known as fullerenes. Members of the fullerene family are a
major subject of research falling under the nanotechnology umbrella.
Although nanotechnology is a relatively recent development in scientific
research, the development of its central concepts happened over a longer
period of time. The emergence of nanotechnology in the 1980s was
caused by the convergence of experimental advances such as the
invention of the scanning tunneling microscope in 1981 and the discovery
of fiillerenes in 1985, with the elucidation and popularization of a
conceptual framework for the goals of nanotechnology beginning with
the 1986 publication of the book Engines of Creation [1].

The scanning tunneling microscope, an instrument for imaging

surfaces at the atomic level, was developed in 1981 by Gerd Binnig and
Heinrich Rohrer at IBM Zurich Research Laboratory, for which they
received the Nobel Prize in Physics in 1986[2,3]. Fullerenes were
discovered in 1985 by Harry Kroto, Richard Smalley, and Robert Curl,
who together won the 1996 Nobel Prize in Chemistry[4,5].

*'l™T~*!3 Control voltages for piezotube

3 S
•* s i c <•*
S Q
u §
Q£ Tunneling Distance control
J 1 current amplifier and scanning mil

voltage s
Data processing
&M display

Fig. 1.2: Scanning Tunneling Microscope

Around the same time, K. Eric Drexler developed and popularized
the concept of nanotechnology and founded the field of molecular
nanotechnology. In 1979, Drexler encountered Richard Feynman's 1959
talk "There's Plenty of Room at the Bottom". The term "nanotechnology",
originally coined by Norio Taniguchi in 1974, was unknowingly
appropriated by Drexler in his 1986 book Engines of Creation: The
Coming Em of Nanotechnology, which proposed the idea of a nanoscale
"assembler" which would be able to build a copy of itself and of other
items of arbitrary complexity. He also first published the term "grey goo"
to describe what might happen if a hypothetical self-replicating molecular
nanotechnology went out of control. Drexler's vision of nanotechnology
is often called "Molecular Nanotechnology" (MNT) or "molecular
manufacturing," and Drexler at one point proposed the term "zettatech"
which never became popular.
In the early 2000s, the field was subject to growing public
awareness and controversy, with prominent debates about both its
potential implications, exemplified by the Royal Society's report on
nanotechnology[6], as well as the feasibility of the applications
envisioned by advocates of molecular nanotechnology, which culminated
in the public debate between Eric Drexler and Richard Smalley in 2001
and 2003[7]. Governments moved to promote and fund research into
nanotechnology with programs such as the National Nanotechnology
Initiative.
Thereafter, the world also saw the beginnings of commercial
applications of nanotechnology, although these were limited to bulk
applications of nanomaterials, such as the Silver Nano platform for using
silver nanoparticles as an antibacterial agent, nanoparticle-based
transparent sunscreens, and carbon nanotubes for stain-resistant
textiles[8,9].
1.2 FUNDAMENTAL CONCEPTS

Nanotechnology is the engineering of ftinctional systems at the

molecular scale. This covers both current work and concepts that are
more advanced. In its original sense, nanotechnology refers to the
projected ability to construct items from the bottom up, using techniques
and tools being developed today to make complete, high performance
products.

One nanometer (nm) is one billionth, or 10"^, of a meter. By

comparison, typical carbon-carbon bond lengths, or the spacing between
these atoms in a molecule, are in the range 0.12-0.15 nm, and a DNA
double-helix has a diameter around 2 nm. On the other hand, the smallest
cellular life-forms, the bacteria of the genus Mycoplasma, are around
200 nm in length. By convention, nanotechnology is taken as the scale
range 1 to 100 nm following the definition used by the National
Nanotechnology Initiative in the US. The lower limit is set by the size of
atoms (hydrogen has the smallest atoms, which are approximately a
quarter of a nm diameter) since nanotechnology must build its devices
from atoms and molecules. The upper limit is more or less arbitrary but is
around the size that phenomena not observed in larger structures start to
become apparent and can be made use of in the nano device[10]. These
new phenomena make nanotechnology distinct fi'om devices which are
merely miniaturised versions of an equivalent macroscopic device; such
devices are on a larger scale and come under the description of
microtechnology [11].

Basically, Nanotechnology is the study of manipulation and

manufacturing of extremely minute machines or devices.These devices
are so small to the point of manipulating the atoms themselves to form
materials. Nanotechnology can make computers billions of times more
powerful as compared to today and new medical capabilities that will
heal and cure in cases that are now viewed as utterly hopeless. The
properties of manufactured products depend on how those atoms are
arranged. If we know about exactly how many dopant atoms are there in a
single transistor and exactly where each individual dopant atom is located
and placed roughly the right number in roughly the right place, we can
make a working transistor.
 Another improvement in Nanotechnology is self-replication. Self
replication makes an effective route to truly low cost manufacturing.
Our intuitions about self-replicating systems come from biological
systems that surround us, about the properties and characteristics of
artificial self-replicating systems designed for manufacturing purposes.
Artificial systems capable to make a wide range of nonbiological
products like diamond under programmatic control are likely to be more
brittle and less adaptable in their response to changes in their
environment than biological systems. At the same time they should be
simpler and easier to design. Thus the progress of technology around the
world has already given us more precise, less expensive manufacturing
technologies that can make an unprecedented diversity of new products.
Everything requires the computer, is a major reason why people should
research and develop Nanotechnology. A basic definition of
Nanotechnology is the study, manipulation and manufacture of extremely
minute machines/devices. In a few decades, this emerging manufacturing
technology will let us inexpensively arrange atoms and molecules in most
of the ways permitted by physical law.
Nanotechnology could, in the future, be used to rapidly identify
and block attacks. Distributed surveillance systems could quickly identify
arms buildups and offensive weapons deployments, while lighter,
stronger and smarter materials controlled by powerful molecular
computers would let us make radically improved versions of existing
weapons able to respond to such threats. Replicating manufacturing
systems could rapidly chum out the needed defenses in huge quantities.
 While Nanotechnology does propose to use replication, it does not
propose to copy living systems. Living systems are wonderfully adaptable
and can survive in a complex natural environment. Instead,
Nanotechnology proposes to build molecular machine systems that are
similar to small versions of what you might find in todays modem
factories. Robotic arms shrunk to submicron size should be able to pick
up and assemble molecular parts like their large cousins in factories
around the world pick up and assemble nuts and bolts. Unfortunately, our
intuition are about replicating systems can be led seriously astray by a
simple fact: the only replicating systems most of us are familiar with are
biological self-replicating systems.

The first section Nanotechnology revolution describes the

background to NT under the headings, driving forces, envisioned
potentials of technology and the global initiatives taken in the major
industrialised countries.
Nanotechnology is a broad and interdisciplinary area of
research and development activity that has been growing explosively
worldwide. This NT revolution promises to revolutionize the ways, in
which materials and products are created; and the wide range and
nature of functionalities that can be accessed. With in the next few
years we can expect to see major technological changes brought by the
tiny atom-atom based manufacturing techniques.
1.3 GLOBAL INITIATIVES
The first section Nanotechnology revoludon describes the
background to NT under the headings, driving forces, envisioned
 potentials of technology and the global initiatives taken in the major
industrialised countries.
1.3.1 Vision and Driving Force
Nanotechnology is a broad and interdisciplinary area of research
and development activity that has been growing explosively worldwide.
This NT revolution promises to revolutionize the ways, in which
materials and products are created; and the wide range and nature of
functionalities that can be accessed. With in the next few years we can
expect to see major technological changes brought by the tiny atom-atom
based manufacturing techniques. Theexpectations lie on the driving force
behind this revolution, its envisioned potentials and the global initiatives
taken worldwide in the major industrialised countries.
The technique of manipulation of atom was first demonstrated,
when in April 1990, a team in the IBM research division placed thirty-
five xenon atoms in a precise pattern and spelled out the letters "IBM".
The logo is 60 billionths of an inch wide, or 13 millionths of the diameter
of a human hair (IBM Corporation, 2001).

Figure 1.3: Nano-scale IBM Logo (Source: IBM Corporation, 2001).

1.3.2 Envisioned Potentials of Technology

According to research communities agenda and some of
which as described by the researcher, K. Eric Drexler in his books.
 Nanotechnology promises to show major advances in the fields of
materials and manufacturing, environmental and energy, electronics
and computers, medical and health, and space and aircraft, some of which
are outlined in the following table.

Tablel.l: Major Fields Applications of Nanomaterials

S.No. Major Fields Potential Applications

Materials and Materials will be stronger, lighter, harder, self-repairing and safer.
Manufacturing Structural carbon and ceramic materials ten times stronger than steel
for use in industrial applications.
Environmental Water purification and desalinization with at least 10 times less energy
and Energy that state-of-the-art reverse osmosis,Major improvement in the
efficiency of energy conversion, storage, use of renewable energy
sources, and increasing the efficiency of solar cells,Decontaminating
the contaminated lands,Reducing global warming and healing up the
ozone layer.

Electronics and Nanometre structures for minuscule transistors and memory chips that
computers will improve the computer speed and efficiency by factors of millions.
Changes in communication by increasing bandwidth a hundred times.
Possibilities for thinking and self-replicating machines.
Medical and Effective and less expensive health care by remote and treatment
Health deviceSjUse of tiny medical devices that will minimize collateral
damage of human tissues, Expanding the life spans.

Space and Aircraft Lightweight, fast, low powered, pilot-Iess microspacecraft for
continuous presence in space outside of the solar system,Automobiles
using clean, renewable and inexpensive fuels very efficiently at high
mileage.
 Focussed research programs on Nanotechnology have been
initiated in almost all industrialised countries. Many initiatives are
being proposed and being implemented around the globe. The following
are some of the initiatives, which are detailed in the following table for
major industrialised countries, like USA, European Union and Germany
nations.
1.4 PERCEPTIONS OF NANOTECHNOLOGY

This section describes definition, disciplines, science and state-of-

the-art of Nanotechnology. Under the state-of-the-art of Nanotechnology
its hierarchy stages are described along with their current status of
research and their respective time scale of developments as of today.
1.4.1 Definitions of Nanotechnology
In research community there are statements that NT is still not well
defined (Kumar, 1999, October 21), some defines it on the basis of
physical dimension of structures ranging from 0.1 nm to 100 nm; it
means different for different disciplines of people. Definitions of NT are
as diverse as the applications of it. The following table outlines the set of
definifions related to its disciplines.
Table 1.2: Definitions of Nanotechnology
Definition of Nanotechnology Discipline
The ability to design and control the structure of an object at all Physics
length scales from the atom up to macro scale. (Malsch, 2002)
The core of Nanotechnology consists of systems in the sizepiology
range of nanometres. (Malsch, 2002)
It is assembly of molecules or atoms to make use of their unique Chemistry
properties existing at nano-scale.
Manipulation of individual atoms and molecules to build Science fiction
structures to complex, atomic specifications. (Drexler, 1986,
p.314)

10
 This shows how comprehensive it is. This also reveals the fact that,
Nanotechnology has appHcations in a range of markets and cut across a
variety of disciplines. The simple definition, which the study deals, is
defined below. Nanotechnology (NT) can be defined as the creation and
use of materials, devices and systems in a size range of molecular and
atomic scale.

As it deals with the manipulation of molecules it is also termed as

molecular manufacturing. The prefix, 'Nano' in Nanotechnology
describes a scale nanometre, which is defined below.
1.4.2 Nanometre
A nanometre is one thousand millionth of a metre (1 nm = 10-^ m).
Some practical examples for knowing the nanometre scale are as follows:
It is comparable to
(i.) 1 /80.000 of the diameter of a human hair (Institute of

Nanotechnology, 2002) or
(ii.) 1/10.000 times the size of a bacteria (Drexler, 1986, p.l 1), or
(iii.) 1000timessmaller than the present micro-metre devices or
(iv.) 10 times the diameter of a hydrogen atom.
An early promoter of the industrial applications of
Nanotechnology, Albert Franks, defined it as 'that area of science and
technology, where dimensions and tolerances in the range of O.lnm to
100 nm play a critical role' (ION, 2002).
1.5 DISCIPLINES OF NANOTECHNOLOGY

Nanotechnology is a result of convergence of traditional fields

of physics, biology and chemistry. It depends on contributions from
among these and other disciplines. The convergence of these

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traditional fields and various disciplines is well illustrated in Figure 1.4,
which also shows the scales of the areas of interaction. There is
considerable debate in the scientific community about the boundaries
of the new disciplines emerging from this convergence e.g. between
microtechnology and nanotechnology, but it is becoming clear that, in
practice, no clear division can be made. Thus, for example, sensors and
bio-chips at nano-scale need to be packaged for commercial applications
using microtechnology.

Stiuctun aim

Physics

MA
CR
0

^ 0 J^ O ID

Ml
CR Applications of
Biology nanotechnology

j ; oaum — lite grated

exploitation of
biological principles
NO 4 BlDCiltpi physical laws
chemical properties
Chcmi^
0^1 on
1960 1980 tod^ ID 2D T"n"
2Bm Year

Figure 1.4: Convergence of Different Disciplines in Nanotechnology.

12
 1.6 APPROACHS TO NANOTECHNOLOGY
Nanotechnology involves both top-down and bottom-up
approaches each of them is explained below:
1.6.1 Top-Down Approach

As illustrated in the Figure 1.5 below, traditional industrial

technologies operate from the top-down. Where blocks or chunks of raw
material are cast, sawed, or machined into precisely formed products by
removing unwanted matter. Results of such processes may be rather small
(for example integrated circuits with structures measured in microns) or
very large (ocean liners or jumbo jets). However, in all cases matter is
being processed in chunks far larger than molecular scale. These seek to
create smaller devices by using larger ones to direct their assembly.
(i.) Many technologies that descended from conventional solid-state
silicon methods for fabricating microprocessors are now capable of
creating features smaller than 100 nm, falling under the definition of
nanotechnology. Giant magnetoresistance-based hard drives already
on the market fit this description,[12] as do atomic layer deposition
(ALD) techniques. Peter Griinberg and Albert Pert received the Nobel
Prize in Physics in 2007 for their discovery of Giant
magnetoresistance and contributions to the field of spintronics.[13]
(ii.) Solid-state techniques can also be used to create devices known as
nanoelectromechanical systems or NEMS, which are related to
microelectromechanical systems or MEMS.
(iii.) Focused ion beams can directly remove material, or even deposit
material when suitable pre-cursor gasses are applied at the same time.

13
 For example, this technique is used routinely to create sub-lOOnm
sections of material for analysis in Transmission electron microscopy,
(iv.) Atomic force microscope tips can be used as a nanoscale "write head"
to deposit a resist, which is then followed by an etching process to
remove material in a top-down method.
1.6.2 Bottom-Up Approach
It is envisioned that rather than being produced through large
chunks of material being sawed, planed, and ground to form, tiny
molecular machines, working from the bottom-up (see Figure 2.4),
construct most such objects.

PAST
/
TOP-DOWN

f I
PRESENT
Nano-Scale
Manipulations of
organic and

at atomic and
BOTTOM-UP molecular scale
FUTURE

Fig. 1.5; Top-Down and Bottom-up Approaches of NT

The bottom-up deals with the techniques of organizing individual atoms

and molecules into particular configurations, to create complex products.
For example, the human body begins as a single cell, a fertilized ovum.
Yet a mature human being consists of approximately 75 trillion cells,
complexly arranged and of many different varieties. The molecular

14
machinery responsible for this is capable of such results because it
performs operations in parallel (that is, with many cells operating at the
same time through most of the growth process), and from the bottom-up.
With NT bottom-up approach, atoms will be specifically placed
and connected, all at very rapid rates, in a fashion similar to processes
found in living organisms. Presently, most of the industries are
manufacturing the nano-scale products, but they are approaching a nano-
scale through the traditional technology. Bottom-up approach is still a
vision. Both top-down and bottom-up approach defines the level of
advancement of NT. The key to the application of NT will be the
development of processes that control placement of individual atoms to
form products of great complexity at extremely small scale.
At these scales entirely new physical phenomena occur which can
be exploited to produce new devices, and hence the characteristics of
individual molecules and atoms in the material become more important
than the material's bulk properties. The theme of the field is "novel
performance through nanotechnology" (Siegel, Hu and Roco, 1999, p.4).
These seek to arrange smaller components into more complex assemblies,
(i.) DNA nanotechnology utilizes the specificity of Watson-Crick
base-pairing to construct well-defined structures out of DNA and
other nucleic acids,
(ii) Approaches from the field of "classical" chemical synthesis
(inorganic and organic synthesis) also aim at designing molecules
with well-defined shape (e.g. bis-peptides[14]).
(iii) More generally, molecular self-assembly seeks to use concepts of
supramolecular chemistry, and molecular recognition in particular,

15
 to cause single-molecule components to automatically arrange
themselves into some useful conformation,
(iv) Atomic force microscope tips can be used as a nanoscale "write

head" to deposit a chemical upon a surface in a desired pattern in a

process called dip pen nanolithography. This technique fits into the
larger subfield of nanolithography.
1.6.3 Process Involved
The broad field of science and technology of NT can be
most conveniently organised according to the Figure 1.6 shown below.
The basis of the field is any type of material (metal, ceramic, polymer,
semiconductor, glass, composite) created from nano-scale blocks
(nanoparticles, nanolayers, etc.) that are themselves synthesized from
atoms and molecules. Thus, the controlled synthesis of those building
blocks and their subsequent assembly into nanostructures is one
fundamental theme of this field (Siegel, Hu and Roco, 1999, p.5).
Full-fledged NT promises nothing less than complete control over the
physical structure of matter the same kind of control over the molecular
and structural makeup of physical objects. For example, there is already
such a system that is "nature". All the goals of NT are already fulfilled in
living systems and this attempt of NT is to learn these systems and apply
them.

16
 Building Blocks
A t o m y Mojecu^e^^^
inanqpartlcleSj
nano layers, etc.]

Assembly

Nanostructures

•" ^-f^. /%« ^ ^ M T ^ ^ T ^ ^

Fig. 1.6: Process behind NT

The atom-atom construction is still a vision, but currently there are

techniques through which the advantages of nano-scale of a matter are
taken, and some of them are:
(i.) Direct control of solids,
(ii.) Transformation of liquid solutions to gel and then to

solids/deposition, and

(iii.) Chemical vapour deposition.

1.7 STATE-OF-THE-ART OF NANOTECHNOLOGY

The current stage of NT is still under top-down approach, where

chunk of material is reduced to nanosize. The bottom-up stage of NT is
still emerging and at the primitive stage, but for nanomaterials and
nanotubes commercial production already started. The present state of the
art of NT can be well understood through its hierarchy stages described
below.

17
 2015
Future
Research
Agenda
2008
Under
Research

=- 2003
In Products &.
Under
Research

Development
Hierarchy Stages Time Scale of
Phases as of Today Developments

Fig. 1.7: Development Phases, Hierarchy Stages, and Time Scale of

Developments of - NT.

1.7.1 Hierarchy of Stages

Figure 1.7 illustrates the present day development phases on the
left side; alongwith the corresponding hierarchy stages in the middle,
and on right side. The time scale of respective developments
(approximate estimations), showing when will the particular
development gain maturity. The hierarchy of stages are explained in

detail as follows:
1. Nanoparticles: At the simplest level are the nanoparticles.
Nanoparticles are sometimes referred to as nanomaterials. This is
evident, as the research communities have not reached consensus on NT
definition and its related terms. But there are working definitions among
the research group working in this area. Nanoparticles contain few
thousand atoms some are like quantum dots[15]. Presently,
nanoparticles exist in various products like paints, inks and ceramics. But
their range is expected to grow rapidly.

2. Nanomaterials (Nanostructures): At the second stage under

hierarchy are the nanomaterials, some are under research phase and few

18
in market. Nanomaterial is defined as any material that has unique
or novel properties, due to nanoscale[16] (nanometre-scale)
structuring (Ausman, 2003, February 14). These are formed by
incorporation or structuring of nanoparticles. Nanomaterials are the
main building blocks in NT processes; these are subdivided into
nanocrystals, nanotubes, nanopowders[17].The worldwide study
conducted by World Technology Evaluation Center (WTEC) panel on
research and development status of nanoparticles, nanostructured
materials and nanodevices states under its overarching findings that, it
is clear that materials can be nanostructured for novel performance
(Siegel, Hu and Roco, 1999, p.4). The study also revealed that, the
synthesis and control of materials in nanometre dimensions could access
new material properties and device characteristics in an unprecedented
way.

3. Nanodevices and Nanosystems: The next stage is the complex

era of NT, which is the combination of nanostructured materials into
nanosystems and nanodevices. This stage is far to see, but it is included
in research agenda of countries like USA.
There are parallel efforts under every stage and huge amount of money is
flowing under its research and development agendas, and hence
development may occur earlier than expected.
1.8 THE MOORE'S LAW:

In fact, the technology is going to smaller and smaller regime year

by year. The 1965 observation by Intel co-founder Gordon Moore that the
transistor count for integrated circuits seemed to be doubling every 18-
24 months. The rule seemed to be almost whimsical then. When he made

19
this rule, the IC's were just invented. But the rule has since been
followed for forty five years, as shown in Fig. 1.8:

transistors
tG,0»,M0.000

Owal-Cweihyi* (t»*)ifi' X Processor

MOORiSLAW
100,000<000

icomooo
tmc}* Pefrtjutn* ^Pisaissr.,
Mel4S6*'iPnii^jS6
! t.OOQ.OOS

100,000

10,000
80 OS
4064 : r * ^
1.000
1i70 1S7S !i80 1985 1990 1995 2000 2005 2010

Fig. 1.8: The Moore's Law

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