Introduction to Nano science and Nanotechnology

Introduction Nano science and Nanotechnology

In the past few decades, a tiny word paying enormous attention, interest and investigation

around the world: “nano”. It has considerably changed every aspect of the way that we think

in science and technology and will absolutely bring more and more surprises into our daily

life as well as into the world in the future.[1-8] Nano science research has been rapidly

increasing across the world during the last decade. It is accepted by the world scientific,

industrial, government and business communities that nanoscience will be integral part in the

development of future technologies. Nanotechnology will take part in an important position

in the field of energy. The present natural energy resources will exhaust one day. The future

generation will have to look for the alternative energy sources like solar energy and hydrogen

based fuels. There is considerable research is going on to tap hydrogen fuel by splitting water

using sun light in presence of nano materials. Materials like carbon nano tubes used for

hydrogen storage. Current cost of carbon nano tubes is very high but scientists are trying to

find out very economical way of preparing them in large quantities. Numerous electronic

gadgets need rechargeable, light weight batteries or cells. Some metal hydride nano particles

like nickel hydrides or high surface area, ultra light weight materials like aerogels are found

to be better options than the conventional materials in improved batteries.

Nano science is the scientific study at the atomic and molecular scale of molecular structures

with at least one dimension measuring between 1 and 100 nanometers in order to understand

their physico-chemical properties and identify ways to manufacture, manipulate, and control

them. More generally, “nano science” can mean research on any structure of matter that

comprises of at least one nano metric dimension, without necessarily being aimed at the

manufacture of objects or materials for a specific purpose. The results of certain studies on

the behavior of ultrafine particles with dimensions at this scale (e.g., from diesel engine

emissions) that are accidentally released into the air can be used in nanotechnology to better

understand the behavior of nanoparticles designed and made in the laboratory. Therefore, the
difference between nano science and nanotechnology essentially reflects the conceptual

distinction between science and technology. The word “nanotechnology” was first introduced

in the late 1970. While many definitions for nanotechnology exist, most groups use the

National Nanotechnology Initiative (NNI) definition. The NNI calls something

“nanotechnology” only if it involves all of the following: - Research and technology

development at the atomic, molecular, or macromolecular levels, in the length scale of

approximately 1 to 100 nanometer range. Creating and using structures, devices, and systems

that have novel properties functions because of their small and/or intermediate size. Ability to

control and manipulation of matter at nanometer dimensions.

In 1959 at the annual meeting a known physicist by the name Richard P Feynman quoted that

there’s plenty of room at the bottom. “in his introduction to the topic of his lecture he said, I

would like to describe a field in which little has been done but in which an enormous amount

can be done in principle. This field will not tell us much of fundamental physics but it might

tell us much of great interest about strange phenomena that occur in complex situation. What

I want to talk about is the problem of manipulating and controlling things on a small scale.

Nano science research has been rapidly increasing across the world during the past decades.

Nano science is interdisciplinary nature; its practice requires chemists, physicists, materials

scientists, engineers and biologists to work together. The collaboration between these

disciplines will enable to tackle the most challenging scientific problems.

Now a day’s nano science is a combination of bottom up chemistry and top down

engineering techniques. There is an explosion of novel ideas and strategies for making and

manipulating, visualizing nano scale materials and structures. Nano scale science and

technology has emerged as a fast growing research area. Nano chemistry presents a unique

approach to building devices with molecular scale precision. The challenges to full utilization

of nano chemistry focus on understanding new rules of behavior, because nano scale systems

lie at the threshold between classical and quantum behavior and exhibit behaviors that do not

exist in bulk material.

Quantum Dots

Quantum dots (QD) are nanometer scale “boxes” for selectively holding or releasing

electrons. Quantum dots are tiny devices that contain free electrons. They are made up of

semiconductor materials and have typical dimensions of a few nanometers. The size and

shape of these structures and thus the number of electrons they contain can be controlled.

QDs are semiconductor structures in which electron wave function is confined to all three

dimensions by the potential energy barriers that form the QD’s boundaries, QD’s of desired

properties can be created by tailoring the size, shape and composition. The energy levels in a

quantum dot become quantized due to the confinement of electrons.

Semiconductor quantum dots signify a class of materials in which quantum confinement

effects are investigated in detail. They are also referred to as “semiconductor nano crystals”.

Quantum dots refer to semiconductor particles and nano crystal can be any inorganic material

in which there is a crystalline arrangement of atoms or ions. In a bulk form of semiconductor

crystal, the energy level form bands. At 0˚ K the valence band is completely filled and the

conduction band is completely empty and these bands are separated with a energy gap E g.

When an electron is excited due to thermal excitations, an electron hole pair is created. The

electron in the conduction band and the hole in the valence band can be bound when they

approach each other at a finite distance. This bound pair is called “exciton” which is

delocalized throughout the crystal.

The Bohr radius of exciton is given as

Where

ε = dielectric constant

me= effective mass of electron

mh= effective mass of hole

 e = elementary charge and h = Planck’s constant

Quantum size effects are manifested when the length of nano crystal made, d, is comparable
to the exciton radius.

Few properties which change appreciably as a function of size are the optical properties,
together with both the absorption and emission of light. These particles are called quantum
dots as their electrons are confined to a point in space. They have no freedom in any
dimension and electrons are said to be localized at a point, implying that a change in all
directions changes the properties.

A perfect quantum dot is probable only when the electronic states within the quantum dot
face a discontinuity at the edge of the material. Therefore the electron within the dot feels an
interact able barrier at the edge. When a material is condensed at the surface, the surface
atoms have unsatisfied valences. In order to decrease the surface energy, the surface
reconstructs, which leads to energy levels in the prohibited gap of the semiconductor. The
electrical and optical properties of material are degraded by these traps. In an ideal
semiconductor nanomaterial, the surface atoms are bonded to other materials so as to
eliminate the defects. Thus a quantum dot is enclosed with a material of larger band gap. In
an ideal semiconductor quantum dot, when there are no defect sites for charges to get trapped,
the quantum yield of luminescence will be very high and emission will also be sharp. Better
light emission occurs as the electrons and holes are confined spatially. This is achieved by
chemically protecting the surface with protecting molecules called “capping agents”. Since
surface of nano crystal can be modified by various capping molecules, and quantum yield can
be improved.

Nano material

Nano materials are traced to the Roman period .Romans were skilled at impregnating glass
with metal particles to achieve dramatic effects. It was in 1857 that Michael Faraday carried
out path breaking work on what he called divided metals .Faraday identified the essential
nature of nano scale metal particles. He stated gold is reduced in very fine particles which
becoming diffused produces a beautiful fluid. The various preparation of gold whether ruby
green, violet or blue etc; consists of that substance in a metallic divided state. One type of
gold particles prepared by Faraday are still preserved in the Royal Institution in London .In
the nano world we cannot see objects with our necked eyes, we cannot touch or manipulate
them by our hands or any of the tools that we generally use. The objects that we deal with the
nano world are very tiny and are close to the size of the atoms and molecules. The effects of
gravity and inertia are less dominating in the nano world, but surface tension and other
molecules forces do play a role. Comparing an object with diameter of nanometer to that of
meter is like comparing the size of the marble to the size of the earth. A single strand of
human hair around 20000 nanometers diameter. Bulk materials properties are independent of
its size, where as when particles are reduced to nano size it depends on its size. In nano
materials

1) Large fraction of surface atoms

2) High surface energy

3) Spatial confinement

4) Reduced number imperfections that do not exist in the corresponding bulk

materials.

A few properties in which differences between nanomaterials and bulk

materials are summarized bellow.

 The melting point ( m.p) drastically falls when the particle size is much reduced
to nanosize.Them.p depression is most evident in nano wires

nanotubes and nano particles, which all melt at lower temperature than bulk from the

same materials.The change is m.p is because , nano scale materials have much large

surface to volume ratio than bulk materials.

 All nano materials posses high mechanical strength than bulk.The cutting tools
should be harder than the materials which is to be cut are made of

nanomaterials .These cutting tools are higher erosion - resistant and durable than their

bulk materials.

 Electrical conductivity may decrease or increase when particles are in nano

scale.
 Optical properties of nano materials are much different from their bulk
materials. This is because of effect on the Plasmon resonce. In addition, the

increased energy level spacing is another criteria for this behavior.Due to increased

band gap for semiconductor nano particles absorption edge shift towards shorter wave

lengths.

 Chemical properties of the materials are changed when they are in

nanorange,due to the increase of exposed surface area of the nano particles

compared with bulk materials.

Preparation of Nanomaterials

The methods of producing nanoparticles are classified into two main categories,

“top-down” and “bottom-up” approaches.

Top down Approach

The top-down method involves the systematic breakdown of a bulkmaterial into

smaller units using some form of grinding mechanism. This is beneficial and simple to

execute and avoids the use of volatile and poisonous compounds frequently found in the

bottom-up techniques. However, the quality of the nanoparticles formed by grinding is

accepted to be poor in comparison with the material produced by modern bottom up

methods. The main drawbacks include defect problems from grinding equipment, low

particle surface areas, asymmetrical shape and size distributions and high energy needed

to produce relatively small particles. Apart from these disadvantages, it must be

distinguished that the nano-material produced from grinding still finds use, due to the

simplicity of its manufacture, in applications including magnetic , catalytic and

structural properties.

Bottom up Approach
 The bottom-up approach uses atomic or molecular feed -stocks as the source of

the material to be chemically transformed into larger nanoparticles. This has the

advantage of being potentially much more convenient than the top down approach. By

controlling the chemical reactions and the environment of the growing nanoparticle,

then the size, shape and composition of the nanoparticles may all be affected. For this

reason nanoparticles produced by bottom up, chemically based and designed, reactions

are normally seen as being of higher quality and having greater potential applications.

This has led to the growth of a host of common bottom up strategies for the synthesis of

nanoparticles.Many of these techniques can be tailored to be performed in gas, liquid,

solid states, hence the applicability of bottom -up strategies to a wide range of end

products. Most of the bottom up strategies requires suitable organometallic complexes

or metal salts to be used as chemical precursors, which are decomposed in a controlled

manner resulting in particle nucleation and growth. One of the key differences that can

be used to sub divide these strategies into different categories is the method by which

the precursor is decomposed . It is beyond the scope of this thesis to describe all

thecurrent and historical bottom up synthesis methods of nanoparticles, as there are

huge number of variations.

down approach. By controlling the chemical reactions and the environment of

the growing nanoparticle, then the size, shape and composition of the nanoparticles may

all be affected. For this reason nanoparticles produced by bottom up, chemically based

and designed, reactions are normally seen as being of higher quality and having greater

potential applications. This has led to the growth of a host of common bottom up

strategies for the synthesis of nano particles. Many of these techniques can be tailored

to be performed in gas, liquid, solid states, hence the applicability of bottom -up

strategies to a wide range of end products. Most of the bottom up strategies requires

suitable organometallic complexes or metal salts to be used as chemical precursors,

 which are decomposed in a controlled manner resulting in particle nucleation and

growth. One of the key differences that can be used to sub divide these strategies into

different categories is the method by which the precursor is decomposed . It is beyond

the scope of this thesis to describe all the current and historical bottom up synthesis

methods of nanoparticles, as there are huge number of variations

Types of Nanomaterials
There are different types of nano materials. They range from zero dimensional atom clusters
to 3D equiaxed grain structure. Each class has at least one dimension in the nanometer range.
Any multilayered material with layer thickness in nanometer range is classified as one
dimensionally modulated. Layers in the nanometer thickness range consisting of ultrafine
grains are 2D modulated. This includes coatings hidden layers and thin films. The last class is
that consisting of 3D modulated microstructures or nanophase materials. To achieve this goal,
researchers are trying to follow the “top -down” as well as “bottom-up” approaches. Among
these, the top-down approach can be considered as the one with which the human race first
learned to fabricate materials and in due course of time, perfected this art by being able to
engineer structures at submicron levels.
Metal oxides
Metal oxides play a very important role in many areas of chemistry, physics and

materials science [74-78]. The metal elements are able to form a large diversity of oxide

compounds [79]. These can adopt a vast number of structural geometries with an
electronic structure that can exhibit metallic, semiconductor or insulator character. In

technological applications, oxides are used in the fabrication of microelectronic circuits,

sensors, piezoelectric devices, fuel cells, coatings for the passivation of surfaces against

corrosion , and as catalysts. In the emerging field of nanotechnology, a goal is to make

nanostructures with special properties with respect to those of bulk or single particle

species[80-84] .Metal Oxide nanoparticles can exhibit unique physical and chemical

properties due to their limited size and a high density of corner or edge surface sites.

Particle size is expected to influence three important groups of basic properties in any

material. The first one comprises the structural characteristics, namely the lattice

symmetry and cell parameters. Bulk oxides are usually robust and stable systems with

well-defined crystallographic structures. However, the growing importance of surface

free energy and stress with decreasing particle size must be considered: changes in

thermodynamic stability associate with size can induce modification of cell parameters

or structural transformations [85-87] and in extreme cases the nanoparticle can

disappear due to interactions with its surrounding environment and a high surface free

energy. In order to display mechanical or structural stability, a nanoparticle must have a

low surface free energy. As a consequence of this requirement, phases that have a low

stability in bulk materials can become very stable in nanostructures[88-91].Among the

metals oxides,copper oxide(CuO), zinc oxide (ZnO)[92], tin oxides and industrially

employed metal oxides since last fifty years. These oxides have become important both

scientifically and industrially because of their applications for sound and picture

recording, data storage, humidity and gas sensors, conducting composite super

capacitors, electrochromic display devices, etc.

In the present study the following metal oxides are used.

 Copper forms compounds in the oxidation states +1 and +2 in its normal

chemistry but under special circumstances some compounds of trivalent are also found,

it is known that this trivalent copper survives not more than few seconds in that

particular state. Copper (I) compound are dimagitic nature with few exception they are

all colorless. Cuprous oxide (Cu 2O) is an important industrial compound and cupric

oxide (CuO) has a lot of commercial application. CuO is a promising material for

fabricating solar cells due to the photoconductive and photochemical properties.

 Among the Copper oxides only cupric oxide (CuO) phase is rep orted as gas

sensing material. CuO exhibit p-type of semiconducting properties with narrow band

gap of 1.2eV, with low electrical resistance values. The electrical conductivity

9
decreases, when it is exposed to the reducing gases. In the ground state CuO has 3d

electonic configuration, it is an anti ferromagnetic material with band gap of about

1.4eV. The band gap is identitical as being of charge-transfer origin rather than arising

from d →d transitions.

The copper oxide has a monocyclic structure and has covalently associated with

Cu-O bond, the copper oxide atom is co-ordinated by 4 oxygen atoms in a square

planner configuration. No phase transformation is known in CuO at ordinary

pressure.CuO is a semiconductor and resistivity studies at high pressure seem to

indicate a phase transition. The magnetism of the Cu (II) ion in different environments

has been studied because of its relevance to high temperature super conductivity in

several CuO based ceramics. Dilute Cu(II) system have been investigated for low

dimensional magnetic correlations.

Copper oxide is used as a pigment in ceramic to produce blue, red & green

colour. It is also used in welding with copper alloys. It is also used to dispose hazardous

materials such a cyanides, hydrocarbons etc.

 Tin

forms two series of compounds stannous or tin (II) compounds and stanic or tin (IV)

compounds. Both are stable oxidation state . Stannous oxide is blue black crystaline

O
product. It is thermally stable in air up to 385 c, and above this temperature it gets

convertrd into stannic oxide, a white coloured compound. In Chemical industries, SnO

is used in making tin salts for regents and SnO2 is popular in the petroleum industry as a

heterogeneous oxidation catalyst.

Among the various semiconducting metal oxides, SnO 2 has been the most

popular gas sensing material. SnO 2 Crystalizes in the tetragonal crystal system and is

isostrucutral with rutile phase. Each unit cell consists of two tin atoms and four oxygen
atoms. The octahedral are sharing edges and form linear chains along the c-axis.The n-

type SnO2 has been explored and widely used for transparent conductive electronic

applicaiotns. In the past four decades, SnO 2 is the most extensively studied for gas

sensing applications, by using bulk, thick and thin films to fabricate gas sensors. Most
of the commercially available gas sensors are made mainly of SnO 2 in the form of thick

films, thin films, or porous pellets. The well-known advantage of this material includes

its low-cost, high sensitivities for different gaseous species. SnO 2 in pure form is a

semiconductor with a band gap of 3.6eV [94].

ZnO is a versatile

material that exhibits semiconducting, piezoelectric as well as pyroelectric properties.

ZnO is a material that has a diverse range of nanostructures, whose configurations are

far richer than any other known nanomaterials including carbon nanotubes . Zinc oxide

is a group II-VI semiconductor that most commonly exhibits wurtzite structure in its

unstrained phase. It belongs to the C46v space group, also known as P63mc. At pressures

above 8 GPa it undergoes a phase change to rock salt structure. It has also been shown

to grow in zinc blend phase as a thin film on Ga As substrates[95]. Electrical properties

Zinc oxide (ZnO) has a wide direct band gap (3.37 eV) and a relatively large excitation

binding energy (60 meV). Owing to its unique properties wide band gap and large
excitation binding energy, ZnO has the potential to be applied chemical sensors, solar

cells, luminescence devices etc. ZnO nanowires are also reported to have behaved like

n-type semiconductor due to the presence of interstitial defects and vacancies [9 6-100].

The major road block of ZnO for wide spread applications in electronics and photonics

is its problems with p-type doping. Quite a few p-type doping efforts have been

reported like Ga and N co - doping method which resulted in the formation of low

resistivity (0.5 Ohms/cm) p-type ZnO thin films. Successful p-type doping for ZnO

nanostructures will give a boost to their future prospects in nanoscale electronics and in

the field of optoelectronics. P-type and n-type ZnO nanowires can serve as p-n junction

diodes and LEDs. Field effect transistors (FETs) fabricated from them can be used to

make complementary logic circuits [101-105].