Nanomaterials and Applications

Dr Pradip Kumar Ghosh

Department of Physics
Abhedananda Mahavidyalaya
Sainthia, Birbhum, W.B. India.
Preface

Now a days, scientists around the world have made rapid and significant advances in the

field of nanostructure semiconductor physics. Many new materials and devices which possess

specific properties for special purpose of application is now available, but material limitations

are often major deterrent to the achievements of new technological advancement. Scientists

around the world are now particularly interested in developing materials that maintained its

required properties even under extreme environmental condition. In general the aim of the

engineers is to find the possible ways of improving quality and increasing productivity with the

optimum use of the materials, whilst reducing the manufacturing costs. This can be achieved

with the development of better synthesis techniques, which is capable of large area coating as

well as cost effective.

The basic properties of transparent conducting thin films such as structural and

morphological, electrical conductivity and optical transparency are most important for practical

applications. With the increasing device sophistication based on semiconductor transparent

coating, better quality, exhibited properties of the films are very much essential. One of the

most important interesting field in material science is the fundamental aspects and application

of semiconducting thin films like cadium oxide. The technological interest of the study of

transparent semiconducting thin films has been generated mainly by some interesting exhibited

properties and their possible potential application in industry and research. The highly

conducting transparent thin films have been widely used for variety of applications such as
solar cells, photovoltaic cells, heat reflector, protective coating, gas sensor, temperature

control coating in satellites, surface layer application, etc.

One of the most important fields of current interest in nanostructured materials is the

fundamental aspects and possible applications in nanostractured form in nanodevices for

better performances. Although considerable progress has been achieved in the theoretical

understanding of the properties of nanomaterials, there still exists a number of problem, which

should have to be solved and well understood, before this new technology can be applied in

real applications. As the surface plays the crucial role in determining the different electrical and

optical properties, hence motivated studies are necessary of carefully synthesized the thin films

of these nanostructured materials.

The whole attempt in this book is devoted to the interest of the students, material

scientists and technologists working in diverse fields of micro/nano-semiconducting materials.

If my book on nanomaterial raises the interests and encouragements to the students,

engineers and scientists, then the purpose of the book will be served.

Dr Pradip Kumar Ghosh

Department of Physics
Abhedananda Mahavidyalaya
Sainthia, Birbhum, W.B. India.
Chapter I

NANOSCALE SYSTEMS:

Length scales in physics, Nanostructures: 1D, 2D and 3D nanostructures (nanodots, thin films,
nanowires, nanorods), Band structure and density of states of materials at nanoscale, Size
Effects in nano systems, Quantum confinement: Applications of Schrodinger equation Infinite
potential well, potential step, potential box, quantum confinement of carriers in 3D, 2D, 1D
nanostructures and its consequences.
1. Introduction

1.1. Historical perspectives of nanoscience and nanotechnology

Richard Feynman’s 1959 lecture “There is plenty of room at the bottom” has often been

quoted when people talk about nanoscience and nanotechnology. He predicted that “we will get

an enormously greater range of properties that substances can have, and of different things that

we can do” if atoms and molecules can be arranged in the way we want. However, the real take-

off of nano-related research and technological exploitation started at about 15 years ago. This is

a logical consequence of the developments of science and technology.

The 20th Century has been called the Century of Physics because of the revolutionary

development of physics and its tremendous impacts. A solid foundation has been laid to describe

the Nature at the elementary particle level at one end to the evolution of the Universe at the

other. Of close relevance to our life (and economy), quantum mechanics has helped us to reveal

the nature of atoms, molecules and solids. Solid state physics led to the creation and great

success of semiconductor science and engineering. Integrated circuits, laser and magnetic disks

are indispensable to the Information Technology and our daily life.

Our understanding and exploitation of material world around us have been pushing

forward in two opposite directions: from the bottom up and from the top down. In the bottom-up

approach, we start with electrons and nucleons as the building blocks. The properties of atoms

and most of relatively simple molecules (this can be called the sub-nm world) have been well

understood. At increasing complexity levels, we are dealing with macro-molecules, polymers,

clusters and bio-molecules (These are relatively small nanostructures we will deal with). On the

other hand, we have been reducing the sizes of solid state devices (e.g., transistors, date storage

bits) from macroscopic scales to deep sub-micron (~ 0.1-0.2 m), as shown in the 1999

International Technology Roadmap for Semiconductors (ITRS) in Table 1, and into deep sub-

0.1-m scale in ten years. So far, the physical principle of device operation has not changed

dramatically in the scaling-down process. But this will not likely be the case for the next decade.

The top-down and bottom-up approaches have largely developed independently in the

past. Today, these two meet at the nanoscale territory. This means that people along the top-

down line have to consider the behavior of nature at the atomic scales, while those taking the

bottom-up approach are ready to fabricate novel devices and materials with numerable atoms and

molecules as the building blocks. More importantly, these atomic or molecular devices will not

just be toys played by researchers for fun or writing academic papers and thesis, but really work

with indispensable functions in our PCs, mobile phones, cars, home appliances, and in health

products and services. Nanoscience and nanotechnology should not be considered as a

fashionable hot subject. Rather, they are a logic development stage of research and development

that is built on previous achievements.

As demonstrated very well in the development of integrated circuits, with device scaling

down, the cost of manufacturing for each device and the energy consumption of each logic

operation are reduced. Meanwhile, making devices smaller can have an electronic system

working faster and with stronger functionalities. With nanoscience/nanotechnology, in addition

to smaller devices operating based on the same principle as the bigger ones, we can have devices

with novel functions not available from the conventional devices.

 The invention and maturing of a variety of fabrication and characterization tools are also

essential to the booming of nanoscience and nanotechnology. In fact, the development of

nanoscience and nanotechnology has been mainly experimental-driven which is often related

with applications of new fabrication and characterization techniques. Among them, scanning

probe microscopy (SPM) (including scanning tunneling microscopy (STM), atomic force

microscopy (AFM), and their variants), molecular beam epitaxy (MBE), various nanostructural

self-assembly processes, as well as evolving microelectronic fabrication technologies have been

playing particularly important roles.

Nanoscience and nanotechnology are still in their rapid-development stage. In some

areas, although many experimental and theoretical works have been performed, clear

fundamental understandings are yet to be searched. The territory of nanoscience and

nanotechnology is not well-defined, and it is still expanding. Although some people have drawn

a roadmap for the development of nanoelectronics similar to that in microelectronics, future

discoveries will definitely lead to new routes. Furthermore, nanoscience and nanotechnology are

considered important pillars of the knowledge-based economy, and have been drawing great

interests both in and out of the academic community.

1.2. Scope of this course

This course is designed for graduate students to comprehend the physical foundation of

nanoscience and nanotechnology. A proper background in undergraduate-level quantum

mechanics, statistical mechanics and solid state physics is required. More theoretical

descriptions of physical processes involving advanced quantum and statistical mechanics

approaches are avoided in this lecture. Interested readers are provided with references on such
advanced descriptions. Nanoscience and nanotechnology are multi-disciplinary and rapidly

evolving topics that are related to many branches of science and engineering. An up-to-date

comprehensive description is beyond both the lecturer’s capability and the time constraint. We

will focus on the basic physics, chemistry and materials science issues of nanostructures, which

are long-life-time foundations of nanoscience and nanotechnology.

We shall begin with a review of quantum mechanics of reduced dimensional systems and

solid state physics. A brief coverage of surface and thin sciences will also be given. Then,

widely used nano-fabrication and characterization techniques will be introduced. In the second

half of this course, several prototypical nanostructural systems will be analyzed to demonstrate

the science of nano-world. These systems are chosen also because of their application

perspectives. Again, due to the limits of both the lecturer’s capability and available time, some

important subjects, such as bio-objects and micro-electromechanical systems (MEMS), will not

be covered.

So far, I have not found a single textbook that covers all the contents of this course.

Therefore, journal articles and book chapters will be used as reference materials. A few books

have been placed at the course reservation desk in the Science Library. Each topic will not be

described in great detail in our lectures. This leaves room for students to do projects based on

literature studies or your own research work. The project is an important part of this course since

it is a required training for your future research and development activities. Preferably two

students in a group choose a topic you are interested in (and also of interest to others). Through

the search and in-depth study of literatures, in particular those reflecting the most recent research

and development activities. Near the end of the semester, each group will give a presentation (~

15min talk + 5min Q&A) on the project topic followed with discussion in seminar-like sessions.
The project topics can be in the range covered in the lectures, but it is also highly encouraged to

choose one out of the range. It has been shown in the past years that the project study,

presentations and discussion are an effective way, both for students and the lecturers, to learn

some most recent advancement and real examples of nano-related research and development.

It is unrealistic to expect that one becomes an expert in nanoscience after finishing this

course. We hope that the introduction and overview of nanoscience/nanotechnology topics

(including those in the projects done by your and others) and the literatures listed in the

references will be helpful in your future nano-related exploration.

1.3. Length scales in physics

The special properties of nanomaterials do not derive from different laws of physics,

which are the same for objects large and small. For example, Newton's second law (F=ma),

Coulomb's law, and the laws of energy and momentum conservation are the same for buckyballs

(C60) and full-size soccer balls. Nevertheless, the physics of electrons, atoms, and photons

naturally produce characteristic length scales. For example, in we discovered that the mean free

path of an electron in a good metal is about 40 nm. we learned that the Bohr radius of an electron

or hole in doped Si is about 4 nm, and that the coherence length of Cooper pairs in

semiconductors is somewhere between a few nm and 1 µm. When objects become small relative

to these characteristic lengths, their physical properties change in interesting ways. Materials that

exist at the relevant length scale are called mesoscopic (meso = "between," scopic = "size")

meaning that they cross over from one kind of behavior - the bulk behavior of large objects - to

another. This length scale is different for different kinds of properties, but for many it happens

between 1 and 100 nm.

1.4. What are nanostructures?

The word "nano" means a billionth (10-9) part of a unit in general. In our course, it refers

specifically to the length scale: nanometer or nm,

1 nm = 10-9 m = 10-3 m = 10 Å

Nanostructures refer to materials systems with length scale in the range of ~ 1-100 nm in at least

one dimension. In a nanostructure, electrons are confined in the nanoscale dimension(s), but are

free to move in other dimension(s). One way to classify nanostructures is based on the

dimensions in which electrons move freely:

Quantum well: electrons are confined in one dimension (1D), free in other 2D. It can be

realized by sandwiching a narrow-bandgap semiconductor layer between the wide-gap ones. A

quantum well is often called a 2D electronic system.

Quantum wires: confined in two dimensions, free in 1D (so it is called a 1D electronic

system). Real quantum wires include polymer chains, nanowires and nanotubes.

Quantum dots: electrons are confined in all dimensions, as in clusters and nano-crystallites

Nanostructures are unique as compared with both individual atoms/molecules at a smaller

scale and the macroscopic bulk materials. They are also called mesoscopic structures.

Nanoscience research focuses on the unique properties of nanoscale structures and materials that

do not exist (or only very weakly exist) in structures of same material composition but at other

scale ranges.
1.5. What makes nanostructures unique and interesting?

For bulk materials (e.g., a Cu wire, a cup of water), their intrinsic physical properties, such as

density, conductivity and chemical reactivity, are independent of their sizes. For example, if a

one-meter Cu wire is cut into a few pieces, those intrinsic properties of the shorter wires remain

the same as in the original wire. If the dividing process is repeated again and again, this

invariance cannot be kept indefinitely. Certainly, we know that the properties are changed

greatly when the wire is divided into individual Cu atoms (even more at the level of electrons,

protons and neutrons). Significant property changes often start when we get down to the

nanoscales. The following phenomena critically affect the properties of nanostructural materials:

Quantum confinement: the confinement of electrons in the nanoscale dimensions result in

quantization of energy and momentum, and reduced dimensionality of electronic states

Quantum coherence: certain phase relation of wave function is preserved for electrons

moving in a nanostructure, so wave interference effect must be considered. But in

nanostructures, generally the quantum coherence is not maintained perfectly as in atoms and

molecules. The coherence is often disrupted to some extent by defects in the nanostructures.

Therefore, both quantum coherent and de-coherent effects have to be considered, which often

makes the description of electronic motion in a nanostructure more complicated than in the

extreme cases.

Surface/interface effects: a significant fraction (even the majority) of atoms in nanostructure

is located at and near the surfaces or interfaces. The mechanic, thermodynamic, electronic,

magnetic, optical and chemical states of these atoms can be quite different than those interior

atoms.
 These factors play roles to various degrees (but not 100%) of importance. For example, the

confinement and the coherent effects are not as complete as that in an atom. Both the crystalline

(bulk) states and the surface/interface states cannot be ignored in nanoscale structures. The

different mixture of atomic/molecular, mesoscopic and macroscopic characters make the

properties of nanostructures vary dramatically. Nanostructural materials are often in a

metastable state. Their detailed atomic configuration depends sensitively on the kinetic

processes in which they are fabricated. Therefore, the properties of nanostructures can be widely

adjustable by changing their size, shape and processing conditions. The situation is similar to

molecular behavior in chemistry (e.g., N vs. N2) in certain aspect. Because of the rich and often

surprising outcomes, it will be extremely interesting and challenging to play with nanostructural

systems. Nanoscience and nano-engineering have been an area where many breakthroughs have

been and will continue to be produced.

1.6. Low dimensional system:

In general, the low dimensional systems are of three types: so-called two dimensional

system (2D) which include thin films, layer structures, quantum wells; one dimensional system

(1D) such as nanowires, nanorods etc; zero dimensional system (0D) such as quantum dots,

nanoparticles. Quantum confinement effects are observed in nanoparticles because of smaller

sizes of the particles, which restrict the size of the potential well in which the carrier moves.

1.7. Density of states:

The concentration of free carriers, neutral impurities, and ionized impurities in a

semiconductors depend upon a large numbers of parameters such as bandgap energy, impurity

atom concentration, free carrier mass and dielectric constant. The dependence of the majority
and minority carrier concentrations, impurity concentration, impurity ionization energy and some

other materials parameters are obtained from semiconductor statistics, and also whether a

electronic state is vacant or populated that is described with the semiconductor statistics. The

localized impurity states as well as delocalized conduction and valence band states are also

included in the electronic states. The states in the bands and their dependence on energies are

described by the density of states function. In heterostructures form of semiconductors, the

motions of the free carriers are restricted to two, one or zero special dimensions. To describe

such systems of reduced dimensions, the density of states (DOS, defined as a function of energy

g(E)) of quantum wells (two dimensions), quantum wires (one dimension), and quantum dots

(zero dimensions), must have to be known earlier.

To find the available electron states in a system we have to solve Schrodinger's

equation: H  E . However, it is easier to calculate the density of states as the number of

dn dn dk
states (n)/energy (E)/volume =   (1.1)
dE dk dE

2k 2
For free electron model: E  and
2m 

dk m m 1
 2  . (1.2)
dE  k 2k 2 E

Now in k-space for finite size of the sample L, the periodic boundary condition is

 2 
e ikx  e ik ( x  L ) and kL  2n or, k  n  (1.3)
 L 
 2
Therefore in k-space the states are spaced by and in d-dimensions states in k-space have a
L

d
 L  2 2
density = 2      Ld   volume (1.4)
 2  (2 ) (2 ) d
d

where multiplication factor 2 is due to the spin degeneracy  and  and Ld is volume in d-

dimensions.

Therefore the number of states in between k and k +dk = dn.

 2 Ldk d 1
2dk  

2 Ld  kL2 dk
dn    2kdk  d 2 (1.5)
(2 ) d  
 k 2 L2 dk
 4k 2
dk  d 3
 2

2 d 1


dn dn  k
Now, in k-space become,  d 2 (1.6)
dk dk 
k2
 2 d 3


Therefore the density of states in k-space / volume comes out,

 Degrees of freedom Density of states

g(E)
g 3 D = constant  E

3D
g(E)

g 2 D = constant

E
g(E)

1
g1D = constant 
E
2D

E
g(E)

  E 
1
g 0 D = constant 
E
1D
E

Figure 1.1. Schematic diagram of dependence of energy on density of states in

different dimensions
  1 2m 
 d 1
 E
dn dn dk  m 
   d 2 (1.7)
dE dk dE  2
 m  2m  E
 d 3
  2  2

The dependence of energy (E) on density of states (g) in different dimensions (degrees

of freedom) are shown in the schematic diagram as in Figure 1.1.

Therefore we see that the density of states for 3-D is parabolic, 2-D is constant, for 1-D it

which is a delta function  E  . From

1 1
is proportional to and for 0-D it is proportional to
E E

these discussions it can be concluded about the general trends of the density of states that the

lower the dimension, more peaky the density of states at the bottom of the band. The Figure

1.2. Shows the schematic diagram of variations of density of states for different dimensions.

In general the density of states (g(E)) changes with the change of dimension (d) of

crystal lattice as follows:

d 1
g ( E )dE  E 2
dE (1.8)

The variation of density of states in 3, 2, 1 and 0D are very interesting. Every time when

we go to a lower dimensionality system, the dependence of density of states on energy changes

1
by E 2
. The variations of density of states for different dimensions with energy are shown in

Figure 1.2.
 Density of states

Bulk (3D)

Quantum well (2D)

Quantum wire (1D)

Quantum dot (0D)

Energy

Figure 1.2. Schematic diagram of density of states for different dimensions

1.8. Quantum confinement:

If the electrons are confined in a potential well, then their energy levels En are

quantised. Quantum confinement effect modifies the electronic structure of nanocrystals

when the sizes of the nanoparticles are comparable to that of Bohr excitonic radius ( rB ) of

those materials.

h 2  1 1 
rB   * *  (1.9)
e 2  me mh 

where  is the permittivity of the sample, m*e is the effective mass of electron and m*h is the

effective mass of hole in the nanomaterial.

 These phenomena can be explained by a simple example for a particle of mass m in an

infinite square well potential of width L in one dimension,

0 for x L
V x    2 (1.10)
 for x L
2

The solution of Schrodinger equation with these potential, the energy can be obtained.

The allowed energy levels (En) of the particles in the well can be expressed as,

n2h2
En  (where n = 1, 2, 3, …) (1.11)
8mL2

The energy of these levels is inversely proportional to the square of the well size.

Therefore, it is observed that for large well size (for bulk material), the energy level spacing

tends to zero and size dependency is removed. As the width of the well (particle size)

decreases, the levels spacing increases and the particle is strongly bounded by the well.

The values of particle radius (r) in the nanocrystalline materials are less than Bohr radius

( r  rB ), the strong quantum confinement effects take place. For particle radius (r) greater

than Bohr radius ( r  rB ), the weak quantum confinement effects take place because the

particle is weakly bound by the nucleus.

1.9. Objectives

This book reports on the synthesis and characterizations such as structural, optical,

compositional and electrical properties of nanostructures thin films. The nanostructural

properties can be studied by scanning electron microscope (SEM), transmission electron

microscope (TEM), and proper phase confirmation can be done by X-ray diffraction (XRD) and

selected area electron diffraction (SAED) patterns. Bonding information, compositional

analyses and optical properties of the films can be obtained by Fourier transform infrared

spectroscopy (FTIR), energy dispersive X-ray analyses (EDX) and UV-Vis-NIR spectrophotometer

respectively. The electrical properties can be studied by four probe methods, Hall

measurement, etc. The thickness of the films can be measured by cross-sectional SEM and the

spectroscopic ellipsometry (Nano-view) analysis.

Many new materials and devices which posses specific properties for special purpose of

application is now available, but material limitations are often major deterrent to the

achievements of new technological advancement. Scientists around the world now particularly

interested in developing materials that maintained its required properties even under extreme

environmental condition. In general the aim of the engineers is to find the possible ways of

improving quality and increasing productivity with the optimum use of the materials, whilst

reducing the manufacturing costs. This can be achieved by the material scientists with the

development of better synthesis technique with low costs.

References

[1]. T. J. Coutts and R. Hill, Third International Conference on Future Energy Sources,

London, U.K. (IEE, London, 1981), pp. 147–150.

[2]. R. D. Brown, http://minerals.usgs.gov/minerals/pubs/commodity/indium/

index.html#myb.
[3]. B. Andersson, in PV and the Environment, edited by V. Fthenakis, K. Zweibel, and P.

Moskowitz (Brookhaven National Laboratory, 1998), Vol. BNL-5257.

[4]. B. A. Andersson, C. Azar, J. Holmberg, and S. Karlsson, Energy 23, 407 (1998).

[5]. J. Plachy, http://minerals.usgs.gov/minerals/pubs/commodity/cadmium/ index.html#myb.

[6]. K.K. Chattopadhyay and A. N. Banerjee, Introduction to Nanoscience and Technology

(PHI Learning Private Limited).

Chapter II

SYNTHESIS OF NANOSTRUCTURE MATERIALS:

Top down and Bottom up approach, Photolithography. Ball milling.Gas phase

condensation.Vacuum deposition. Physical vapor deposition (PVD): Thermal evaporation, E-
beam evaporation, Pulsed Laser deposition. Chemical vapor deposition (CVD). Sol-Gel.Electro
deposition. Spray pyrolysis. Hydrothermal synthesis.Preparation through colloidal
methods.MBE growth of quantum dots.
2.1. Top down and Bottom up approach

The fabrication structures at the nano level can be broken down into two main methods;

top down and bottom up construction.

The most common top-down approach to fabrication involves lithographic patterning

techniques using short-wavelength optical sources. A key advantage of the top-down approach—

as developed in the fabrication of integrated circuits—is that the parts are both patterned and

built in place, so that no assembly step is needed. Optical lithography is a relatively mature field

because of the high degree of refinement in microelectronic chip manufacturing, with current

short-wavelength optical lithography techniques reaching dimensions just below 100 nanometres

(the traditional threshold definition of the nanoscale). Shorter-wavelength sources, such as

extreme ultraviolet and X-ray, are being developed to allow lithographic printing techniques to

reach dimensions from 10 to 100 nanometres. Scanning beam techniques such as electron-beam

lithography provide patterns down to about 20 nanometres. Here the pattern is written by

sweeping a finely focused electron beam across the surface. Focused ion beams are also used for

direct processing and patterning of wafers, although with somewhat less resolution than in

electron-beam lithography. Still-smaller features are obtained by using scanning probes to

deposit or remove thin layers.

These nanoscale printing techniques offer several advantages beyond the ability to use a

wider variety of materials with curved surfaces. In particular, such approaches can be carried out

in ordinary laboratories with far-less-expensive equipment than that needed for conventional

submicron lithography. The challenge for all top-down techniques is that, while they work well
at the microscale (at millionths of a metre), it becomes increasingly difficult to apply them at

nanoscale dimensions. A second disadvantage is that they involve planar techniques, which

means that structures are created by the addition and subtraction of patterned layers (deposition

and etching), so arbitrary three-dimensional objects are difficult to construct.

2.1.1. Top Down Fabrication

Top down fabrication can be likened to sculpting from a block of stone. A piece of the

base material is gradually eroded until the desired shape is achieved. That is, you start at the top

of the blank piece and work your way down removing material from where it is not required.

Nanotechnology techniques for top down fabrication vary but can be split into mechanical and

chemical fabrication techniques.

2.1.2. Top Down Fabrication Techniques

The most top down fabrication technique is nanolithography. In this process, required

material is protected by a mask and the exposed material is etched away. Depending upon the

level of resolution required for features in the final product, etching of the base material can be

done chemically using acids or mechanically using ultraviolet light, x-rays or electron beams.

This is the technique applied to the manufacture of computer chips.

2.1.3. Bottom Up Fabrication

Bottom up fabrication can be likened to building a brick house. Instead of placing bricks

one at a time to produce a house, bottom up fabrication techniques place atoms or molecules one

at a time to build the desired nanostructure. Such processes are time consuming and so self

assembly techniques are employed where the atoms arrange themselves as required.
Bottom-up, or self-assembly, approaches to nanofabrication use chemical or physical forces

operating at the nanoscale to assemble basic units into larger structures. As component size

decreases in nanofabrication, bottom-up approaches provide an increasingly important

complement to top-down techniques. Inspiration for bottom-up approaches comes from

biological systems, where nature has harnessed chemical forces to create essentially all the

structures needed by life. Researchers hope to replicate nature’s ability to produce small clusters

of specific atoms, which can then self-assemble into more-elaborate structures.

2.1.4. Bottom Up Fabrication Techniques

Self assembling nanomachines are regularly mentioned by science fiction writers but

significant obstacles including the laws of physics will need to be overcome or circumvented

before this becomes a reality. Other areas involving bottom up fabrication are already quite

successful. Manufacturing quantum dots by self-assembly quantum dots has rendered the top

down lithographic approach to semiconductor quantum dot fabrication virtually obsolete.

2.2. Lithography - Application

The main technology to realize a very tiny feature size for nano-components is

lithography. Optical lithography is the key technology to be utilized today and it is expected to

be relevant beyond 70 and 100 nm with the use of 157-nm wavelength and 193-nm wavelength

tools, respectively.

The reduction of feature sizes as low as 50 nm and below will need more sophisticated

lithography tools. Extreme ultraviolet (EUV) lithography is the candidate for the futuristic

microelectronics sector, and it is now robustly supported. At the 13-nm wavelength, EUV

lithography will attain feature size at 45 nm and below.

2.2.1. Photolithography Applications and Properties

Photolithography can be defined as a selective process that is used for patterning a

required design onto the material that is used to fabricate with (the wafer in the semiconductor

sector). As the first step, a photoresist is applied while applying a pattern in an even film. The

mask is a metal sheet holding the real pattern that will be later etched into the photoresist.

This mask is subsequently cut so that the exposed parts of the photoresist become the real

pattern, upon illuminating a UV light from behind. These exposed parts will continue to remain

on to the fabricated device (negative resist) or can be subsequently cleaned away (positive

resist).

With photolithography being the leading constraining factor on the size of wafer fabrication, this

is the domain where most of the studies have been devoted. The very first form of

photolithography is contact printing. In this form, the mask was directly positioned on top of the

photoresist at the time of the exposure process. While this process provided an excellent

resolution, at times, it also caused slight damage to the mask and the wafer.

The next breakthrough, projection printing, was able to separate the mask from the photoresist,

and overcame the problems.

2.2.2. Nanolithography

Nanolithography is a growing field of techniques within nanotechnology dealing with

the engineering (etching, writing, printing) of nanometer-scale structures. From Greek, the word

can be broken up into three parts: "nano" meaning dwarf, "lith" meaning stone, and "graphy"

meaning to write, or "tiny writing onto stone." Today, the word has evolved to cover the design

of structures in the range of 10−9 to 10−6 meters, or structures in the nanometer range. Essentially,
field is a derivative of lithography, only covering significantly smaller structures. All

nanolithographic techniques can be separated into two categories: those that etch away molecules

leaving behind the desired structure, and those that directly write the desired structure to a

surface (similar to the way a 3D printer creates a structure).

The field of nanolithography was born out of the need to increase the number of

transistors in an integrated circuit in order to maintain Moore's Law.

While lithographic techniques have been around since the late 18th century, none were applied to

nanoscale structures until the mid-1950s. With evolution of the semiconductor industry, demand

for techniques capable of producing micro- and nano-scale structures

skyrocketed. Photolithography was applied to these structures for the first time in 1958

beginning the age of nanolithography.[1] Since then, photolithography has become the most

commercially successful technique, capable of producing sub-100 nm patterns.[2] There are

several techniques associated with the field, each designed to serve its many uses in the medical

and semiconductor industries. Breakthroughs in this field contribute significantly to the

advancement of nanotechnology, and are increasingly important today as demand for smaller and

smaller computer chips increases. Further areas of research deal with physical limitations of the

field, energy harvesting, and photonics.[2]

2.2.3. Electron Beam (e-beam) Lithography

Currently, electron-beam lithography, or EBL, is used for making the tiniest parts on

silicon substrates and is the most effective technique for producing patterns on substrates, like X-

ray masks and photomasks. Electrons are utilized to directly etch onto the photoresist. Through a
range of lenses and coils, the electrons’ path is controlled by a computer to expose the right

sections of the photoresist.

Efforts for next-generation e-beam lithography are targeted on elaborating a matrix of a

micro-fabricated e-gun for e-beam masker. The main aim is to parallelize the electron beam

lithography.

2.2.4. X-Ray Lithography

X-ray lithography employs the same process as above, except that an X-ray source is

used instead of UV.

2.3. Ball milling

It is a ball milling process where a powder mixture placed in the ball mill is subjected to

high-energy collision from the balls. This process was developed by Benjamin and his coworkers

at the International Nickel Company in the late of 1960. It was found that this method, termed

mechanical alloying, could successfully produce fine, uniform dispersions of oxide particles

(Al2O3, Y2O3, ThO2) in nickel-base superalloys that could not be made by more conventional

powder metallurgy methods. Their innovation has changed the traditional method in which

production of materials is carried out by high temperature synthesis. Besides materials synthesis,

high-energy ball milling is a way of modifying the conditions in which chemical reactions

usually take place either by changing the reactivity of as-milled solids (mechanical activation —

increasing reaction rates, lowering reaction temperature of the ground powders)—or by inducing

chemical reactions during milling (mechanochemistry). It is, furthermore, a way of inducing

phase transformations in starting powders whose particles have all the same chemical
composition: amorphization or polymorphic transformations of compounds, disordering of

ordered alloys, etc.

The alloying process can be carried out using different apparatus, namely, attritor, planetary mill

or a horizontal ball mill. However, the principles of these operations are same for all the

techniques. Since the powders are cold welded and fractured during mechanical alloying, it is

critical to establish a balance between the two processes in order to alloy successfully. Planetary

ball mill is a most frequently used system for mechanical alloying since only a very small

amount of powder is required. Therefore, the system is particularly suitable for research purpose

in the laboratory. The ball mill system consists of one turn disc (turn table) and two or four

bowls. The turn disc rotates in one direction while the bowls rotate in the opposite direction. The

centrifugal forces, created by the rotation of the bowl around its own axis together with the

rotation of the turn disc, are applied to the powder mixture and milling balls in the bowl. The

powder mixture is fractured and cold welded under high energy impact.

The impact energy of the milling balls in the normal direction attains a value of up to 40

times higher than that due to gravitational acceleration. Hence, the planetary ball mill can be

used for high-speed milling.

During the high-energy ball milling process, the powder particles are subjected to high

energetic impact. Microstructurally, the mechanical alloying process can be divided into four

stages: (a) initial stage, (b) intermediate stage, (c) final stage, and (d) completion stage.

(a) At the initial stage of ball milling, the powder particles are flattened by the

compressive forces due to the collision of the balls. Micro-forging leads to changes in the shapes
of individual particles, or cluster of particles being impacted repeatedly by the milling balls with

high kinetic energy. However, such deformation of the powders shows no net change in mass.

(b) At the intermediate stage of the mechanical alloying process, significant changes

occur in comparison with those in the initial stage. Cold welding is now significant. The intimate

mixture of the powder constituents decreases the diffusion distance to the micrometer range.

Fracturing and cold welding are the dominant milling processes at this stage. Although some

dissolution may take place, the chemical composition of the alloyed powder is still not

homogeneous.

(c) At the final stage of the mechanical alloying process, considerable refinement and

reduction in particle size is evident. The microstructure of the particle also appears to be more

homogenous in microscopic scale than those at the initial and intermediate stages. True alloys

may have already been formed.

(d) At the completion stage of the mechanical alloying process, the powder particles

possess an extremely deformed metastable structure. At this stage, the lamellae are no longer

resolvable by optical microscopy. Further mechanical alloying beyond this stage cannot

physically improve the dispersoid distribution. Real alloy with composition similar to the starting

constituents is thus formed.

For all nanocrystalline materials prepared by high-energy ball milling synthesis route,

surface and interface contamination is a major concern. In particular, mechanical attributed

contamination by the milling tools (Fe or WC) as well as ambient gas (trace impurities such as

O2, N2 in rare gases) can be problems for high-energy ball milling. However, using optimized

milling speed and milling time may effectively reduce the contamination. Moreover, ductile
materials can form a thin coating layer on the milling tools that reduces contamination

tremendously. Atmospheric contamination can be minimized or eliminated by sealing the vial

with a flexible “O” ring after the powder has been loaded in an inert gas glove box. Small

experimental ball mills can also be completely enclosed in an inert gas glove box. As a

consequence, the contamination with Fe-based wear debris can be reduced to less than 1–2 at.%

and oxygen and nitrogen contamination to less than 300 ppm. Besides the contamination, long

processing time, no control on particle morphology, agglomerates, and residual strain in the

crystallized phase are the other disadvantages of high-energy ball milling process.

2.4. Gas-Phase Condensation of nanoparticles

The process utilises a gas, which is typically inert, at pressures high enough to promote

particle formation, but low enough to allow the production of spherical particles. Gas-phase

condensation uses a vacuum chamber that consists of a heating element, the metal to be made

into nano-powder, powder collection equipment and vacuum hardware. Metal is introduced onto

a heated element and is rapidly melted. The metal is quickly taken to temperatures far above the

melting point, but less than the boiling point, so that an adequate vapour pressure is achieved.

Gas is continuously introduced into the chamber and removed by the pumps, so the gas flow

moves the evaporated metal away from the hot element. As the gas cools the metal vapour,

nanometer-sized particles form. These particles are liquid since they are still too hot to be solid.

The liquid particles collide and coalesce in a controlled environment so that the particles grow to

specification, remaining spherical and with smooth surfaces. As the liquid particles are further

cooled under control, they become solid and grow no longer. At this point the nanoparticles are

very reactive, so they are coated with a material that prevents further interaction with other

particles (agglomeration) or with other materials.

 Synthesis methods of nanoparticles in the gas phase The synthesis methods for

nanoparticles can be divided into three main groups. The first group comprises the liquid-phase

methods, which apply chemical reactions in solvents. This leads to colloids, in which the

nanoparticles formed can be stabilized against aggregation by surfactants or ligands. The second

group consists of methods basing on surface growth under vacuum conditions. Diffusion of

atoms or small clusters on suitable substrates can lead to island formation, which can be seen as

nanoparticles. An important example is Stranski-Krastanow growth, which is used for growing

III-V quantum dots. The last group, gas-phase synthesis.

Most synthesis methods of nanoparticles in the gas phase are based on homogeneous

nucleation in the gas phase and subsequent condensation and coagulation. The ablation of a solid

source with a pulsed laser can also yield nanoparticles, but the formation mechanism is at present

not very clear. A micronsized aerosol droplet may also yield nanoparticles by evaporating a

solute-containing droplet. Electrospray systems are often applied as droplet generators, as they

produce very small droplets being quite monodisperse in comparison to other spray processes.

Additionally, droplet explosion due to an electrical charge which exceeds the Rayleigh limit

during evaporation may yield even smaller droplets. Finally, initiating homogeneous nucleation

inside aerosol droplets can result in many nanosized nuclei in the droplet, which upon drying will

yield nanoparticles. This is, in fact, not a formation mechanism in the gas phase but for sake of

completeness it will be shortly discussed here, as this so-called spray pyrolysis is a well-known

aerosol synthesis route. The generation of nanoparticles from the vapor phase requires the

establishment of supersaturation. This is made possible by physical or chemical methods. The

physical methods involve some form of cooling of the monomers, by expansion, by mixing with

a cooler gas or by heat transfer to the surroundings.

 Supersaturation can be achieved also by chemical reactions which produce a nonvolatile

condensable product. These reactions are usually decomposition reactions initiated by a rise in

temperature and used extensively in laser and flame reactors. Various heating and evaporation

methods of interest will be dealt with in the next section. Furthermore, methods for rapidly

cooling the vapor will be described because fast cooling processes are especially important when

very small particles have to be synthesized and when the formation of hard agglomerates has to

be avoided.

2.4.1. Furnace flow reactors

Oven sources are the simplest systems to produce a saturated vapor for substances

having a large vapor pressure at intermediate temperatures up to about 1700°C. A crucible

containing the source material is placed in a heated flow of inert carrier gas. This has the

disadvantage that the operating temperature is limited by the choice of crucible material and that

impurities from the crucible might be incorporated in the nanoparticles. Nanoparticles are

formed by subsequent cooling, such as natural cooling or dilution cooling. For very small

particles a rapid temperature decrease is needed which can be achieved by the free jet expansion

method. Materials with too low vapor pressure for obtaining appreciable particle density have to

be fed in the form of suitable precursors, such as organometallics or metal carbonyls, in the

furnace. These decompose in the oven to yield a condensable material. Using furnace flow

reactors, elemental nanoparticles such as Ag (Scheibel and Porstendorfer, 1983) and Ga (Deppert

et al., 1996) and also compounds such as PbS (Kruis et al., 1996) can be obtained.

2.4.2. Laser reactors

 In the laser pyrolysis technique, being a special class of laser processing techniques

(Peled et al, 1996), a flowing reactant gas is heated rapidly with an IR laser such as a cw CO2

laser. The source molecules are heated selectively by absorption of the laser beam energy,

whereas the carrier gas is only indirectly heated by collisions with the reactant molecules. A gas

phase decomposition of the reactants takes place due to the temperature increase and

supersaturation is created. The main advantage of laser-heating in gas-flow systems is the

absence of heated walls which reduces the danger of product contamination.

UV lasers can be used to obtain photochemical dissociation.

2.4.3. Laser vaporization of solids

This technique uses a laser which evaporates a sample target in an inert gas flow reactor.

The source material is locally heated to a high temperature enabling thus vaporization. The vapor

is cooled by collisions with the inert gas molecules and the resulting supersaturation induces

nanoparticle formation. Kato (1976) used a continuous-wave CO2 laser with a power of 100 W.

Nanoparticles between 6 and 100 nm of many complex refractory oxides such as Fe3O4,

CaTiO3 and Mg2SiO4 were synthesized under an inert gas pressure of 1 mbar to 5 bar from

powders, single crystals or sintered blocks. Nanocomposites can also be produced. They

evaporated simultaneously a metallic and a ceramic target by a cw CO2 laser creating a

composite film close to the target. The matrix consisted of Al and the dispersed phase consisted

of amorphous SiO2 fibers with diameters between 25 and 120 nm.

2.4.4. Flame reactors

 Nanoparticles are produced by employing the flame heat to initiate chemical reactions

producing condensable monomers. The flame route has the advantage of being an inexpensive

method, however usually it yields agglomerated particles. An example is the oxidation of TiCl4,

SiCl4 or SnCl4 in a CH4/O2 flame leading to TiO2, SiO2 or SnO2 particles with primary

particle sizes between 10 and 100 nm (Vemury et al., 1997). More complex products can be also

obtained. Zachariah et al. (1995) added small amounts of Fe(CO)5 and SiO2(CH3)6 to a

premixed CH4/O2 flame with temperatures at about 2000°C, forming Fe3O4 particles of 5-10

nm embedded in larger SiO2 host particles. The synthesis was conducted at relatively high

temperatures under oxygen-rich conditions to minimize carbon contamination. A method to

reduce the agglomeration of nanoparticles, avoiding oxidation, is to encapsulate them within a

material which can be later removed. Dufoux and Axelbaum (1995) applied a Na coflow flame

with a burner consisting of several concentric tubes. A TiCl4 vapor was fed to the central tube

while the Na vapor was fed to the concentric surrounding tube. An inert gas acts as a sheath gas

between these two flows and shields the flame from ambient air. Ti particles with sizes of 10-30

nm were produced and were confined within larger NaCl particles. The NaCl can be removed by

washing with water, glycerin or by sublimation.

2.4.5. Plasma reactors

A plasma can also deliver the energy necessary to cause evaporation or initiate chemical

reactions. The plasma temperatures are in the order of 104 °C, decomposing the reactants into

ions and dissociating atoms and radicals. Solid powder feeds can also be decomposed by the

plasma. Nanoparticles are formed upon cooling while exiting the plasma region. Main types of

the thermal plasmas are dc plasma jet, dc arc plasma and rf induction plasma (Young and

Pfender, 1985). A small laboratory plasma system, the inductively coupled plasma (ICP), is often
used at atmospheric pressures in combination with an aerosol spray system employing an

ultrasonic atomizer. This technique is called spray-ICP (Kagawa et al., 1993). As the residence

time of the droplets in the plasma is very short it is important that the droplet sizes are small in

order to obtain complete evaporation. Complex materials such as multicomponent oxides can be

obtained by using appropriate mixtures. By using a solution of Ba(NO3)2 and Fe(NO3)3 in

water, Mizoguchi et al. (1994) obtained by spray-ICP BaFe12O19 nanoparticles with sizes

between 10 and 50 nm. In most cases, the plasma-generated vapors are quenched by mixing with

a cold gas. This leads to high cooling rates, but also to nonuniform cooling which deteriorates the

uniformity of the produced particles. Rao et al. (1995a,b) used a subsonic nozzle expansion after

a dc arc plasma in order to obtain more uniform cooling rates. Another method uses a

microwave-generated plasma, in which temperatures between 300°C and 900 °C can be

obtained. The plasma enhances the kinetics of the chemical reactions leading to nanoparticle

formation due to ionization and dissociation of the reactive molecules. Since the lower

temperature decreases the sinter rate, the formation of hard agglomerates is reduced (Vollath and

Sickafus, 1992).

2.4.6. Spark source and exploding wire

A high-current spark between two solid electrodes can be used to evaporate the electrode

material for creating nanoparticles. At the electrodes a plasma is formed. This technique is used

for materials with a high melting point such as Si or C, which cannot be evaporated in a furnace.

Saunders et al. (1993a) used an electric spark with an energy between 50 mJ and 150 mJ to

evaporate material from crystalline Si electrodes. A continuous flow of Ar transports Si

crystallites formed, of sizes 2 - 4 nm, to the collection substrate. Reactive evaporation is also

possible by adding a suitable reactant gas. As an example, SiC nanoparticles were formed when
an arc source generated a discharge between two Si electrodes in 500 mbar of CH4, and Al2O3

was obtained from Al electrodes in a mixture of 130 mbar O2 and 420 mbar Ar (Hayashi, 1987).

A closely related technique is the exploding wire, in which the wire material is vaporized

instantaneously by a capacitor in a chamber filled with an inert gas. This method has the

disadvantage of being non-repetitive. As an example, GaAs nanoparticles were synthesized by

using a GaAs wire (Saunders et al., 1992).

2.4.7. Inert gas condensation

One of the earliest methods used to synthesize nanoparticles, is the evaporation of a

material in a cool inert gas, usually He or Ar, at low pressures conditions, of the order of 1 mbar.

It is usually called ‘inert gas evaporation’. Common vaporization methods are resistive

evaporation (Tasaki et al., 1965), laser evaporation (Chow et al., 1989) and sputtering (Hahn and

Averback, 1990). A convective flow of inert gas passes over the evaporation source and

transports the nanoparticles formed above the evaporative source via thermophoresis towards a

substrate with a liquid N2 cooled surface (Granqvist and Buhrman, 1976). A modification which

consists of a scraper and a collection funnel allows the production of relatively large quantities of

nanoparticles, which are agglomerated but do not form hard agglomerates and which can be

compacted in the apparatus itself without exposing them to air. This method was pioneered by

the group of Birringer and Gleiter (Birringer et al., 1984). Increased pressure or increased

molecular weight of the inert gas leads to an increase in the mean particle size. This so-called

Inert Gas Condensation method is already used on a commercial scale for a wide range of

materials. Also reactive condensation is possible, usually by adding O2 to the inert gas in order

to produce nanosized ceramic particles (Siegel, 1994). Another method replaces the evaporation
boat by a hot-wall tubular reactor into which an organometallic precursor in a carrier gas is

introduced. This process is known as Chemical Vapor Condensation referring to the chemical

reactions taking place as opposed to the inert gas condensation method (Kear and Strutt, 1995).

Finally, the Gas Deposition Method is also used in industry. In this method, nanoparticles are

formed by evaporation in an inert gas at atmospheric pressure and transported by a special

designed transfer pipe to the spray chamber at a pressure of about 0.3 mbar. By moving the

nozzle at the end of the transfer pipe, the particles which have a mean velocity of 300 m/s can be

deposited in required places on the substrate in the spray chamber. Using this technique writing

micron-sized patterns was demonstrated. (Oda et al., 1992).

2.5. Laser ablation of solids

Laser ablation is a technique in which a pulsed laser rapidly heats a very thin (< 100 nm)

layer of substrate material, resulting in the formation of an energetic plasma above the substrate.

This technique should be distinguished from laser vaporization, as apart from atoms and ions

also fragments of solid or liquid material are ablated from the substrate surface which vary in

size from sub-nanometric to micrometric. Therefore it cannot be considered as a pure

homogeneous nucleation process. The pulse duration and energy determines the relative amounts

of ablated atoms and particles. The nonequilibrium nature of the short-pulse (10-50 ns) laser

heating enables the synthesis of nanoparticles of materials which normally would decompose

when vaporized directly, such as most semiconductors and superconductive materials. Typically

used lasers are the Nd:YAG (532 nm) and excimer (191, 248 and 308 nm) lasers. The material

removal rate by laser ablation decreases with longer target exposure times, therefore the target is

usually rotated. When used for producing films, this technique is called pulsed laser deposition

(PLD). Here, the fine particles are not desired as they deteriorate the film quality and the
operating conditions are chosen so as to minimize particle formation (Venkatesan and Green,

1996). Yamamoto and Mazumder (1996) showed that laser ablation of NbAl3 at He pressures of

0.1 mbar did not produce any nanoparticles while an operating pressure of 1 mbar resulted in the

formation of 6 nm nanoparticles with the same stoichiometry as the substrate. Typical production

rates are in the order of micrograms per pulse with pulse frequencies of about 50 Hz, yielding

10-100 mg powder per hour. Reactive laser ablation in which a reaction of the ablated material

with the reactor gas occurs is also used. Johnston et al. (1992) ablated an Al target in an O2

atmosphere, producing Al2O3 nanoparticles.

2.6. Electrospray systems

A simple way to produce nanoparticles is to evaporate micron-sized droplets of a dilute

solution. By choosing the appropriate solute concentration, nanosized particles consisting of the

solid residue can be obtained. For instance, drying a 1 µm droplet containing a 1 ppm solution of

NaCl will yield a 10 nm NaCl particle. A serious problem here is that all the impurities present in

the liquid will concentrate in the solid residue (Rulison and Flagan, 1994). Furthermore, it is

necessary to start from small droplet sizes which are difficult to obtain in normal spray systems.

Chen and Pui et al. (1995) showed that an electrospray system operated in the cone-jet mode

could yield small droplets with a narrow size distribution. To avoid droplet explosion during

evaporation, the highly charged aerosol is first passed through a radioactive neutralizer before

the evaporation takes place. It is important here to avoid droplet explosion since that would

deteriorate the narrowness of the size distribution. Using a sucrose solution, particles as small as

4 nm were obtained. In another work (Hull et al., 1997) Ag particles with a mean size of 10 nm

were produced by electrospraying a dilute AgNO3 solution in methanol onto a grounded

substrate. A 1 mW He-Ne laser focused just below the capillary tip of the electrospray catalyzed
the reduction of the Ag+ ion. The droplets were not discharged before evaporation in this case,

so Rayleigh explosion is probable. Kim and Rye (1994) developed a special charge injection

technique in order to obtain very high charge densities. It is stated that the higher the surface

charge density of the electrospray jet is, the smaller is the size of the ejected droplets. The system

consists of a spray capillary containing a sharp needle connected to a high voltage supply. This

charge injection system stabilizes the multijet-mode, in which a large number of small droplet-

emitting jets form on the wetted capillary surface. Spraying a 10 vol.-% TEOS solution in

ethanol in a chamber filled with O2 resulted in 30-100 nm sized SiO2 particles.

2.7. Spray pyrolysis

In spray pyrolysis, a droplet containing a solute is evaporated or dissociated by a

chemical reaction. During the shrinkage of the droplet, a supersaturated solution is created, as the

amount of solute remains constant, and small particles may form inside the droplet Spray

pyrolysis normally results in micron-sized particles which often have a hollow shape. This

method is intermediate between gas-phase and liquid-phase, as the droplet are gas-carried, but

the particle formation inside the droplets is in vthe liquid phase. In some cases, nanoparticles

were obtained. Lyons et al. (1992) obtained nanocrystalline PdO and V2O5 particles by spray

pyrolysis. The droplets containing a precursor solution were decomposed at relatively low

temperatures. This method avoids grain growth and densification, while the temperature is still

high enough to fully decompose the precursors. The product consisted of 5 to 10 nm crystallites

packed together in spheres, showing the form of the originating droplet and demonstrating that

the droplets were not fragmented. This possibility was suggested theoretically by Leong (1987)

who pointed out that formation of multiple crystals in a droplet is possible when the solubility is

low, the solute mass is high or the rate of solvent evaporation is high. Kang et al.(1995) showed
that in spray pyrolysis of ultrasonically nebulized nitrate or acetate solutions the particle size can

be reduced to about 10 nm by using a low pressure system (80 mbar). The same phenomenon

was observed when zinc acetate droplets of 2 µm were generated by expanding a liquid through

a glass filter into a low pressure chamber and subsequently pyrolyzed,

Chemical Processes: There are several chemical processes for deposition of thin films such as sol-gel,

chemical bath deposition, spray pyrolysis, solution growth, electrolysis etc, among them I shall discuss

about sol-gel process as the oxide based materials generally synthesized by sol-gel process.

2.8. Sol-gel process:

It is also a simpler and cost effective process and it allows the coating over the large

area of complex shaped substrates. In sol-gel dip coating technique, the sol is prepared in

general by heating and stirring the solution with the magnetic stirrer. Then this solution is

agged for certain time and this is utilized for dip coating. In this process the cleaned substrates

are inserted into the solution containing hydrolysable organometallic compound and then

pulled out at a constant speed. The substrate is then dried and this diping-withdrowing-drying

process is repeated to obtain the desirable thickness of the film. Finally the film heated at

desire temperature to get proper phase.

For the sol-gel synthesis of II-VI semiconducting oxide materials, the formation of

inorganic polymerization (-M-O-M-) takes place as follows:

2M(OR)2 + H2O  R – M – OH + R – M – R + ROH

 R – M – O – M – R + ROH
 During annealing at high temperature, water and carbon groups are removed. The

overall generalized reaction can be written as:

nM(OR)2 + nH2O = nMO + 2nROH

where M is a metal of valence +2 and R is an alkyl group.

Different workers have been utilized different chemical processes for synthesis of

polycrystalline cadmium oxide thin films such as sol-gel spraypyrolysis, etc. Ghosh et al. have

used sol-gel process for synthesis of fluorine doped polycrystalline cadmium oxide thin films.

The films were deposited on glass and Si substrates using sol-gel dip coating process. Different

solutions were prepared by mixing cadmium acetate (99.99% Cd(COOCH3)2) and ammonium

fluoride (99.95% NH4F) with different atomic ratios of Cd : F, dissolved in a mixture of isopropyl

alcohol and double distilled water (2:1). The pH of the solution was controlled at 5 by adding

appropriate amounts of acetic acid (99.95% CH3COOH). The solution was stirred by a magnetic

stirrer and heated at a constant temperature of 80oC for a one hour. The solution was aged for

two hours. Before dip coating the glass substrates were cleaned by mild soap solution, washed

thoroughly by distilled water and then in boiled water. Finally it was degreased in alcohol

vapor. Si substrates were cleaned at first in 20% HF solution for 5 minutes and then washed in

acetone in an ultrasonic cleaner. The cleaned substrates were dipped vertically into the solution

and withdrawn very slowly at a speed of ~ 8 cm/min and dried at ~ 100 oC for 15 minutes for

quick gel formation. This process was repeated for six to seven times. Finally the coated

substrate was heated at ~ 400oC for two hours in open air; the films suddenly turn into a

yellow-brown color due to the formation of CdO.

 We have chosen the dip-coating method because of its many advantages such as easier

composition control, better homogeneity, low processing temperature, lower cost, easier

fabrication of large area films, possibility of using high purity starting materials and having an

easy coating process of large and complex shaped substrates.

Physical processes: There are several physical processes for deposition of

nanocrystalline semiconducting thin films such as vacuum evaporation, sputtering (reactive and

non-reactive forms of DC and rf-magnetron sputtering), ion beam deposition technique, pulse

laser deposition technique (PLD), molecular beam epitaxy etc, among them here I discuss about

sputtering technique for synthesis of nanocrystalline thin films.

2.9. Sputtering technique:

Sputtering is a well known and one of the most versatile technique for the deposition of

very good and high quality’s thin films. Compared with other techniques, the sputtering process

produces films with high purity and better controlled composition, provides films with greater

adhesive strength and better homoginity and permits better control of film thickness. The

sputtering process involves the creation of gas plasma (usually inert gas such as argon) by

applying voltage between the cathode and the anode. The cathode contains target and anode

contains substrate. The bombardments of a target with energetic particles (usually positive

ions), which cause some surface atoms to be ejected from the target by momentum transfer

and deposited on the substrate in the form of thin film.

Normally for polycrystalline film synthesis, the sputtering is performed at gas pressure ~

10-3 mbar with substrate temperature ~ 500 K. This would allow the adatoms on the substrate
enough mobility for growing bigger crystallites. But for nanocrystalline film synthesis the

pressure has been increased ~ 10-1 mbar to (minimize the agglomeration probability) increases

the scattering probability of the ejected target materials as the particles those eject out from

the target suffer several collisions with the gas molecules in between the electrodes.
 Matching Box RF generator

Water
outlet Water inlet

Liquid N2 inlet

Magnetron

Target

View port

Liquid N2 cooled
substrate holder

Substrate heater
Gas inlet
Gauges

Shutter

Vacuum pump

Figure 2.1. The schematic diagram of RF magnetron sputtering chamber.

The lower substrate temperature is generally used for synthesis of nanostructured

materials. This is due to the fact that at lower substrate temperature, as soon as the particles
that eject out from the target just touches to the substrate, release its thermal energy to the

substrate and hence more quickly the stability is gain than that of the substrate at higher

temperature.

Normally two modes of powering of the sputtering system are there, (a) DC sputtering

and (b) rf sputtering. In DC sputtering, the direct voltage is applied between the cathode and

the anode and this process is restricted to conducting target. In rf sputtering, which is suitable

for both conducting and insulting targets, a high frequency generator is connected between the

electrodes. For high deposition rates and low deposition temperature magnetron sputtering is

utilized.

Cadmium oxide have been synthesized by different physical process by different groups

of scientist in the world such as activated reactive evaporation technique, sputtering technique

etc.

Vacuum Systems

The vacuum system consists of a oil diffusion pump, backed by a rotary pump. An

optically dense cold trap of non-magnetic stainless steel is located between the diffusion pump

and the baffle valve, which in turn, is connected to the base plate of the sputtering chamber via

a stainless steel collar. With the above assembly, the pressure of the sputtering chamber could

be attained upto 10-6 mbar. Two Pirani gauges, one mounted in the rotary vacuum pump line

and other on the chamber, to measure roughing and backing pressure (range: 0.5 mbar to 10 -3

mbar). One Penning gauge, mounted on the chamber was used to measure fine pressure in the

sputtering chamber (range: 10-2 to 10-6 mbar). The vacuum is essential for deposition of thin
 films via physical process and some characterizations of the films such as electrical conductivity,

thermoelectric properties, etc. The schematic diagram of pumping system for vacuum coating

sputtering unit is as shown in the Figure 2.2.

Figure 2.2. Schematic diagram of pumping system of sputtering vacuum coating unit.
 Sputtering is one of the most versatile techniques generally used for the deposition of

polycrystalline thin films when device quality films are required. Compared to other deposition

techniques, the sputtering technique produces films with higher purity and better controlled

composition, provides films with greater adhesive strength and homogeneity and permits

better controlled of films thickness. The RF-magnetron sputtering technique provides some

extra facilities compared to other sputtering techniques such as it can sputter from both

conducting target as well as insulating target with enhanced rate and even at low substrate

temperature also. The lower substrate temperature is essential for preparation of

nanostructured II-VI semiconductor.

2.9.1. One example of Nanocrystalline film synthesis

The thin films of CdO have been deposited on glass and Si substrates using sol-gel dip

coating process. Cadmium acetate (99.99% Cd(COOCH3)2) has been taken as the source

cadmium and 2-methoxy ethanol and monoethanol amine have been taken as solvent and

stabilizer respectively. The solution of cadmium acetate dissolving in 2-methoxy ethanol was

stirred by a magnetic stirrer and heated at a constant temperature of 80 oC for a one hr. The

solution was aged for three hrs. Before dip coating the glass substrates were cleaned by mild

soap solution, washed thoroughly by distilled water and then in boiled water. Finally, it was

degreased in alcohol vapor. Si substrates were cleaned at first in 20% HF solution for 5 minutes
and then washed in acetone in an ultrasonic cleaner. The cleaned substrates were dipped

vertically into the solution and withdrawn very slowly at a speed of ~ 8 cm/min and dried at 60

oC for 15 minutes for quick gel formation. This process was repeated for eight to nine times.

Finally the coated substrates were annealed at desired constant temperature 200oC, 250oC,

300oC and 350oC for one hr. in open air.

For study of nanostructure by trasmission electron microscopy we prepared the samples as

follows: at first, the films (CdO nanoparticles), deposited on glass substrates annealed at

different temperature, were scratched out carefully by a sharp knife edge from some portion of

the substrates. These particles were dispersed in ethanol by ultrasonication and then a few

drop of this solution, was placed on carbon coated copper grid and it was allowed to dry out.

For different annealed temperature different carbon coated copper grids were used and the

materials on carbon coated copper grid were utilized to measure the TEM image.

In case of the sol-gel synthesis of CdO, the formation of inorganic polymerization (-Cd-O-

Cd-) may be represented as follows:

2Cd(CH3COO)2 + H2O 

CH3COO – Cd – OH + CH3COO – Cd - CH3COO + CH3COOH

 CH3COO – Cd – O – Cd - CH3COO + CH3COOH

During annealing at high temperature (~ 4000C), water and carbon groups are removed. The

overall generalized reaction can be written as:

nCd(CH3COO)2 + nH2O = nCdO + 2nCH3COOH

 Each of the productions processes have their merits and demerits. The main criterion in

the development of device quality thin films is to adopt cost-effective deposition technique,

which would yield films with predetermined properties with a reproducible manner for large-

scale production of the films in high-technology applications. The sol-gel dip coating technique

has been adopted for production of nanostructured thin films. The sol-gel processes have many

advantages such as easier composition control, better homogeneity, low processing

temperature, lower cost, easier fabrication of large area films, possibility of using high purity

starting materials and having an easy coating process of large and complex shaped substrates.

2.10. Hydrothermal synthesis

Hydrothermal synthesis includes the various techniques of crystallizing substances

from high-temperature aqueous solutions at high vapor pressures; also termed "hydrothermal

method". The term "hydrothermal" is of geologic origin.[1] Geochemists and mineralogists have

studied hydrothermal phase equilibria since the beginning of the twentieth century. George W.

Morey at the Carnegie Institution and later, Percy W. Bridgman at Harvard University did much

of the work to lay the foundations necessary to containment of reactive media in the temperature

and pressure range where most of the hydrothermal work is conducted.

Hydrothermal synthesis can be defined as a method of synthesis of single crystals that

depends on the solubility of minerals in hot water under high pressure. The crystal growth is

performed in an apparatus consisting of a steel pressure vessel called an autoclave, in which a

nutrient is supplied along with water. A temperature gradient is maintained between the opposite
ends of the growth chamber. At the hotter end the nutrient solute dissolves, while at the cooler

end it is deposited on a seed crystal, growing the desired crystal.

Advantages of the hydrothermal method over other types of crystal growth include the

ability to create crystalline phases which are not stable at the melting point. Also, materials

which have a high vapour pressure near their melting points can be grown by the hydrothermal

method. The method is also particularly suitable for the growth of large good-quality crystals

while maintaining control over their composition. Disadvantages of the method include the need

of expensive autoclaves, and the impossibility of observing the crystal as it grows if a steel tube

is used.[2] There are autoclaves made out of thick walled glass, which can be used up to 300°C

and 10 bar.[3]

A large number of compounds belonging to practically all classes have been synthesized

under hydrothermal conditions: elements, simple and complex oxides, tungstates, molybdates,

carbonates, silicates, germanates etc. Hydrothermal synthesis is commonly used to grow

synthetic quartz, gems and other single crystals with commercial value. Some of the crystals that

have been efficiently grown are emeralds, rubies, quartz, alexandrite and others. The method has

proved to be extremely efficient both in the search for new compounds with specific physical

properties and in the systematic physicochemical investigation of intricate multicomponent

systems at elevated temperatures and pressures.

2.10.1. Equipment for hydrothermal crystal growth

The crystallization vessels used are autoclaves. These are usually thick-walled steel

cylinders with a hermetic seal which must withstand high temperatures and pressures for

prolonged periods of time. Furthermore, the autoclave material must be inert with respect to
the solvent. The closure is the most important element of the autoclave. Many designs have been

developed for seals, the most famous being the Bridgman seal. In most cases, steel-corroding

solutions are used in hydrothermal experiments. To prevent corrosion of the internal cavity of the

autoclave, protective inserts are generally used. These may have the same shape as the autoclave

and fit in the internal cavity (contact-type insert), or be "floating" type inserts which occupy only

part of the autoclave interior. Inserts may be made of carbon-

free iron, copper, silver, gold, platinum, titanium, glass (or quartz), or Teflon, depending on the

temperature and solution used.

2.10.2. Temperature-difference method

This is the most extensively used method in hydrothermal synthesis and crystal growing.

Supersaturation is achieved by reducing the temperature in the crystal growth zone. The nutrient

is placed in the lower part of the autoclave filled with a specific amount of solvent. The

autoclave is heated in order to create two temperature zones. The nutrient dissolves in the hotter

zone and the saturated aqueous solution in the lower part is transported to the upper part by

convective motion of the solution. The cooler and denser solution in the upper part of the

autoclave descends while the counterflow of solution ascends. The solution becomes

supersaturated in the upper part as the result of the reduction in temperature and crystallization

sets in.

2.10.3. Temperature-reduction technique

In this technique crystallization takes place without a temperature gradient between the

growth and dissolution zones. The supersaturation is achieved by a gradual reduction in

temperature of the solution in the autoclave. The disadvantage of this technique is the difficulty
in controlling the growth process and introducing seed crystals. For these reasons, this technique

is very seldom used.

2.10.4. Metastable-phase technique

This technique is based on the difference in solubility between the phase to be grown and

that serving as the starting material. The nutrient consists of compounds that are

thermodynamically unstable under the growth conditions. The solubility of the metastable phase

exceeds that of the stable phase, and the latter crystallize due to the dissolution of the metastable

phase. This technique is usually combined with one of the other two techniques above.

2.11. Preperation of Colloidal Solutions

Lyophilic colloids readily form a sol by bringing them into contact or by warming those with the

medium due to their strong affinity for the dispersion medium. For example, Only heating with

water in enough for preparing the sols of starch, gelatin, gum arabic etc. But it is not so easy to

prepare the sols of lyophobic colloids practically as they have no affinity for the dispersion

medium. Special methods are required for the preparation of lyophobic sols. There are number of

special methods used for preparation of lyophobic sols which can broadly be divided in to the

following categories.
 Dispersion methods and

 Condensation or aggregation methods

Dispersion Methods

In dispersion methods, the bigger particles of any substance are broken down into small particles

of colloidal size. The small particles thus obtained are stabilized by adding some stabilizing

agents. Some of the dispersion methods are discussed below :

 Mechanical dispersion method: In this method, the large particles of the material whose sol

is to be prepared are broken down in a machine called colloid mill. Colloid mill consists of

two heavy steel discs separated by a little gap. The can be adjusted according to the particle

size desired. The two discs rotate at high speed (about 8000 revolutions per minute) in the

opposite direction.

A suspension of the substance in water is added into the mill. The particles present in the

suspension are grinded to form the particles of colloidal size and als get dispersed in water to

form a sol.

Finer dispersion can be obtained by adding an inert diluents which prevents the colloidal

particles to grow in size. For example, glucose is used as diluents in the preparation of sulphur

sol.
 Electrical dispersion method (Bredig’s arc method): This method is used for the

preparation of sols metals such as gold, silver, platinum etc. In this method, two electrodes of

the metals whose sol is to be prepared are immersed into the dispersion medium and an

electric arc is produced bas passing high voltage current. The dispersion medium is cooled by

surrounding it with a freezing mixture. Due the heat produced from electric arc , the metal

starts vaporizing and the vapour condense into the cold dispersion medium to form to the

particles of colloidal size on cooling.

 Ultrasonic dispersion: The sound waves of high frequency are usually called ultrasonic

waves. These waves can be produced when quartz crystal discs are connected with high

frequency generator. The application of ultrasonic waves for the preparation of colloidal

solutions was first introduced bt wood and Loomis, in 1927. Various substances like oils,

mercury, sulphides and oxides of metals can be dispersed into colloidal state easily with the

help of ultrasonic waves.

 Peptization: Peptization is the method of breaking down the freshly prepared precipitate

particles into the particles of colloidal size. This is done by adding suitable electrolytes. The

electrolyte added is called peptizing agent.

Brown coloured colloidal solution is obtained by addition of Ferric chloride solution into freshly

precipitated ferric hydroxide .This happened due to adsorption of ferric ions on the surface of

precipitate. Accumulation of positively chafed ferric ions on the surface causes repulsion

between them because of which the large precipitate particles break down into small particles of

colloidal size.
 Condensation method

Some chemical reactions may be used to aggregate smaller particles of atomic or ionic sizes to

form large particles of colloidal dimensions.The dispersed phase are fromed as insoluble reaction

product in these reactions. Here are some important reactions used forthe formation of

hydrophobic sols

 By Exchange of Solvents: If a solution of sulphur or phosphorus prepared in alcohol is poured

into water, a colloidal solution of sulphur or phosphorus is obtained due to low solubility of

sulphur or phosphorus in water. Thus, there are number of substances whose colloidal

solutions can be prepared by taking a solution of the substance in one solvent and pouring it

into another solvent in which the substance is relatively less soluble.

 By change of physical state: Colloidal solution of certain elements such as mercury and

sulphur are obtained by passing their vapours through cold water containing a stabilizer ( an

ammonium salt or a citrate).

2.11. Molecular-beam epitaxy (MBE)

Molecular-beam epitaxy (MBE) is an epitaxy method for thin-film deposition of single

crystals. The MBE process was developed in the late 1960s at Bell Telephone Laboratories by J.

R. Arthur and Alfred Y. Cho.[1][2] MBE is widely used in the manufacture of semiconductor

devices, including transistors, and it is considered one of the fundamental tools for the

development of nanotechnologies.[3] MBE is used

to fabricate diodes and MOSFETs (MOS field-effect transistors) at microwave frequencies, and

to manufacture the lasers used to read optical discs (such as CDs and DVDs).[4]
 Molecular-beam epitaxy takes place in high vacuum or ultra-high vacuum (10−8–

10−12 Torr). The most important aspect of MBE is the deposition rate (typically less than

3,000 nm per hour) that allows the films to grow epitaxially. These deposition rates require

proportionally better vacuum to achieve the same impurity levels as other deposition techniques.

The absence of carrier gases, as well as the ultra-high vacuum environment, result in the highest

achievable purity of the grown films.

In solid source MBE, elements such as gallium and arsenic, in ultra-pure form, are heated

in separate quasi-Knudsen effusion cells or electron-beam evaporators until they begin to

slowly sublime. The gaseous elements then condense on the wafer, where they may react with

each other. In the example of gallium and arsenic, single-crystal gallium arsenide is formed.

When evaporation sources such as copper or gold are used, the gaseous elements impinging on

the surface may be adsorbed (after a time window where the impinging atoms will hop around

the surface) or reflected. Atoms on the surface may also desorb. Controlling the temperature of

the source will control the rate of material impinging on the substrate surface and the

temperature of the substrate will affect the rate of hopping or desorption. The term "beam"

means that evaporated atoms do not interact with each other or vacuum-chamber gases until they

reach the wafer, due to the long mean free paths of the atoms.

During operation, reflection high-energy electron diffraction (RHEED) is often used for

monitoring the growth of the crystal layers. A computer controls shutters in front of

each furnace, allowing precise control of the thickness of each layer, down to a single layer of

atoms. Intricate structures of layers of different materials may be fabricated this way. Such

control has allowed the development of structures where the electrons can be confined in space,
giving quantum wells or even quantum dots. Such layers are now a critical part of many

modern semiconductor devices, including semiconductor lasers and light-emitting diodes.

In systems where the substrate needs to be cooled, the ultra-high vacuum environment

within the growth chamber is maintained by a system of cryopumps and cryopanels, chilled

using liquid nitrogen or cold nitrogen gas to a temperature close to 77 kelvins (−196 degree

Celsius). Cold surfaces act as a sink for impurities in the vacuum, so vacuum levels need to be

several orders of magnitude better to deposit films under these conditions. In other systems, the

wafers on which the crystals are grown may be mounted on a rotating platter, which can be

heated to several hundred degrees Celsius during operation.

Molecular-beam epitaxy is also used for the deposition of some types of organic

semiconductors. In this case, molecules, rather than atoms, are evaporated and deposited onto the

wafer. Other variations include gas-source MBE, which resembles chemical vapor deposition.

MBE systems can also be modified according to need. Oxygen sources, for example, can be

incorporated for depositing oxide materials for advanced electronic, magnetic and optical

applications, as well as for fundamental research.

One of the most accomplished achievements of molecular-beam epitaxy is the nano-

structures that permitted the formation of atomically flat and abrupt hetero-interfaces. Such

structures have played an unprecedented role in expanding the knowledge of physics and

electronics.[5] Most recently the construction of nanowires and quantum structures built within

them that allow information processing and the possible integration with on-chip applications for

quantum communication and computing.[6] These heterostructure nanowire lasers are only
possible to build using advance MBE techniques, allowing monolithical integration on

silicon[7] and picosecond signal processing.[8]

The Asaro–Tiller–Grinfeld (ATG) instability, also known as the Grinfeld instability, is an

elastic instability often encountered during molecular-beam epitaxy. If there is a mismatch

between the lattice sizes of the growing film and the supporting crystal, elastic energy will be

accumulated in the growing film. At some critical height, the free energy of the film can be

lowered if the film breaks into isolated islands, where the tension can be relaxed laterally. The

critical height depends on the Young's modulus, mismatch size, and surface tension.
Chapter III

CHARACTERIZATION:

X-Ray Diffraction. Optical Microscopy. Scanning Electron Microscopy. Transmission

Electron Microscopy. Atomic Force Microscopy, Scanning Tunneling Microscopy.
3. Introducion

Numerous investigations have been made for different properties of the thin films in

order to understand the phenomena involved in it. Transparent conducting oxides exhibit novel

properties such as high electrical conductivity, high optical transparency, etc. Such types of

unique properties of the materials are suitable for varieties of applications. The different

properties of the materials such as structural properties, electrical transport properties and

optical properties have been reviewed by different workers. The optical properties of the

conducting transparent thin films strongly depend on the structure, level of impurity and

growth technique.

As far as characterizations are concerned, XRD analyses of the target as well as thin films

deposited by the all methods have been done to observe the proper phase formation of the

films. Also some important data such as strain and particle size of the films have been derived

from the XRD data. FT-IR spectrophotometric analyses of the films have been done to obtain

the different bonding information in the thin films. EDX measurements have been done for

compositional analysis of the films. UV-Vis-NIR spectrophotometric analyses of the films have

been performed and different important optical parameters as well as bandgap information of

the films have been obtained there from.

3.1. X-Ray Diffraction

X-ray diffraction techniques are used for the identification of crystalline phases of various

materials and the quantitative phase analysis subsequent to the identification. X-ray diffraction

techniques are superior in elucidating the three-dimensional atomic structure of crystalline solids.
The properties and functions of materials largely depend on the crystal structures. X-ray

diffraction techniques have, therefore, been widely used as an indispensable means in materials

research, development and production.

The Bragg equation, nλ = 2dsinθ is one of the keystones in understanding X-ray diffraction.

In this equation, n is an integer, λ is the characteristic wavelength of the X-rays impinging on

the crystallize sample, d is the interplanar spacing between rows of atoms, and θ is the angle of

the X-ray beam with respect to these planes. When this equation is satisfied, X-rays scattered by

the atoms in the plane of a periodic structure are in phase and diffraction occurs in the direction

defined by the angle θ. In the simplest instance, an X-ray diffraction experiment consists of a

set of diffracted intensities and the angles at which they are observed. This diffraction pattern can

be thought of as a chemical fingerprint, and chemical identification can be performed by

comparing this diffraction pattern to a database of known patterns.

After the films were deposited, they were characterized by different techniques with different

instruments. Structural characterization was done by studying X-ray diffraction (XRD, Bruker

D-8 Advance) and scanning electron microscopy (SEM, JEOL-5200).

The information on strain () and particle size (L) of the deposited films has been

obtained from the following relation by Quadri et al.:

 cos 1  sin 
  
 L 
where is the full width at half maximum (FWHM) of the diffraction peak. From the plot of

cosvs. singraph,the slope of the line gives the strain value and the intercept of

the line on cos-axis gave the particle (nm).

3.2. Scanning Electron Microscopy

Scanning Electron Microscopy is a type of electron microscope that produces images of a

sample by scanning the surface with a focused beam of electrons. The electrons interact

with atoms in the sample, producing various signals that contain information about the

surface topography and composition of the sample. The electron beam is scanned in a raster

scan pattern, and the position of the beam is combined with the intensity of the detected signal to

produce an image. In the most common SEM mode, secondary electrons emitted by atoms

excited by the electron beam are detected using a secondary electron detector (Everhart-Thornley

detector). The number of secondary electrons that can be detected, and thus the signal intensity,

depends, among other things, on specimen topography. SEM can achieve resolution better than 1

nanometer.

Principles and Capacities

The signals used by a scanning electron microscope to produce an image result from

interactions of the electron beam with atoms at various depths within the sample. Various types

of signals are produced including secondary electrons (SE), reflected or back-scattered

electrons (BSE), characteristic X-rays and light (cathodoluminescence) (CL), absorbed current

(specimen current) and transmitted electrons. Secondary electron detectors are standard
equipment in all SEMs, but it is rare for a single machine to have detectors for all other possible

signals.

In secondary electron imaging (SEI), the secondary electrons are emitted from very close

to the specimen surface. Consequently, SEI can produce very high-resolution images of a sample

surface, revealing details less than 1 nm in size. Back-scattered electrons (BSE) are beam

electrons that are reflected from the sample by elastic scattering. They emerge from deeper

locations within the specimen and, consequently, the resolution of BSE images is less than SE

images. However, BSE are often used in analytical SEM, along with the spectra made from the

characteristic X-rays, because the intensity of the BSE signal is strongly related to the atomic

number (Z) of the specimen. BSE images can provide information about the distribution, but not

the identity, of different elements in the sample. In samples predominantly composed of light

elements, such as biological specimens, BSE imaging can image colloidal gold immuno-labels of

5 or 10 nm diameter, which would otherwise be difficult or impossible to detect in secondary

electron images.[13] Characteristic X-rays are emitted when the electron beam removes an inner

shell electron from the sample, causing a higher-energy electron to fill the shell and release

energy. The energy or wavelength of these characteristic X-rays can be measured by Energy-

dispersive X-ray spectroscopy or Wavelength-dispersive X-ray spectroscopy and used to identify

and measure the abundance of elements in the sample and map their distribution.

Due to the very narrow electron beam, SEM micrographs have a large depth of

field yielding a characteristic three-dimensional appearance useful for understanding the surface

structure of a sample.[14] This is exemplified by the micrograph of pollen shown above. A wide

range of magnifications is possible, from about 10 times (about equivalent to that of a powerful
hand-lens) to more than 500,000 times, about 250 times the magnification limit of the best light

microscopes.

3.3. Transmission Electron Microscopy (TEM)

The transmission electron microscope is a very powerful tool for material science. A high

energy beam of electrons is shone through a very thin sample, and the interactions between the

electrons and the atoms can be used to observe features such as the crystal structure and features

in the structure like dislocations and grain boundaries. Chemical analysis can also be performed.

TEM can be used to study the growth of layers, their composition and defects in semiconductors.

High resolution can be used to analyze the quality, shape, size and density of quantum wells,

wires and dots.

The TEM operates on the same basic principles as the light microscope but uses electrons

instead of light. Because the wavelength of electrons is much smaller than that of light, the

optimal resolution attainable for TEM images is many orders of magnitude better than that from

a light microscope. Thus, TEMs can reveal the finest details of internal structure - in some cases

as small as individual atoms.

Imaging

The beam of electrons from the electron gun is focused into a small, thin, coherent beam

by the use of the condenser lens. This beam is restricted by the condenser aperture, which

excludes high angle electrons. The beam then strikes the specimen and parts of it are transmitted

depending upon the thickness and electron transparency of the specimen. This transmitted

portion is focused by the objective lens into an image on phosphor screen or charge coupled

device (CCD) camera. Optional objective apertures can be used to enhance the contrast by

blocking out high-angle diffracted electrons. The image then passed down the column through

the intermediate and projector lenses, is enlarged all the way.

The image strikes the phosphor screen and light is generated, allowing the user to see the

image. The darker areas of the image represent those areas of the sample that fewer electrons are
transmitted through while the lighter areas of the image represent those areas of the sample that

more electrons were transmitted through.

Diffraction

Fig2. shows a simple sketch of the path of a beam of electrons in a TEM from just above

the specimen and down the column to the phosphor screen. As the electrons pass through the

sample, they are scattered by the electrostatic potential set up by the constituent elements in the

specimen. After passing through the specimen they pass through the electromagnetic objective

lens which focuses all the electrons scattered from one point of the specimen into one point in

the image plane. Also, shown in fig 2 is a dotted line where the electrons scattered in the same

direction by the sample are collected into a single point. This is the back focal plane of the

objective lens and is where the diffraction pattern is formed.

3.4. Atomic Force Microscopy

Since the introduction of the Nobel Prize-winning scanning tunneling microscope (STM) and

then the invention of the atomic force microscopy (AFM) from the landmark publication by

Binnig, Quate, and Gerber, the field of scanning probe microscopy has exploded well beyond

using interatomic forces to image topography on the nanometer scale. The ability to measure

intermolecular forces and see atoms is scientifically tantalizing.

Topography imaging alone does not always provide the answers that researchers need and the

surface topology often does not correlate to the material properties. For these reasons, advanced

imaging modes have been developed to provide quantitative data on a variety of surfaces. Now,

many material properties can be determined with AFM techniques, including friction, electrical
forces, capacitance, magnetic forces, conductivity, viscoelasticity, surface potential, and

resistance.

The atomic force microscope (AFM) was developed to overcome a basic drawback with

STM – it can only image conducting or semiconducting surfaces. The AFM has the advantage of

imaging almost any type of surface, including polymers, ceramics, composites, glass, and

biological samples.

Binnig, Quate, and Gerber invented the AFM in 1985. Their original AFM consisted of a

diamond shard attached to a strip of gold foil. The diamond tip contacted the surface directly,

with the interatomic van der Waals forces providing the interaction mechanism. Detection of the

cantilever’s vertical movement was done with a second tip – an STM placed above the

cantilever.

How an Atomic Force Microscope works

Analogous to how an Scanning Tunneling Microscope works, a sharp tip is raster-

scanned over a surface using a feedback loop to adjust parameters needed to image a surface.

Unlike Scanning Tunneling Microscopes, the Atomic Force Microscope does not need a

conducting sample. Instead of using the quantum mechanical effect of tunneling, atomic forces

are used to map the tip-sample interaction.

Often referred to as scanning probe microscopy (SPM), there are Atomic Force

Microscopy techniques for almost any measurable force interaction – van der Waals, electrical,

magnetic, thermal. For some of the more specialized techniques, modified tips and software

adjustments are needed.

In addition to Angstrom-level positioning and feedback loop control, there are 2 components

typically included in Atomic Force Microscopy: Deflection and Force Measurement.

3.5. Scanning Tunneling Microscopy

The development of the family of scanning probe microscopes started with the original

invention of the STM in 1981. Gerd Binnig and Heinrich Rohrer developed the first working

STM while working at IBM Zurich Research Laboratories in Switzerland. This instrument would

later win Binnig and Rohrer the Nobel prize in physics in 1986.

3.5.1. The Quantum Corral

The STM image below shows the direction of standing-wave patterns in the local density of

states of the Cu(111) surface. These spatial oscillations are quantum-mechanical interference

patterns caused by scattering of the two-dimensional electron gas off the Fe atoms and point

defects.

3.5.2. How an STM Works

First, a voltage bias is applied and the tip is brought close to the sample by coarse

sample-to-tip control, which is turned off when the tip and sample are sufficiently close. At close

range, fine control of the tip in all three dimensions when near the sample is
typically piezoelectric, maintaining tip-sample separation W typically in the 4-7 Å (0.4-0.7 nm)

range, which is the equilibrium position between attractive (3<W<10Å) and repulsive (W<3Å)

interactions.[4] In this situation, the voltage bias will cause electrons to tunnel between the tip and

sample, creating a current that can be measured. Once tunneling is established, the tip's bias and

position with respect to the sample can be varied (with the details of this variation depending on

the experiment) and data are obtained from the resulting changes in current.

If the tip is moved across the sample in the x-y plane, the changes in surface height and

density of states causes changes in current. These changes are mapped in images. This change in

current with respect to position can be measured itself, or the height, z, of the tip corresponding

to a constant current can be measured.[4] These two modes are called constant height mode and

constant current mode, respectively. In constant current mode, feedback electronics adjust the

height by a voltage to the piezoelectric height control mechanism.[7] This leads to a height

variation and thus the image comes from the tip topography across the sample and gives a

constant charge density surface; this means contrast on the image is due to variations in charge

density.[8] In constant height mode, the voltage and height are both held constant while the

current changes to keep the voltage from changing; this leads to an image made of current

changes over the surface, which can be related to charge density.[8] The benefit to using a

constant height mode is that it is faster, as the piezoelectric movements require more time to

register the height change in constant current mode than the current change in constant height

mode.[8] All images produced by STM are grayscale, with color optionally added in post-

processing in order to visually emphasize important features.

In addition to scanning across the sample, information on the electronic structure at a

given location in the sample can be obtained by sweeping voltage and measuring current at a
specific location.[3] This type of measurement is called scanning tunneling spectroscopy (STS)

and typically results in a plot of the local density of states as a function of energy within the

sample. The advantage of STM over other measurements of the density of states lies in its ability

to make extremely local measurements: for example, the density of states at an impurity site can

be compared to the density of states far from impurities.[9]

Framerates of at least 25 Hz enable so called video-rate STM.[10][11] Framerates up to

80 Hz are possible with fully working feedback that adjusts the height of the tip.[12] Due to the

line-by-line scanning motion, a proper comparison on the speed requires not only the framerate,

but also the number of pixels in an image: with a framerate of 10 Hz and 100x100 pixels the tip

moves with a line frequency of 1 kHz, whereas it moves with only with 500 Hz, when measuring

with a faster framerate of 50 Hz but only 10x10 pixels. Video-rate STM can be used to scan

surface diffusion.[13]

The scanning tunneling microscope (STM) works by scanning a very sharp metal wire tip over a

surface. By bringing the tip very close to the surface, and by applying an electrical voltage to the

tip or sample, we can image the surface at an extremely small scale – down to resolving

individual atoms.
The STM is based on several principles. One is the quantum mechanical effect of tunneling.

It is this effect that allows us to “see” the surface. Another principle is the piezoelectric

effect. It is this effect that allows us to precisely scan the tip with angstrom-level control.

Lastly, a feedback loop is required, which monitors the tunneling current and coordinates the

current and the positioning of the tip. This is shown schematically below where the tunneling

is from tip to surface with the tip rastering with piezoelectric positioning, with the feedback

loop maintaining a current setpoint to generate a 3D image of the electronic topography:

2.5.3. Tunneling

Tunneling is a quantum mechanical effect. A tunneling current occurs when electrons

move through a barrier that they classically shouldn’t be able to move through. In classical

terms, if you don’t have enough energy to move “over” a barrier, you won’t. However, in the

quantum mechanical world, electrons have wavelike properties. These waves don’t end abruptly

at a wall or barrier, but taper off quickly. If the barrier is thin enough, the probability function

may extend into the next region, through the barrier! Because of the small probability of an

electron being on the other side of the barrier, given enough electrons, some will indeed move

through and appear on the other side. When an electron moves through the barrier in this fashion,

it is called tunneling.

Quantum mechanics tells us that electrons have both wave and particle-like properties.

Tunneling is an effect of the wavelike nature.

The top image shows us that when an electron (the wave) hits a barrier, the wave doesn’t

abruptly end, but tapers off very quickly – exponentially. For a thick barrier, the wave doesn’t

get past.

The bottom image shows the scenario if the barrier is quite thin (about a nanometer). Part of the

wave does get through and therefore some electrons may appear on the other side of the barrier.

Because of the sharp decay of the probability function through the barrier, the number of

electrons that will actually tunnel is very dependent upon the thickness of the barrier. The current

through the barrier drops off exponentially with the barrier thickness.

To extend this description to the STM: The starting point of the electron is either the tip or

sample, depending on the setup of the instrument. The barrier is the gap (air, vacuum, liquid),

and the second region is the other side, i.e. tip or sample, depending on the experimental setup.

By monitoring the current through the gap, we have very good control of the tip-sample distance.

2.5.4. Piezoelectric Effect

The piezoelectric effect was discovered by Pierre Curie in 1880. The effect is created by

squeezing the sides of certain crystals, such as quartz or barium titanate. The result is the creation

of opposite charges on the sides. The effect can be reversed as well; by applying a voltage across

a piezoelectric crystal, it will elongate or compress.

These materials are used to scan the tip in an scanning tunneling microscopy (STM) and most

other scanning probe techniques. A typical piezoelectric material used in scanning probe

microscopy is PZT (lead zirconium titanate).

Feedback Loop

Electronics are needed to measure the current, scan the tip, and translate this information into a

form that we can use for STM imaging. A feedback loop constantly monitors the tunneling

current and makes adjustments to the tip to maintain a constant tunneling current. These

adjustments are recorded by the computer and presented as an image in the STM software. Such

a setup is called a constant current image.

In addition, for very flat surfaces, the feedback loop can be turned off and only the current is

displayed. This is a constant height image.

References:

1. C. Julian Chen (1993). Introduction to Scanning Tunneling Microscopy (PDF). Oxford

University Press. ISBN 978-0-19-507150-4.

2. ^ SPECS. "STM 150 Aarhus - High Stability Temperature Control" (PDF). specs.de.

Retrieved 23 February 2017.

3. ^ "STM References - Annotated Links for Scanning Tunneling Microscope Amateurs".

Retrieved July 13, 2012.

4. ^ Jump up to:a b c K. Oura; V. G. Lifshits; A. A. Saranin; A. V. Zotov & M. Katayama

(2003). Surface science: an introduction. Berlin: Springer-Verlag. ISBN 978-3-540-

00545-2.
5. ^ Jump up to:a b c d D. A. Bonnell & B. D. Huey (2001). "Basic principles of scanning

probe microscopy". In D. A. Bonnell (ed.). Scanning probe microscopy and

spectroscopy: Theory, techniques, and applications (2 ed.). New York: Wiley-

VCH. ISBN 978-0-471-24824-8.

6. ^ Pan, S. H.; Hudson, EW; Lang, KM; Eisaki, H; Uchida, S; Davis, JC (2000). "Imaging

the effects of individual zinc impurity atoms on superconductivity in

Bi2Sr2CaCu2O8+delta". Nature. 403 (6771): 746–750. arXiv:cond-

mat/9909365. Bibcode:2000Natur.403..746P. doi:10.1038/35001534. PMID 10693798.

7. ^ G. Schitter; M. J. Rost (2008). "Scanning probe microscopy at video-rate". Materials

Today. 11 (special issue): 40–48. doi:10.1016/S1369-7021(09)70006-9. ISSN 1369-

7021. Archived from the original (PDF) on 2009-09-09.

8. ^ R. V. Lapshin; O. V. Obyedkov (1993). "Fast-acting piezoactuator and digital feedback

loop for scanning tunneling microscopes" (PDF). Review of Scientific

Instruments. 64(10): 2883–2887. Bibcode:1993RScI...64.2883L. doi:10.1063/1.1144377.

9. ^ M. J. Rost; et al. (2005). "Scanning probe microscopes go video rate and

beyond" (PDF). Review of Scientific Instruments. 76 (5): 053710–053710–

9. Bibcode:2005RScI...76e3710R. doi:10.1063/1.1915288. hdl:1887/61253. ISSN 1369-

7021.

10. ^ B. S. Swartzentruber (1996). "Direct measurement of surface diffusion using atom-

tracking scanning tunneling microscopy". Physical Review Letters. 76 (3): 459–

462. Bibcode:1996PhRvL..76..459S
Chapter IV

OPTICAL PROPERTIES:

Coulomb interaction in nanostructures. Concept of dielectric constant for nanostructures and

charging of nanostructure.Quasi-particles and excitons. Excitons in direct and indirect band gap
semiconductor nanocrystals. Quantitative treatment of quasi-particles and excitons, charging
effects. Radiative processes: General formalization-absorption, emission and luminescence.
Optical properties of heterostrctures and nanostructures.
4.1. Coulomb interaction in nanostructures

Interaction processes are of great importance for the understanding of the electronic

transport properties of quantum coherent samples, although the conditions under which such a

system can be considered as coherent depend strongly. on the absence of phase-breaking

Scattering. Among the many possibilities. electron-phonon (e-p) and electron-electron (e-e)

interaction are most important [l]. In this contribution we discuss three aspects which

demonstrate some most striking features in connection with electron transport in submicrometre

structures. First, we consider the interaction of acoustic phonons with the electrons in a quasi-

one-dimensional quantum wire. We’will demonstrate that it is only above a certain critical Fermi

velocity that the phonons can influence the electron states significantly [2]. As a consequence,

we predict a characteristic temperature dependence of the plateaus in the linear conductance as a

function of a magnetic field which should he experimentally observable. The Coulomb

interaction between the electrons in a system that contains a quantum dot leads to rather sharp

and regular resonance-like peaks in the linear conductance [3]. When the mean distance between

the electrons in the dot is comparable to the Bohr radius (of the order of 10 nm for AlGaAs based

heterostructures) the excitation spectrum of the interacting electrons shows fine structure which

is related to the formation of a localized charge distribution, a Wigner molecule [4]. We show

that the excitation spectrum can be understood in terms of vibrational and tunnelling modes [SI.

Nonlinear transport properties of interacting electrons in a quantum dot that is coupled to semi-

infinite leads yield detailed information about the excitation spectrum. Using a master equation

we present an investigation which includes also the spin degrees of freedom of the electrons [6,

71. We demonstrate that correlations between the electrons lead to novel eRects in the current.
Negative direrential resistances related to spin selection rulesare predicted in accordance with

recent experiments [S, 91. Furthermore, asymmetric conductance peaks occur due to

asymmetries in the coupling.

Introduction Electron-electron (e-e) interaction becomes fundamentally important in one-

dimensional structures. The interaction of 1D electrons turns out to be so significant that the

Fermi liquid concept breaks down. More adequate becomes a strongly correlated state known as

Luttinger liquid (LL) with boson-like excitations [1]. But there are important problems in

application of this approach to actual quantum wire structures. First, the commonly used LL

model treats the e-e interaction as a short-range one, though in reality the Coulomb interaction is

essentially nonlocal. Second, the conductance of mesoscopic quantum wire structure is

substantially determined by the wire contacts with leads, so the interaction of quantum wire

electrons with leads is to be taken into consideration. Third, when applied voltage is compared

with the Fermi energy, the balance of electron flows through the wire breaks down giving rise to

a charging of the wire. This paper aims to examine these problems and investigate phase

coherent transport of electrons in a real situation of mesoscopic quantum wire structures with

leads. Electron-electron interaction potential Mesoscopic structure under consideration consists

of a quantum wire coupled to two bulky (2D or 3D) highly-conducting regions which serve as

leads. The electron in the wire interacts with other ones both directly and via the surface charges

which are induced by other electrons on the leads. The actual form of the e-e interaction potential

U(x, x') was obtained upon solving the Poisson's equation for electric potential generated by the

charges localized inside the quantum wire with account of the highly conducting electrodes as

equipotential surfaces. The potential U (x, x') decreases as

4.2. Concept of dielectric constant for nanosized systems

The screening properties of dielectric nanocrystals are analyzed. General arguments

confirmed by detailed numerical calculations are presented. It is shown how macroscopic

components of the electric field can still be defined for sizes larger than a few Fermi wavelengths

and can still be obtained from the bulk dielectric function. The decrease of the average dielectric

response with decreasing size is found to be due to the breaking of polarizable bonds at the

surface and is not due to the opening of the band gap induced by the confinement.

Dielectric materials with high dielectric constant, low loss and small temperature

coefficient of resonant frequency are used as frequency stabilising elements in microwave

integrated circuits.' Nanophase dielectric materials are now used to make various components in

microwave circuits. In the case of nanophase materials the dielectric properties change with

particle size. The use of nanophase materials definitely improve the quality with size reduction in

electronic components. Dielectric materials are characterised by their dielectric parameters such

as dielectric constant, electrical conductivity and polarisation. These parameters change with

frequency, temperature and particle size. Nano crystalline M Al2O4 [M = Mg, Sr, Nil has wide

applications in industry, defence and scientific fields

4.3. Concept of Quasiparticles

In the beginning, it sounded interesting to treat excitations as particles. But let‘s think

about what matter is. According to Einstein’s theory of relativity, we know that matter and

energy are essentially the same. The matter can be converted into energy, as in fission and fusion

reactors, or else, energy can be converted into matter.

 The introduction of this concept has considerably simplified the methods for describing

the variety of processes in many particle systems with great interaction. The idea of

quasiparticles has reduced the complex dynamics of systems composed of strongly interacting

particles to simpler dynamic systems.

Quasiparticle, in physics, a disturbance, in a medium, that behaves as a particle and that

may conveniently be regarded as one. A rudimentary analogy is that of a bubble in a glass of

beer: the bubble is not really an independent object but a phenomenon, the displacement of a

volume of beer by carbon dioxide gas, but, because of the characteristics of the surface

of liquid in contact with the gas, the bubble retains a certain identity as it rises and floats. It, like

a quasiparticle, carries properties characteristic of objects, such as size, shape, energy, and

momentum. Two bubbles can bounce off each other; quasiparticles, too, undergo collisions.

Some specific quasiparticles are the exciton, phonon, magnon, and polaron (qq.v.).

Quasiparticles are studied in connection with solid-state physics and nuclear physics because

they play an important role in determining the properties of matter. There is reason to suspect,

however, that all particles may actually be disturbances in some underlying medium and, hence,

are themselves quasiparticles.

4.3.1. Exciton

Exciton, the combination of an electron and a positive hole (an empty electron state in a

valence band), which is free to move through a nonmetallic crystal as a unit.

Because the electron and the positive hole have equal but opposite electrical charges, the exciton

as a whole has no net electrical charge (though it transports energy). This makes excitons

difficult to detect, but detection is possible by indirect means.

 When an electron in an exciton recombines with a positive hole, the original atom is

restored, and the exciton vanishes. The energy of the exciton may be converted into light when

this happens, or it may be transferred to an electron of a neighbouring atom in the solid. If the

energy is transferred to a neighbouring electron, a new exciton is produced as this electron is

forced away from its atom.

The Concept of Exciton

The absorption of photon by an interband transition in a semiconductor or insulator create

an electron in the conduction band and hole in the valence band. This oppositely charged

particles attract each other though Coulomb interaction, and there may be the probability of the

formation of neutral electron-hole pair called an Exciton.

It can affect essentially only the motion in the remaining unrestricted degrees of freedom.

Thus, the problem of an exciton as a bound state of electron and hole due to Coulomb interaction

becomes low D=3-I dimensional. Here I is the number of freedom degrees in which the free

motion of electrons and holes is confined to intervals small compared to the exciton radius and D

the effective dimensionality of the exciton.

4.3.2. Phonon,

Phonon, in condensed-matter physics, a unit of vibrational energy that arises from

oscillating atoms within a crystal. Any solid crystal, such as ordinary table salt (sodium

chloride), consists of atoms bound into a specific repeating three-dimensional spatial pattern

called a lattice. Because the atoms behave as if they are connected by tiny springs, their

own thermal energy or outside forces make the lattice vibrate. This generates mechanical waves

that carry heat and sound through the material. A packet of these waves can travel throughout the

crystal with a definite energy and momentum, so in quantum mechanical terms the waves can be

treated as a particle, called a phonon. A phonon is a definite discrete unit or quantum of

vibrational mechanical energy, just as a photon is a quantum of electromagnetic or light energy.

Phonons and electrons are the two main types of elementary particles or excitations in solids.

Whereas electrons are responsible for the electrical properties of materials, phonons determine

such things as the speed of sound within a material and how much heat it takes to change

its temperature.

In addition to their importance in the thermal and acoustic properties, phonons are essential in

the phenomenon of superconductivity—a process in which certain metals such

as lead and aluminum lose all their electrical resistance at temperatures near absolute

zero (−273.15 °C; −459.67 °F). Ordinarily, electrons collide with impurities as they move

through a metal, which results in a frictional loss of energy. In superconducting metals at

sufficiently low temperatures, however, electrons—which ordinarily repel each other—slightly

attract each other through the intermediate effect of phonons. The result is that the electrons

move through the material as a coherent group and no longer lose energy through individual
collisions. Once this superconducting state has been achieved, any initial flow of electrical

current will persist indefinitely.

4.3.3. Magnon

Magnon, small quantity of energy corresponding to a specific decrease

in magnetic strength that travels as a unit through a magnetic substance.

In a magnetic substance, such as iron, each atom acts as a small individual magnet. These atomic

magnets tend to point in the same direction, so that their magnetic fields reinforce each other.

When the direction of one atomic magnet is reversed, the total magnetic strength of the group is

decreased. A definite amount of energy is required to reverse such a magnet. This energy,

involving the decrease in magnetic strength of the group of atoms, constitutes a magnon.

According to the laws of quantum mechanics, the reversal of a single atomic magnet is

equivalent to a partial reversal of all the atomic magnets in a group. This partial reversal spreads

through the solid as a wave of discrete energy transferal. This wave is called a spin wave,

because the magnetism of each atom is produced by the spin of unpaired electrons in its

structure. Thus, a magnon is a quantized spin wave.

As the temperature of a magnetic substance is increased, its magnetic strength decreases,

corresponding to the presence of a large number of magnons.

4.3.4. Polaron

Polaron is a quasi particle used in condensed matter to describe the interaction of electron

with atom in solids. In fact it is self trapped electron which moves from one place to another by

lattice distortion associated with it. The mobility of polaron is decreased and effective mass is

increased as compared to electron. It requires thermal energy in addition to electric field to move
as hopping is required for conduction to take place. Conductivity in this process is low and

increases with temperature. This concept has been used in amorphous semiconductors also. The

magnitude of conductivity is material sensitive. In ceramic samples also conductivity will

depend on the material.

One common example of a quasiparticle is the polaron. When a charge carrier (an

electron or hole) is placed into a solid, the surrounding ions can interact with it (e.g., positive

ions will be slightly attracted to a negatively charged carrier). The ions can adjust their positions

slightly, balancing their interactions with the charge carrier and the forces that hold the ions in

their regular places. This adjustment of positions leads to a polarization locally centered on the

charge carrier. The combo of the carrier + the surrounding polarization is a polaron. There are

"large" and "small" polarons, defined by whether or not the polarization cloud is much larger

than the atomic spacing in the material. Polarons are a useful way of thinking about carriers in

ionic crystals, materials with "soft" vibrational modes (such as the manganites), and organic

semiconductors (very squishy, deformable systems held together by van der Waals rather than

covalent bonding).

Not content to let the general relativity fans have all the fun, I can describe this with a

ball-rolling-on-a-rubber-sheet analogy. The ball is the charge carrier; the deformation of the

rubber sheet is the polarization "cloud". Consider tilting the rubber sheet - this is analogous to

applying an electric field to the material. The ball will roll in response to the tilt, but it will be

slowed down compared to how it would roll on a hard tilted surface, since it has to put energy

into deforming the sheet. In real materials, this shows up as a correction to the effective mass of

the charge carrier. All other things being equal, polarons are heavy compared to bare

quasiparticles.
 We can carry this analogy further. Suppose we have two balls on the rubber sheet. In this

classical picture, if the balls are so close together that their sheet deformations touch, the balls

will be attracted together and end up in one deformation, held apart by their mutual hard-core

repulsion. This is a crude analogy for bipolaron formation, which does happen in real materials.

(Though, in real bipolarons the (purely quantum mechanical) spins of the individual polarons are

important to stabilizing the bipolaron. The spins form a singlet....) Furthermore, suppose the

rubber sheet takes some time to respond to the balls, and takes some time to restore itself to its

undeformed state once a ball passes by. You can picture a ball rolling in some direction, leaving

behind itself a little groove in the sheet that "fills in" at some rate. This would lower the energy

of some other ball if that other ball were traveling in, say, the exact opposite direction of the first

ball. This is a very crude way of thinking about the attractive pairing interaction between

electrons in low temperature superconductors.

Finally, suppose the rubber sheet is really stretchy. A ball dropped on the sheet will pull

the sheet down so far that it'll look like a little punching bag. Now if you try to tilt the sheet, the

sheet will have stretched so tightly that the ball won't want to roll at all. Instead, the little

punching bag will hang there at an angle relative to the sheet. Something analogous to this can

happen in real materials, too - polarons can self-trap. That is, the charge carrier deforms the local

environment so much that it basically digs itself such a deep potential well that it can't move

anymore. Chemists have their own name for this, by the way. A molecule that deforms to self-

trap an extra electron is a radical anion, and a molecule that deforms to self-trap a hole is

a radical cation.
4.3.5. Differences Between Quasiparticles and Elementary Particles

The quasiparticles and the usual elementary particles have both similarities and key

differences. Like normal particles, quasiparticles can be confined in space and maintain their

localization in motion; they can interact with both particles and other quasiparticles. In contrast,

quasiparticles cannot exist outside of a medium, whose elementary excitations are essential for

their existence.

Quasiparticles are studied in connection with modern solid-state physics and nuclear

physics because they play a significant role in determining the properties of matter. However,

that all particles may really be disturbances in some original medium.

4.4. Direct band gap and indirect band gap

In semiconductor physics, the band gap of a semiconductor can be of two basic types,

a direct band gap or an indirect band gap. The minimal-energy state in the conduction

band and the maximal-energy state in the valence band are each characterized by a certain crystal

momentum (k-vector) in the Brillouin zone. If the k-vectors are different, the material has an

"indirect gap". The band gap is called "direct" if the crystal momentum of electrons and holes is

the same in both the conduction band and the valence band; an electron can directly emit a

photon. In an "indirect" gap, a photon cannot be emitted because the electron must pass through

an intermediate state and transfer momentum to the crystal lattice.

 Examples of direct bandgap materials include amorphous silicon and some III-V

materials such as InAs, GaAs. Indirect bandgap materials include crystalline silicon and Ge.

Some III-V materials are indirect bandgap as well, for example AlSb.

Figure 1.1 Energy level diagram of (a) direct and (b) indirect band gap
semiconductors.
 4.5. Electronic and Optical Properties of Semiconductor Nanoparticles

In the case of semiconductor nanocrystals, the effect of particle size on the

optical properties is interesting. In order to understand the size dependent optical and
electronic properties of semiconductor nanoparticles, it is important to know the physics
behind what is happening at the nano level. The important parameters of the semiconducting
nanoparticles are discussed in the following sections.

When an electron is excited from the valence band to conduction band, an electron-hole pair
is created. This bound state electron-hole pair is called exciton and it requires a minimum
energy to excite it. Changes in the band gap due to particles size, leads to the corresponding
changes in the properties of the material.

Table1.1 Band gap and exciton Bohr radius of some common semiconductors

Semiconductors Band gap [Eg (eV)] Exciton Bohr radius [aB nm)]

Si 1.12 4.3

PbS 0.41 20
PbSe 0.26 46
CdS 2.58 2.5
CdSe 1.84 5.5
ZnO 3.37 2.34
SnS 1.3 7
GaAs 1.43 14

4.6. LMINESCENCE
Luminescence is the process of emission of electromagnetic radiation from a material upon

excitation. Based upon the means of excitation there are various types of luminescence like:

(a) Photoluminescence produced by absorption of light or photons,

(b) radioluminescence produced by the impact of higher energy particles from cosmic rays or

radioactive matter, high energy particles from accelerators etc.,

(c) electroluminescence produced by the application of an electric field,

(d) mechano or triboluminescence produced by the application of mechanical force,

(e) cathodoluminescence produced by cathode rays or electrons,

(t) chemiluminescence produced by chemical process,

(g) sonoluminescence produced by high frequency sound waves or phonons and

bioluminescence produced by biological processes,

(h) Thermoluminescence, which should actually be called thermally stimulated luminescence,

however is different in mechanism. It refers to emission during the warming up of a material

previously excited in some fashion. In optically stimulated luminescence stimulation is by

electromagnetic radiation of wavelength higher than that of exciting radiation. In all these cases

luminescent material may be considered as a transformer of energy. Even though luminescence

is observed in all forms of matter, the main applications involved are in solid luminescent

materials. A luminescent material is often called a phosphor, which means 'light bearer'. These

are materials, which absorb radiant energy of a certain wavelength range and reradiate at
longer wavelengths. These phosphors are mainly inorganic materials, which are prepared by

proper heat treatment i.e. by high temperature solid-state reactions. Comparatively few pure

solids like silicates, sulphides selenides and oxides of Ca, Zn, Ba. Sr and Hg, luminesce efficiently

at room temperature. The luminescence emission from these phosphors can be modified by

incorporating certain impurities, known as activators and co-activators. The native defects

which develop in the materials under normal thermodynamic considerations as well as those

produced during incorporation of impurities during preparation, also play a part in controlling

luminescence properties. The alkaline earth sulphides (AES) like CaS, Bas and SrS belong to a

class of efficient phosphors, which emit radiation (of wave length ultraviolet to infrared) in the

presence of suitable activators. Suitable solid solutions among them are also good phosphors.

Luminescence emission occurs as a result of photo effect inside the complicated discrete

luminescence centers. The process generally involves two steps.

(a) Excitation, where by the system temporarily attains a higher energy state and

(b) Emission, in which absorbed energy is released by radiative or non-radiative transitions.

(a) Excitation

It is a process where a primary particle or a photon of energy E gives up some or all of its energy

to raise electrons from occupied low energy levels to unoccupied higher energy levels. On the

basis of band theory of solids with respect to electronic energy levels, the forbidden gap can be

imagined to contain some acceptor / donor levels. Interaction of ionizing radiation with the

solid can transfer sufficient energy to electrons in the valence band for transferring them to the

conduction band. A good number of these liberated electrons return immediately to the ground
state accompanied or unaccompanied by light emission (causing fluorescence or

phosphorescence or internal heating). A fraction of these can be captured at the donor levels

called traps with the corresponding holes at the acceptor levels or traps. The donor / acceptor

levels are metastable states associated with crystal defects including impurities.

Depending on the depth and lifetime of these levels, the holes and electrons are detrapped and

radiative or non-radiative recombination takes place. Considering photons or particles used for

excitation, cathode rays are less penetrating. The absorption of electrons occurs in relatively

thin layer of phosphor, so a higher excitation density is available with cathode rays. In the case

of excitation by ionizing radiations like gamma rays, X- rays, ultra violet rays, charged particles

are produced in equal numbers and thus charge neutrality is maintained and absorbed energy

is dissipated in the host. Ionization of the activator is another process of excitation in

photoluminescence event. Here luminescence centre absorbs energy directly or through the

lattice. A hole in the valence band and an electron in the conduction band appear in such

processes.

(b) Emission

Radiative transitions A photon can be emitted when an electron drops from an upper to lower

energy level. These levels can be intrinsic band states or impurity levels. Radiative transitions

can be classified in to

(a) band-to-band transition involving free electrons and holes, which are some times called free

to free transitions. Direct gap materials (II - VI and III - V compounds) permit

momentumconserving transitions between conduction and valence bands, and indirect gap
materials (group IV semi conductors and some III-V compounds) require the emission or

absorption of a phonon to complete the lowest energy transition across the energy gap. Band

to band radiative transitions are therefore much probable across a direct gap.

(b) Transition between band and impurity in which a radiative transition can be between an

impurity state and an intrinsic band (conduction band to acceptor or donor to valence band).

Such a free to bound transition can be highly probable if the impurity is deep, since the wave

function of deep levels extends throughout the momentum space thus permitting momentum-

conserving transitions even in indirect gap materials.

(c) Transition at a localized centre: - In wide gap materials it is possible to excite an impurity

with out ionizing it i.e. without placing its electron in the conduction band. When an electron of

such a deep center returns to the ground state, it emits a narrow spectrum having

characteristic of an atomic transition.

(d) Transition at iso-electronic centers, which are formed by replacing one atom of the host

crystal by another atom of the same valency. An iso-electronic centre can capture an electron in

a short range potential, thus getting charged and becoming very attractive to holes; then a

bound exciton is formed. Since the exciton bound to an iso-electronic centre is very localized, it

has very high radiative recombination probability.

(e) Donor to acceptor transitions: - These transitions can be very efficient. Most light emitting

diodes use this mechanism. In the phosphor literature acceptors and donors are called

acfivarors and co-activators. Such pairs can be thought of as molecular impurities, when they

occur in neighbouriny sites. The coulomb interaction between a donor and an acceptor is a
strong function of the over lap of the electron and hole wave functions. In some materials (Ge,

Gas) the coulomb energy increment for the nearest pairs can be larger than the activation

energies of the impurities, thus making the excitation energy for that pair greater than the

energy gap. Once excited such an electron hole pair will relax to the band edges and recombine

via some other transitions, such as via a more distant pair. The emission spectrum of donor to

acceptor transition is broad owing to the large range of separations possible between the

impurities. The nearest pairs contribute the highest energy photons, often in well-resolved

spectral peaks. Distant pairs contribute the lowest energy photons in a rather broad band. A

distinguishing characteristic of donor acceptor transition is their time resolved spectra. On

switching off the excitation source, emission spectrum shifts to lower energies. The nearest

pairs contribute highest energy with fast decay rate, while the distant pairs produce low energy

photons with slowest decay. Relative deep donors and acceptors are desirable for effective

radiative recombination, since

1. momentum conservation is easier with deep impurities,

2. the binding energy of deep nearest pairs can be lower than the band gap and

3. recombination at nearest pairs does not require tunneling. Fluorescence and

Phosphorescence They are radiative emission transitions from the higher to the lower energy

states. The classification of the two is based on the persistence of emission after the source of

exciting energy is removed. Fluorescence and phosphorescence are having wide applications in

varying Maney substances continue to luminesce for extended periods even after the exciting

energy is cut off. The delayed emission is generally called phosphorescence and emissioh during
the time of excitation is called fluorescence. More clearly the emission with in a lifetime is

indisputably fluorescence and the long-lived emissions are phosphorescence. The various

processes that are important in luminescence analysis. If a molecule does not undergo a

photochemical reaction after it absorbs electromagnetic radiation in the UV or visible region, it

is normally promoted to a vibrational level in the excited electronic singlet state (4a). The time

for a molecule to pass from the ground state to an electronically excited state. Since this time

period is so short, the atomic nuclei in the molecule do not appreciably change their relative

positions. So as per Franck Condon Principle, electronic transitions essentially occur with out

change in positions of nuclei. Immediately after excitation by electromagnetic radiation, a

molecule has the same geometry and is in the same environment as it was in the ground state.

The upper vibrational levels for an excited electronic state of the molecule relax. The vibrational

relaxation process is accompanied by a loss in thermal energy. Once the molecule is in the

lowest vibrational level of the lowest excited singlet state, a radiative transition can occur in

which the molecule drops to one of a number of possible vibrational levels of the ground

electronic state. This radiative transition is called fluorescence. These almost always occur from

the lowest vibrational level of the lowest excited singlet state in a molecule. The decay time of

fluorescence is about the same order of magnitude as the lifetime of an excited singlet state.

Because of spectroscopic selection rules, the transition from an excited singlet state to a singlet

ground state is spin allowed and thus occurs with a high degree of probability. After the

fluorescence transition, vibration relaxation take place and the molecule then arrive in a ground

state equilibrium configuration.

The other processes can compete with fluorescence. The excited molecule can loose energy by

other means such as internal conversion and inter-system crossing. Internal conversion is a

radiation less process whereby a molecule passes from a higher to lower electronic state with

out emission of a photon. After the internal conversion, vibration relaxation follows to the

lowest vibrational level of the lower electronic state. However, a radiationless transition

between the first excited singlet state to the lowest excited triplet state is called inter-system

crossing. A change in spin occurs with inter-system crossing, and thus spin selection rules

cannot be obeyed rigorously. However inter-system crossing can take place because of spin

orbit coupling between an excited singlet state and an excited triplet state. The net result of

spin orbit coupling is the mixing of triplet character in to the singlet state and singlet character

in to triplet state. Thus the mixing of states removes the spin forbidden nature of the

transitions between pure singlet and pure triplet states. If inter system can favourably compete

with fluorescence or internal conversion to ground state, the molecule can pass from lowest

excited singlet state to a triplet state. Then the molecule will undergo vibrational relaxation to

arrive at the lowest vibrational level of the lowest excited triplet state. From this state,

molecule can undergo radiative transition or undergo inter-system crossing to the ground state.

This radiative transition results in phosphorescence. Since phosphorescence originates from the

lowest triplet state in a molecule, its decay time is similar to the lifetime of the triplet state,

which is about lo4 to10 seconds. The radiative transition from the triplet excited state to a

singlet ground state is a spin forbidden transition because it involves a change in spin. Because

phosphorescence is a spin forbidden process, the rate of phosphorescence is relatively slow

compared to other processes associated with excited molecules. This fact gives the electronic
triplet state its long lifetime. Emission from rare earths. Non-radiative transitions They are

transitions from upper to lower state with out emitting a photon. Nonradiative recombination

processes are difficult to identify or to study directly because their occurrence can only be

inferred from the low emission efficiency. The non-radiative recombination can occur due to

(i) Multi phonon emission This can be explained by configuration coordinate diagram, which

shows the energy of an electron in both the lower and upper states as a function of generalized

coordinates representing the average distance of atoms surrounding the atom with which this

electron is associated. If an atom moves to r, (e.g. due to thermal vibration), the electron can

escape the excited state at the crossing C of the two states and return to the minimum energy

at r,, while the atoms move to the corresponding lower equilibrium distance. The atomic

displacement generates phonons. Since the phonon energy is much smaller than the total

energy of the electrons in the excited state, many phonons must be generated. The multi

phonon emission is temperature dependent, since the electrons in the excited state must

overcome the barrier E,

(ii) Auger effect. A recombining electron can transfer energy it would have radiated, to another

electron in the excited state. The second electron is then raised to higher energy. This is auger

process. The second electron can now return to a lower energy excited state by multi phonon

emission.

(iii) Non-radiative defects Surface recombination is non-radiative because a continuum of

states may join the conduction band to the valence band. The recombination at the surface

sites dissipates the excess energy by phonon emission. crystal defects such as grain boundaries,
pores, dislocations etc. provide regions where a localized continuum of states bridges the

energy gap and allows non-radiative recombination. Clusters of vacancies also form such non-

radiative centres. All defects are not recombination centres. Some times the local strain

induced by the defect may either widen the energy gap, thus repelling both carriers or create

local field, which separates the electron hole pairs. In either case although the carriers are

conserved, they do not recombine radiatively at each site.

QUENCHING

In some cases, when the appropriate conditions for efficient luminescence emission are not

met, the competing non-radiative dissipation dominates resulting in a decrease of

luminescence emission which is called quenching. This can be due to dopant concentration,

temperature effects or due to inclusion of killer impurities or imperfections.

(a) Concentration quenching Emission from the activator is proportional to the number of

emitting species and emission per activator ion should be constant at all concentrations of the

activators and sensitizers used. But in practice, as the concentration is increased emission

increases first reaches a maximum and then decreases for further increase of concentration of

the dopant. This is due to the coupling of the wave function of the activator or sensitizer and

host ion. Anion lattice acts as a carrier for a band process through which energy can be coupled

through out the structure. In the case of rare earth dopants the interaction depends on (1) the

strength of interaction of f-orbital electron wave functions with valence electrons

(2) the strength of interaction of these ions with the anions of the lattice and
(3) the distance between rare earth ions. If the lifetime is reduced, the likelihood that the

migrating energy reaches a sink before emitting is always more resulting in the loss of

efficiency.

(b) Temperature quenching Rise of temperature above a maximum may show a quenching of

luminescence due to the following processes.

(1) Thermal ionization of excited state

(2) thermal expansion of lattice due to phonon fluctuations

(3) broadening of electron and hole energy levels

(4) increased electron- phonon interactions.

The change in the energy level difference between excited and ground states of potential

energy curve may bring the crossover point nearer where as increased oscillations of the

excited state may facilitate non- radiative decay of the energy.

(c) Quenching by killer impurities. Certain impurities at very low concentration produce levels in

the forbidden region and facilitate radiationless dissipation of excitation energy. Impurity ions

with such behaviour are known as killers. Certain environments may also cause

(d) Quenching by imperfections Certain defects act as traps for migrating energy while others

may produce levels in the forbidden region to cause reduced emission.

TRANSFER OF ENERGY IN LUMINESCENCE PROCESSES

Energy transfer occurring in luminescence processes during absorption and emission are not

confined to the same centre. Energy transfer plays an important role in luminescence

phenomena. When there are two activators in a crystal, though emission lines may not change

due to second activator, the following changes are possible.

(1) Intensity of the luminescence spectrum of one ion can gain in strength at the expense of

the other.

(2) An ion not luminescent at a given concentration in a given crystal becomes luminescent

in the presence of another ion in the same crystal.

(3) Luminescence of an ion can be observed under conditions of excitation in which it is not

luminescent with out the presence of another ion.

(4) With complete quenching of one centre, intensified luminescence can be observed from

the other centre.

These changes in luminescence of one ion in the presence of other, is due to the transfer of

excitation energy from one to the other. Luminescence of ions excited as a result of the energy

transfer from one to the other excited ion is termed as sensitized luminescence.

4. Optical studies
 The optical bandgap values of the films Eg(film) were determined from the transmission

vs. wavelength traces. The absorption coefficient () was obtained from the standard relation

[15]:

4kx


T=A e 3.2

 16n0 n1 (n 2  k 2 )
where k is extinction coefficient, k and A
4 {( n0  n) 2  k 2 }{( n1  n) 2  k 2 }

n0, n1 and n being the refractive index of air, substrate and films respectively.

For k2 << n2, A is nearly equal to unity and T can be expressed as:

T ~ e-x 3.3

The fundamental absorption, which corresponds to electron excitation from the valance

band to conduction band, can be used to determine the nature and value of the optical band

gap. The relation between the absorption coefficients ( and the incident photon energy (h

can be written as [16],

h  n  Ah  Eg 
1
3.4

where A is a constant and Eg is the bandgap of the material and exponent n depends on the

1
type of transition. For direct allowed n  , indirect allowed transition, n = 2, and for direct
2

3
. To determine the possible transitions, h  n vs. h were plotted and
1
forbidden, n 
2
corresponding bandgap were obtained from extrapolating the straight portion of the graph on

h axis at  = 0.

Figure bellow shows the transmittance vs. wavelength traces which show nearly 75 %

transmittance in the wavelength range of 500 nm to 800 nm.

The optical band gap of thin films can be determined from the transmittance (T) vs.

1
wavelength ( plot. Taking n = , h vs. hgraph, extrapolating the linear portion of the
2

graph to the haxis allowed the direct band gap to be determined from the intercept. The

values of the optical bandgap (Eopt) will be high for nano structure materials.

(A)

10
3.0x10

10
(B)
2.5x10

10
2.0x10
(h) (eV cm )
-2

cf 47
10
1.5x10 cf 45
2

cf 46
10
cf 29
1.0x10
cf 32
2

9
5.0x10

0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0

h (eV)
 Figure .(A). Transmission spectra of F:CdO thin films for five different F concentrations in
the films (a) cf-47, 18.7% F; (b) cf-45, 14.6% F; (c) cf-46, 12.8% F; (d) cf-29, 10.3% F and (e)
cf-32, 5.6% F. (B). To determine the optical bandgap from h vs. hplot.

The properties of nanocrystalline materials change from their corresponding bulk

properties due to the sizes of the crystallites become comparable to the Bohr excitonic radius (

rB ) [25]

h 2  1 1 
rB   * *  3.6
e 2  me mh 

where  is the permittivity of the sample, m*e and m*h are the effective mass of electron and

hole in CdO respectively., where m0 is the mass of a free electron. The values of the particle

size of the CdO thin films, as obtained from TEM studies for annealed temperature below 300

0C, are comparable to the Bohr excitonic radius supporting the quantum size effect.

The values of particle radius (r) in the nanocrystalline CdS thin film, as determined from

that of TEM studies, are less than Bohr radius ( r  rB ) supporting the strong quantum
confinement effect. The shift of band gap might also be utilized in determining the crystal

radius (r) using relation [25-26]:

 h 2  1.8e 2 
E g  E g ( Film)  E g ( Bulk)   2
  3.7
 8r   r 

1 1
where   *
 *
is the reduced mass of electron-hole effective masses and  is the
me mh

permittivity of the sample. From the above equation, the particle sizes have been determined

and these lie in the range 2.56 nm to 4.06 nm and that obtained from TEM measurements

(bellow annealing temperature 300 0C) are also fairly support these results.
Chapter V

ELECTRON TRANSPORT:

Carrier transport in nanostrcutures. Coulomb blockade effect, thermionic emission, tunneling

and hoping conductivity. Defects and impurities: Deep level and surface defects.
5.1. Introduction

Semiconductor nanostructures have gained importance due to their potential application in future

nanoelectronic devices. For such applications, it is extremely important to understand the

electrical properties of semiconductor nanostructures. This review presents an overview of

techniques to measure the electrical properties of individual and clusters of semiconductor

nanostructures using microcopy based techniques or by fabricating metallic electrical contacts

using lithography. Then it is shown that current-voltage (I-V) characteristics can be used to

determine the conduction mechanism in these nanostructures. It has been explained that various

material parameters can be extracted from I-V characteristics. The frequently observed

conduction mechanism in these nanostructures such as thermally activated conduction, space

charge limited current (SCLC), hopping conduction, Poole Frenkel conduction, Schottky

emission and Fowler Nordheim (FN) tunneling are explained in detail.

5.1.1. Overview of carrier transport models

Semiconductor devices and nanostructures are open systems that interact with their environment,

e.g. through leads/contacts, phonons or electromagnetic fields. The effect of these interactions,

especially the electric field created by the voltage applied between the contacts [1-5] , is so

strong that the statistical distribution of particles (charge carriers) strongly deviates from the

statistics applicable in equilibrium, e.g. the Fermi-Dirac distribution. The results of linear

response theory, e.g. the relaxation time approximation, are no longer sufficient for an accurate

description [6, 7]. The non-equilibrium distribution can be determined by solving a transport

equation which describes the movement of particles under the influence of external forces.
There exists a plethora of transport models, each having its limitations and advantages. The

choice of a model depends on the application (phenomena) to be simulated and the

computational resources/time available. From a physical point of view it is attractive to choose

the most fundamental models, but these may not computationally feasible, nor required, for a

given task. The aim of this section is to provide an overview of the most important transport

models used for semiconductor devices and nanostructures. The capabilities and limitations of

the models are highlighted to be able to appreciate the position and capabilities of transport

simulations based on the Wigner formalism.

In the following the most important semi-classical transport models will be covered first, because

they still find application today in nanoscale devices when augmented with quantum

models/corrections. Thereafter, the full-fledged quantum transport models are introduced. The

considerations are presented based on intuitive concepts, like particles and distribution functions,

which characterize the historical evolution of the field of transport models. Many of these

classical attributes are retained in the Wigner formalism which bridges the two limiting transport

regimes (semi-classical/diffusive and quantum/coherent) presented hereafter.

In the following a single-particle description is deemed sufficient to describe a particle ensemble

in a statistical manner [8]. Moreover, only interactions between different kinds of particles are

considered, e.g. electron with phonons. Many-particle phenomena, like Coulomb interaction, that

occur between particles of the same kind are not considered explicitly and are only accounted for

via the Poisson equation.

5.1.2. Classification of transport models

The physics that governs carrier transport depends on three characteristic lengths as related to the

dimensions of a device [9]:

1. De Broglie wavelength: the wavelength associated to a particle with a

momentum p by λ = ∕h. For an electron in silicon at room temperature λ ≈ 8nm [8],

whereas in GaAs λ ≈ 17nm [10].

2. Mean free path (MFP): the mean distance a carrier travels before a momentum-altering

scattering event occurs, e.g. inelastic phonon scattering. The MFP depends on the electric

field but is in the order of 5-10nm for an electron in silicon at room temperature and up to

an order of magnitude longer for GaAs [11, 12].

3. Phase relaxation length (PRL): the mean distance a carrier travels before a phase-

changing scattering event occurs, e.g. electron-electron scattering. In semiconductors the

relation between the PRL and the MFP depends on the type of semiconductor [13], but

the PRL usually matches or exceeds the MFP [9].

Considering the above, one can distinguish between two limiting cases: the diffusive regime

where the size of the device is much larger than all the characteristic lengths and carrier transport

is predominantly determined by the scattering taking place; the other extreme, in devices shorter

than all the characteristic lengths, is the ballistic regime where negligible scattering occurs and

the transport is completely coherent2 . Whereas transport in the diffusive regime can be

appropriately described by semi-classical transport models, the ballistic regime requires models

which consider the coherent wave nature of particles. The transition between the diffusive and
the ballistic regime is gradual and nanostructures/devices, where both scattering and coherent

transport play a role, demand the most general transport models, as is illustrated in

Figure 1.1 (based on [14]).

An interplay between diffusive and coherent transport is often encountered in mesoscopic

devices with at least one dimension shorter than one of the characteristic lengths mentioned

above. In such devices quantum processes are at play that can be observed macroscopically, e.g.

conductance fluctuations [15].

Quantization effects, due to confinement, start to appear, if at least one physical dimension of a

device is below the De Broglie wavelength of the carriers. Interference effects imply coherent

transport and become significant if the PRL exceeds at least one dimension of a device. Since the

PRL can exceed the MFP in semiconductors, the phase coherence can be retained despite

scattering taking place.

Apart from the physically-grounded distinction between transport models between the ballistic

and diffusive regimes, the models can further be classified as either microscopic or macroscopic.

Microscopic transport models describe the evolution of the distribution function (semi-classical)

or state (quantum) of the system, from which all physical quantities (observables) of interest can

be calculated. Macroscopic models are derived from the microscopic transport equations and

directly solve for physical quantities – often termed engineering quantities – like electron

concentration or current density. The computational efficiency afforded by macroscopic models

comes at the cost of a loss in generality – certain assumptions are made, which limit the scope
where the models remain valid. A thorough treatment of the mathematical derivations of both

semi-classical and quantum macroscopic models is given in [8].

A hierarchy of models can be set up ranging from, at the most fundamental level, a quantum

microscopic model to a semi-classical macroscopic description of carrier transport.

Table 1.1 presents such a hierarchy, along with the device dimensions and applications at which

each model is applicable.

***

5.2. Coulomb gap:

Electrons can be confined into a quantum dot (zero-dimensional or 0D structure). If

the barrier between the 2D reservoir and the quantum dot is such that there is no conducting

channel then the only way electrons can enter the dot is by quantum mechanical tunneling.

h
The resistance is then greater than = 25.8 k. A single-electron transistor can then be
e2

made with a source, drain and gate electrodes capacitively coupled to a quantum dot. A

source to drain current flows by tunneling through the dot. But adding an extra electron to

e2
the dot requires a Coulomb energy. E  eV  , where C is the total capacitance of the
2C

dot to its surroundings and V is the change in voltage on the dot. Hence the current is

e2
inhibited (Coulomb blockade). A Coulomb gap E gap  appears in the density of electron
C

states.
 The gate electrode can be used to control the potential on the dot, through the gate

Cg
capacitance Cg. A bias voltage Vg on the gate changes the dot potential V  V g . As Vg
C

is changed extra electrons tunnel in to and out from the dot and the source to drain current is

e2
periodic in Vg with a period V g  . These are Coulomb blockade oscillations and form
Cg

the basis of a single-electron transistor.

5.3. Thermionic emission

5.3.1. Thermionic emission definition

The process by which free electrons are emitted from the surface of a metal when external heat

energy is applied is called thermionic emission.

Thermionic emission occurs in metals that are heated to a very high temperature. In other words,

thermionic emission occurs, when large amount of external energy in the form of heat is supplied

to the free electrons in the metals.

5.3.2. Metals under normal temperature

When a small amount of heat energy is applied to the metal, the valence electrons gain enough

energy and break the bonding with the parent atom. The valence electron, which breaks the

bonding with the parent atom, becomes free. This electron, which breaks the bonding with the

parent atom, is called as the free electron. The free electrons in the metal have some kinetic

energy. However, they do not have enough energy to escape from the metal. The attractive force
of the atomic nuclei opposes the free electrons, which try to escape from the metal. Free

electrons in the metal have less energy compared to the free electrons in vacuum. Hence, free

electrons require extra energy from the outside source in order to jump into the vacuum.

5.3.3. Metals under high temperature

When heat energy applied to the metal is increased to a higher value, the free electrons gain

enough energy and overcome the attractive force of the atomic nucleus, which holds the free

electrons in the metal. The free electrons, which overcome the attractive force of the nuclei,

break the bonding with the metal and jumps into the vacuum. The free electrons, which are

escaped from the surface of a metal when heat energy is supplied, are called thermions.

Thermionic emission process plays a major role in the operation of electronic devices.

Thermionic emission depends on heat applied to the metal and work function of the metal. The

number of free electrons escaped from the metal is depends on the amount of heat applied to the

metal and the work function of the metal.

5.3.4. Heat applied to the metal:

If large amount of heat is applied to the metal, large number of free electrons gains enough

energy and breaks the bonding with the metal. The free electron, which breaks the bonding with

the metal, jumps into the vacuum.

On the other hand, if less amount of heat is applied to the metal, less number of free electrons

gains enough energy and breaks the bonding with the metal. The free electron, which breaks the

bonding with the metal will jumps into the vacuum.

Hence, the number of free electrons emitted from the metal increases with increase in heat. Thus,

the free electrons emitted from the surface of metals are directly proportional to the temperature

of the metals.

The minimum temperature at which the metal starts emitting the free electrons is called threshold

temperature.

If the temperature of the metal is below the threshold temperature, the metal does not emit the

free electrons. On the other hand, if the temperature of the metal is equal to the threshold

temperature or greater than the threshold temperature, the metal emits the free electrons.

5.3.5. Work function of the metal:

The amount of external heat energy required to remove the free electron from the metal is called

work function or threshold energy. The work function of metals is measured in electron

volts (eV).

Metals that have low work function will require less amount of heat energy to cause the free

electrons to escape from the metal. Hence, the metals with low work function emit large number

of free electrons at high temperature.

On the other hand, metals that have high work function will require more amount of heat energy

to cause the free electrons to escape from the metal. Hence, the metals with high work function

emit less number of free electrons at high temperature.

Thus, the emission of free electrons from the metal is inversely proportional to the work function

of a metal.
5.3.6. Applications of thermionic emission

The components, which are made by the process of thermionic emission are used in the

electronic devices such as cathode ray tube, radio etc.

5.4. Electrical conductivity/resistivity

Transport phenomenon is the motion of charge carriers under the action of internal or

external fields. In the absence of an electric field, the electron gas in a semiconductor is in an

equilibrium state, which is established as a result of the interaction of electrons with lattice

defects. Such defects include lattice imperfections, thermal vibrations of the lattice (phonons)

and impurity atoms. If an electric field E is applied to a material, an electric current will flow,

whose density J is given by

J  E 3.8

where  is called the electrical conductivity of the material. The reciprocal of electrical

conductivity is known as electrical resistivity ρ. Forthin film, the resistance R is given by

 l 
R    3.9
 bt 

where l is the length, b is the width and t is the thickness of the sample. If 1= b, then


R  Rs 3.10
t

The quantity Rs is known as sheet_resistanc of the film it is the resistance of one square of the

film and is independet of the size of the square. The sheet reststance is expressed as resistance
/square.

The conductivity (  ) of the material is also related to resistivity () as

1  bt   bt  V 
    R     3.11
 l   l  I 

where V is the voltage applied to the sample and I is the corresponding current.

The conductivity of a semiconducting material can be expressed in the simplest form,

Ea
   0 exp(  ) 3.12
kT

where Ea is the activation energy, 0 is a temperature independent factor, k is Boltzman

constant and T is absolute temperature. The conductivity () of the films at different

temperature (T) can be measured and from the slope of the plot of lnvs. 1/T, activation

energy can be measured.

Under the influence of an electric field, the electrons begin to move in a specific

direction and such directional motion is termed drift. The average velocity of this motion is

known as drift velocity (Vd). If n is the number density of electrons, the current density is given

by

J = neVd 3.13

where e is the electron charge.

Combining,equations (3.1) and (3.4)

  
Vd    E 3.14
 ne 

 
The factor   is called the mobility (µ) of charge carriers, i.e.
 ne 

 
   3.15
 ne 

The charge carrier mobility, u, is related to the effective mass of the charge carriers (m*) and

the relaxation time ( ) according to

 e 
  * 
3.16
m 

In the case of thin films, the conductivity is greatly influenced by the thickness of the films. The

surface of a thin film affects the conduction of charge carriers by interrupting carrier transit

along their mean free path. They may either be diffusely scattered, in which case they emerge

from the surface with no memory of their previous velocity; or they may be specularly reflected

so that only their velocity component perpendicular to the surface is reversed, their energy

remaining constant. Any surface which is not completely specular in its behaviour will result in a

decrease in conductivity of the films. In addition to size effects, the lattice impurity and the

enormous number of structural defects in films also affect the conductivity.

For semiconductor materials, doping in them often induces dramatic changes in their

electrical and optical properties and may alter the bandgap.

Figure 2.4. Schematic diagram of the apparatus for the measurement of electrical

conductivity
5.5. The Hall effect phenomenon studies

It is often necessary to determine whether the sample is n-type or p-type. The

conductivity measurement does not give this information since it cannot distinguish between

hole and electron conduction. A Hall effect study is usually required to distinguish between the

two types of carriers. It also allows determination of the density of the charge carriers. When a

current is passed through a slab of material in the presence of a transverse magnetic field, a

small potential difference, known as the Hall voltage, is developed, in a direction perpendicular

to both the current and the magnetic field. From the sign of the Hall voltage the type of the

material can be identified. The Hall voltage is expressed as

H
VH  RH I   3.17
 t 

where VH is the Hall voltage, H is the magnetic field, the RH is Hall coefficient and I is the current

flowing through the sample. From Hall effect measurements and the measurement of

conductivity, the mobility of charge carriers can be calculated as follows:

  RH  3.18

The value of mobility of charge carriers determined by Hall measurements is known as Hall

mobility (  H ).

The Hall-Effect of the films for different F concentrations has also been studied at room

temperature (300 K). From the measured values of Hall coefficient (RH), we have calculated

carrier concentrations (n) for different % F doped CdO thin films using the relation R H = -1/ne,
where e is the electronic charge. The carrier concentrations obtained from Hall measurements

are very high ~1021 cm-3, almost metallic. The mobility () of the carriers was also calculated

from the simple relation  RH.

The total expression of Hall coefficient for degenerate conductor is

 3 2 1   2 1 
1  .  1  (4 p  1)( 4 p  3) . 2 
1  24  2   24  
RH   2
3.19
ne  2 1 
1  (2 p  1)( 2 p  3). . 2 
 24  

‘p’ is classical scattering factor = - 1/2

1  3 2 1    2 1 
RH   1   1   3.20
ne  24  2   24  2 

1
RH    3.21
ne

 3 2 1    2 1  2
where  = 1   =E (3 2 n) 3 , ‘k’ is the
2

2 
1 2
, f / kT, ‘E f’ is the Fermi-energy =
 24    24   2m

Boltzmann constant and ‘T’ room temperature in Kelvin.

The value of  for carrier concentration ~ 1018cm-3, comes out 1.0271 and for carrier

concentration ~ 1023 cm-3, it is 1.000228. Therefore, as the carrier concentration increases the

correction factor goes towards unity. So we can use RH = -1/ne very well for degenerate

semiconductor.
 From the electrical resistivity and Hall measurements data it is evident that the increase

of %F doping causes an increase in carrier concentration. This occurs because F atoms can

replace O atoms and donate extra electrons to the charge carriers. At first when percentage of

doping is small, the rate of increase of carrier concentration is high and it is lower when

percentage of doping is high. This phenomenon suggests that the F dopants are not readily

ionized and some of them act as neutral impurities in the CdO thin films. The Hall mobility of

the films first increases with additional doping, reaching a maximum value and then decreases

for higher % F doping. The simultaneous increase of both mobility and carrier concentration is

difficult to explain from the point of view of ionized impurity scattering only, and thus here

grain boundary scattering must also be taken into account. Apparently, there exists competition

between different scattering mechanisms, which control the Hall mobility. Firstly, the increase

of doping lowers the potential barrier height at grain boundaries [35], so the charge carriers can

easily cross the grain boundaries. This increases the carrier mobility. Secondly, additional

doping can cause the formation of more larger angle grain boundaries. The increase of large

angle grain boundaries and both ionized and neutral impurity centers will increase charge

carrier scattering, which results in decrease of carrier mobility. Since the scattering probability

is inversely proportional to the relaxation time and therefore to mobility, the mobilities due to

various scattering mechanisms add inversely

1 1 1 1
   3.22
 L I G

Increase of carrier concentration can be achieved by increased doping. However, it lowers the

mobility due to more charge carrier scattering from ionized impurities. The main scattering
mechanisms for charge carriers in thin films are lattice scattering, ionized impurity scattering

and grain boundary scattering [36]. The lattice scattering mobility, L , is proportional to the

reciprocal of temperature, i.e., L 1/T. Ionized impurity scattering mobility, I, is independent

of T and decreases with increase of carrier concentration. There are different opinions about

the role of grain boundary scattering G. According to Shanthi [37] and Pisarkiewcz [38] the

grain boundary scattering was important in limiting the mobility of their films, while others [36-

39] concluded that it made a very small contribution to the mobility behavior.

5.6. Thermoelectric power studies

The variation of thermoelectric power (S) with temperature is given by [40]

k E f 
S  A   3.23
e kT 

5
with A   s and    0 e  S
2

where k is the Boltzmann constant, e is the electronic charge,  Ef is the energy difference

between Fermi level and the upper edge of the conduction band, s is the relaxation time for

electron scattering, s is a constant, which is different for different scattering mechanism and so is

a constant, which is a function of temperature but independent of the electronic charge, e.

5.7. I-V characteristics (Poole–Frenkel) studies

The study of the carrier transport mechanism in fluorine-doped cadmium oxide thin

films, deposited by the sol–gel dip-coating route has been performed in details. It appears from

the experimental data that the transport mechanism in the films is dominated by the Poole–
Frenkel model of thermionic emission [41]. The manifestation of the Poole–Frenkel effect in the

thin films may be attributed to the presence of trap centers at the grain boundaries. As in

polycrystalline thin films carrier transport through the grain boundaries plays an important role

in controlling the electrical properties of the films; hence the present report may help to

understand the mechanism of electrical transport properties in F doped CdO films. This may be

of use in the production of films with improved electrical characteristics.

The reason behind the Poole–Frenkel effect shown by CdO thin films may be due to the

presence of adsorbed oxygen or dopant fluorine atoms at the grain boundary, which produce

defect states. These defect states trap carriers and thus produce a potential barrier at the grain

boundaries. Under the applied field, the barrier height is reduced and thermal emission of

electrons from interfacial states takes place, increasing the conductivity through the grain

boundary. Mathematically, the expression for current density according to the Poole–Frenkel

model [42]. can be written as

1  57.7eV 
1
2 
J  AT exp
2    1  3.24
KT   1 d  
 

(we have chosen e2 = 14.4 eV Å as a conventional unit), where, ε1 is the high-frequency

dielectric constant of the film, d is the electrode spacing in Å, φt is the depth of the trap

potential well and A is the Richardson constant having a value of 120 A/cm2 K2. According to

Eq. (3.24), ln (J/AT2) vs. V1/2 will be a straight line, and from the intercept on the ln (J/AT2)

axis the trap potential (φt) may be determined. Figure 3.22. shows the ln (J/AT2) vs. V1/2 plots

at different temperatures with F/Cd atomic ratio of 9.7%. The inset of Figure 3.22. shows the
same in log scale. Similar straight-line plots are also obtained for the same films at other

temperatures. The values of φt are the energies required to transfer electrons from the trap level

to the conduction band. The trap levels are placed deeper into the band gap than the donor level

with respect to the bottom of the conduction band. These data are consistent with the band

structure indicated by Simmons [43], as in FTO films donor concentrations are expected to be

higher than that of the trapped charge density. This argument seems reasonable if we compare

the values of the Fermi level obtained from thermopower measurements of our samples. The

values of Ef obtained were around 15–30 meV, smaller than the activation energies. This type of

band structure is typical of a nondegenerate semiconducting material with the donors not fully

ionized. Hence a continuous increase in conductivity with temperature was observed for our

films. Now, to obtain theoretically the position of the Fermi level, we have equated the number

of ionized donor centers (Nd) with the number of occupied traps (Nt), with the assumption that

trapping is effective at all times (i.e. Nt _ n, where n is the number of electrons in the conduction

band). This assumption seems reasonable if we consider the relatively low room temperature

conductivity of our films. Calculations from the above argument result in the following

expression [44]:

N 
E f  Ed  kT ln  d  , provided that Nd >> Nt. 3.25
 Nt 

Recalculation of the relative ratio of ionized donor centers to that of trap charge density (Nd/Nt)

from the above equation with the Ef values obtained from TEP measurement (with T = 300 K)

gives a value of the order of less than 102. Now if we also consider the non-ionized donor

centers present in the film at room temperature (300 K), then it may be concluded that the donor

concentration is higher than the trap charge density. Also we notice a slight increase in the values
of φt with increasing temperature. Whether this is due to the experimental limitations or may be

treated as a trend of temperature dependence of φt may become apparent with further research. It

is well known that the conduction in a thin film can be of two types [44]: bulk limited and

electrode (or contact) limited. For the former case the electrode–film contact should be ohmic

and the current is controlled by the bulk resistance of the film. For the latter case the contact

would be of non-ohmic (or blocking) type and the current is controlled by the contact resistance.

Hence current density will be dominated by Poole–Frenkel emission for bulk-limited cases and

by Schottky emission for electrodelimited cases. However, at lower voltages, as the contact

resistance dominates, most of the voltage will appear across the contact resistance and very little

across the bulk of the film. So in that situation the current conduction may not be treated as bulk

limited. Considering this point of view, we have also tried to fit the Schottky model in the low-

voltage region of the experimental data. However, the fit was far from satisfactory. This can be

explained if we compare the Richardson–Schottky equation and the Poole–Frenkel equation. The

two equations are identical except that the coefficient of V1/2 within the exponential term in Eq.

(3.24) will be reduced by a factor of 2 for the Schottky equation. Therefore, the ln (J/AT2) vs.

V1/2 plot (at a constant temperature) will show two distinct slopes for the two types of

conductions. Hence, the transition from electrode- to bulk-limited conduction will be

characterized by a deviation in the slope of the ln (J/AT2) vs. V1/2 plot with increasing voltage.

Simmons [44] theoretically calculated the limit for the electrode- and bulklimited cases assuming

a certain amount of donor concentration. Stuart [45] observed this type of transition for Al–SiO–

Al thin films. Similar transitions in some organic semiconductor films such as copper

phthalocyanine and others have also been observed [46]. However, for our films we have

obtained almost straight-line plots with single slopes over the entire voltage range, for all three
types of samples. For our nanostructured films, with an approximate grain size of 6.5 nm, a large

number of grain boundaries are present in the films. Hence a considerable number of trap states

are present in these grain boundary regions. Therefore, even if the Schottky effect is present in

the low-voltage region, it is probably masked by the Poole–Frenkel emission from some shallow

traps at grain boundaries. Hence we can conclude that the conduction mechanism in our

nanocrystalline films is dominated by the Poole–Frenkel mechanism.

Figure 3.22. shows the I-V characteristics of the CdO:F thin film for 9.7 % F doping at

different temperatures (T) 308, 358, 408, 458, 508 K and corresponding trapping potentials

were calculated as 685, 802.6, 916, 1031.8, 1155.7 meV respectively. Inset of Figure 3.22.

shows the I-V characteristics in log scale. The curves are non-linear in nature. Non-linearity is

significant above 12 Volt. This is due to the presence of an electron-depleted layer at the grain

boundary and the formation of a potential barrier. This shape of I-V curve is typical of

thermionic emission over the barrier, explained by the Poole-Frenkel model of thermoionic

emissions [47-48]. With the increase in temperature the curves showed more and more

deviation from ohmic behavior. Also trapping potentials increase as temperature increases due

to downward movement of impurity level from minimum of the conduction band.

5.8. Hopping Conductivity

A theory of hopping conduction is developed for compensated crystalline and amorphous

semiconductors subjected to a strong electric field.

The primary benefit of hopping conductivity models is avoiding the requirement of band

structure. Lack of long-range order and periodicity in disordered materials does not lead to good
quantum numbers and the standard band theory approach is not valid. Extended states arise along

segments of the polymer chains, leading to localized sections of band structure. This leads

naturally to hopping from localized state to localized state as the primary conduction mechanism

with a wave-function overlap integral serving to determine hopping probabilities between sites.

Leaving the details of the quantum mechanics to others (Barrie et al., 1986), it is possible to

evaluate hopping models and correlate fitting parameters qualitatively and quantitatively to

physical parameters. While there have been many hopping models developed in past decades,

two have emerged as the most promising approximations of transport behavior in polymers:

thermally assisted hopping and variable range hopping. Thermally assisted hopping (multiple

trapping) was originally formulated for ionic conduction in crystals. It models thermal activation

of a carrier from a shallow trap into a conduction band, followed by nearly immediate recapture

in a nearby trap. Carrier mobility is then a factor of mean trap depth, ∆H, and the energy gained

or lost by the carrier, Ea , as it moves over the distance between traps, a. Two fundamental

behaviors are expected if thermally assisted hopping is a conduction mechanism. At low applied

fields, should be field independent and show a characteristic T-1exp(T-1) dependence. For a

constant temperature, field dependence begins to emerge and near a critical field value, diverges,

indicating a rapid increase in conductivity leading to dielectric breakdown. Low applied fields do

not show considerable field dependence and at moderate temperatures the conductivity is

proportional to T-1exp(T-1). Calculations of activation energies from the model fit are in

reasonable agreement with the broad range of values reported in the literature.

The second potential hopping mechanism is variable range hopping (tunneling), with low

temperature measurements of particular interest. At room temperature, is not expected to play a

contributory role in charge transport. As temperature decreases, the temperature dependent

behavior shifts to a characteristic T-1/4exp(T-1/4) dependence with a transition point. Evaluation of

activation energies reveals a correlating transition as temperatures decrease and the values

obtained at low temperatures are in agreement with values reported in the literature for tunneling

behavior. The T-1/4exp(T-1/4) behavior and reasonable agreement of the values of the physical

parameters indicated that variable range hopping was a viable conduction mechanism.

5.9. Defects:

5.9.1. Crystal defect

Crystal defect, imperfection in the regular geometrical arrangement of the atoms in a crystalline

solid. These imperfections result from deformation of the solid, rapid cooling from high

temperature, or high-energy radiation (X-rays or neutrons) striking the solid. Located at single

points, along lines, or on whole surfaces in the solid, these defects influence its mechanical,

electrical, and optical behaviour.

Point defects include the Frenkel type, the Schottky type, and the impurity type.

The Frenkel defect involves a single ion, which is displaced from its normal lattice point and

shifts to a nearby interstice, or space, between atoms in the lattice. In the Schottky defect, two

ions of opposite sign leave the lattice. Impurity defects are foreign atoms that replace some of the

atoms making up the solid or that squeeze into the interstices; they are important in the electrical

behaviour of semiconductors, which are materials used in computer chips and other electronic

devices.
 Line defects, or dislocations, are lines along which whole rows of atoms in a solid are

arranged anomalously. The resulting irregularity in spacing is most severe along a line called the

line of dislocation. Line defects can weaken or strengthen solids.

Surface defects may arise at the boundary between two grains, or small crystals, within a

larger crystal. The rows of atoms in two different grains may run in slightly different directions,

leading to a mismatch across the grain boundary. The actual external surface of a crystal is also a

surface defect because the atoms on the surface adjust their positions to accommodate for the

absence of neighbouring atoms outside the surface.

5.9.2. Defect in Semiconductor

Impurities are essential for giving semiconductors the properties that render them useful

for electronic and optoelectronic devices. The intrinsic carrier concentrations in most

semiconductors are quite low. Adding small amounts of impurities allows control of the

conductivity of the semiconductor: shallow donors, such as phosphorous in silicon, produce n-

type conductivity (carried by electrons), and shallow acceptors, such as boron in silicon, produce

p-type conductivity (carried by holes). These doped layers and the junctions between them

control carrier confinement, carrier flow, and ultimately the device characteristics.

Every material contains defects; perfect materials simply do not exist. While it may cost

energy to create a defect, configurational entropy renders it favorable to incorporate a certain

concentration of defects, since this lowers the free energy of the system. Therefore, even in

equilibrium we can expect defects to be present; kinetic limitations sometimes lead to formation

of additional defects. Note that all of these considerations also apply to impurities that are

unintentionally present in the growth or processing environment. Of course, impurities are often
intentionally introduced to tailor the properties of materials. Doping of semiconductors with

acceptors and donors is essential for electronic and optoelectronic applications. In the following,

we will use the word “defect” as a generic term to cover both intrinsic defects (vacancies,

selfinterstitials, and antisites) and impurities. Since defects are unavoidable, we must consider

the effects they have on materials properties. These effects can be considerable, to the point of

determining the functionality of the material, as in p- or n-type doping. Point defects play a key

role in diffusion: virtually all diffusion processes are assisted by point defects. Defects are often

responsible for degradation of a device. Even in the absence of degradation, defects can limit the

performance of a device. Compensation by native point defect can decrease the level of doping

that can be achieved. Defects with energy levels within the band gap can act as recombination

centers, impeding carrier collection in a solar cell or light emission from a light-emitting diode.

Sometimes these effects can be used to advantage: luminescence centers in wide-band-gap

materials can be used to emit light at specified wavelengths; or single-spin centers can act as an

artificial atom and serve as a qubit in a quantum information system. Finally, sometimes one

deliberately wants to grow materials with many defects. Examples are materials for ultrafast

optoelectronic switches or semiconductors used to optically generate pulses, where defect

densities should be large enough so that carrier lifetimes are as short as a few picoseconds.

5.9.3. Defect levels and wave functions

The electrically active defects are defects that can exist in different charge states. For example,

single acceptors can exist in either a negatively charged or neutral state. Single donors exist in

either the positively charged or neutral state. Other defects can exhibit more complexity.

Substitutional gold in silicon, for example, can be negative, neutral, or positive. Defects that can

act both as donors and acceptors are called amphoteric. Electrically active defects have at least
one defect level (or transition level) in the band gap, somewhere between the valence-band

maximum (VBM) and conduction-band minimum (CBM). This level has an associated defect

wave function, a state to which the electron is added or removed when the charge state of the

defect changes. If a transition level is positioned such that the defect is likely to be thermally

ionized at room temperature, it is conventionally referred to as a shallow level. Otherwise, it is

called a deep level. An alternative definition is based on the degree of localization of the wave

function of an electron (or hole) associated with the defect. A delocalized wave function (on the

order of many lattice constants) is characteristic of a shallow level, while a wave function

localized on a length scale of an atomic bond indicates a deep level.

5.9.4. Trap states

Trap, in physics, any location within a solid (generally a semiconductor or an insulator)

that restricts the movement of electrons and holes—i.e., equivalent positive electrical charges

that result from the absence of an electron within a crystal structure. A trap consists of either a

chemical impurity or an imperfection in the regular spacing of the atoms that make up the solid.

Traps play a significant role in photoconduction, luminescence, and the operation of various

electronic devices because the ability of a solid to carry an electrical current depends on the flow

of electrons and holes through the solid.

A trap can capture and immobilize an electron or hole and prevent its recombination with

the carrier of opposite charge as an electron-hole pair. Electrons and holes may break free from

traps quickly, or they may remain there for an extended period of time (e.g., several months or

longer). Charge carriers can be released from traps by the addition of energy, such as irradiating

the solid with light or by heating it.

5.9.4.1. Deep-level traps

Deep-level traps or deep-level defects are a generally undesirable type of electronic defect

in semiconductors. They are "deep" in the sense that the energy required to remove an electron or

hole from the trap to the valence or conduction band is much larger than the characteristic

thermal energy kT, where k is the Boltzmann constant and T is temperature. Deep traps interfere

with more useful types of doping by compensating the dominant charge carrier type, annihilating

either free electrons or electron holes depending on which is more prevalent. They also directly

interfere with the operation of transistors, light-emitting diodes and other electronic and opto-

electronic devices, by offering an intermediate state inside the band gap. Deep-level traps shorten

the non-radiative life time of charge carriers, and—through the Shockley–Read–Hall (SRH)

process—facilitate recombination of minority carriers, having adverse effects on the

semiconductor device performance.

5.9.4.2. Surface traps

Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their

atomistic origin and manipulating them chemically have capital importance to design defect-free

colloidal quantum dots and make a leap forward in the development of efficient optoelectronic

devices. Recent advances in computing power established computational chemistry as a powerful

tool to describe accurately complex chemical species and nowadays it became conceivable to

model colloidal quantum dots with realistic sizes and shapes

In perfect semiconductors, there exist a band gap (forbidden band) composed of valence band

(bottom) and conduction band (top). When defects are introduced (such as impurities, vacancies,
interstitial), there exist allowed energy states somewhere in the band gap. The states that are

close to the band edges (either conduction band or valence band), then we call them shallow

traps. If the states are close to the middle of band gap, then we call them deep traps.

1) are the deep (or shallow) traps different for both hole and electron?

2) when people mention deep traps, should not they specify whether the deep traps belong to

electron or hole?

Comment 1: A defect will create an eigenstate or band (depending upon the density of the

defect), but, it is not necessary that this state will lie inside the band-gap.

Comment 2: Shallow states (ionisation energy of the order of kT) generally act as dopants, if

they satisfy some conditions: valency one less or one more than the host atom(s) and is of nearly

the same atomic size.

Dopants are classified as donors or acceptors; donors donate an electron to the

conduction band, whereas acceptors accept an electron from the valence band. Deep traps

generally act as recombination-generation centres and are not classified as donors or acceptor

levels. The reason is that the generation-recombination centres have to capture/emit both

electrons and holes. The capture/emission cross-section of a deep trap will depend upon several

factors: (1) whether the process is capture or emission; (2) the ionisation energy of the trap; (3)

whether the trap is neutral, or positively or negatively charged; (4) whether the trap is in the bulk

or is at the interface.

A deep trap is most effective (e.g. Au in Si) as a recombination centre if the hole capture (from

VB) time is nearly the same as the electron capture (from CB) time.
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[1] International Technology Roadmap for Semiconductors (ITRS).

2015. URL: http://www.itrs2.net.

[2] C. Tavernier, F. Pereira, O. Nier, D. Rideau, F. Monsieur, G. Torrente, M. Haond, et al.

“TCAD Modeling Challenges for 14nm Fully-Depleted SOI Technology Performance

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International Conference on. 2015, pp. 4–7. DOI: 10.1109/SISPAD.2015.7292244.

[3] V. Moroz, L. Smith, J. Huang, M. Choi, T. Ma, J. Liu, Y. Zhang, et al. “Modeling and

Optimization of Group IV and III FinFETs and Nano-Wires”. In: Electron Devices Meeting

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9783642105852.

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[10] D. Dolgos. “Full-Band Monte Carlo Simulation of Single Photon Avalanche Diodes”.

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Chapter VI

APPLICATIONS:

Applications of nanoparticles, quantum dots, nanowires and thin films for photonic devices
(LED, solar cells). Single electron transfer devices (no derivation). CNT based transistors.
Nanomaterial Devices: Quantum dots heterostructure lasers, optical switching and optical data
storage. Magnetic quantum well; magnetic dots - magnetic data storage.Micro
Electromechanical Systems (MEMS), Nano Electromechanical Systems (NEMS).
6. Application of Nanomaterials

One of the most important fields of current interest in nanostructured materials is the

fundamental aspects and possible applications in nanostractured form of materials in

nanodevices for better performances. Although considerable progress has been achieved in the

theoretical understanding of the properties of nanomaterials, there still exists a number of

problem, which should have to be solved and well understood, before this new technology can

be applied in real applications. As the surface plays the crucial role in determining the different

electrical and optical properties, hence motivated study is necessary of carefully synthesized

the thin films of these nanostructured materials.

Tremendous technological advancements in the field of nanostructured materials have

gained immense importance in recent years because of some unconventional properties exhibited

by them and challenging problem thrown up for providing the theoretical concepts in physics

associated with it. The preparations of nanometer size crystallites open the opportunity of

observing the evolution of physical properties of the materials with sizes. The reduction of sizes

with which the bulk properties change remarkably and provide the possibility of observing novel

behaviors such as size dependent structural, electrical and optical properties. The physics

associated with these properties of nanocrystallites of II-VI semiconductors have been very

interesting because of thinking the phenomena in a new point of view with the properties

exhibited by them. Nanocrystalline semiconductors have attracted much attention due to their
novel properties and varieties of promising potentials in extensive applications. Numerous

technical advancements in the field of nanostructured materials have stimulated the wide range

of research interest in recent years because of various new properties exhibited by them.

Recently, nanostructured semiconductor are widely used to design a rich varieties of device for

microelectronics. One-dimensional nanostructured materials have gained special interest in the

assembly of nanodevices. Nanometer-scale electronics have been predicted to play an important

role in device technology. Quantum wires of semiconductors and metallic alloys have found to

exhibit interesting magnetic and electrical properties. The nanostructure transparent conducting

oxides have also gained tremendous importance due to their size dependent optical properties

and possible applications in near future.

6.1. Applications of nanoparticles

Nanotechnology [1] is enabling technology that deals with nano-meter sized objects. It is

expected that nanotechnology will be developed at several levels: materials, devices and systems.

The nanomaterials level is the most advanced at present, both in scientific knowledge and in

commercial applications. A decade ago, nanoparticles were studied because of their size-

dependent physical and chemical properties [2]. Now they have entered a commercial

exploration period [3, 4].

Living organisms are built of cells that are typically 10 μm across. However, the cell parts are

much smaller and are in the sub-micron size domain. Even smaller are the proteins with a typical

size of just 5 nm, which is comparable with the dimensions of smallest manmade nanoparticles.

This simple size comparison gives an idea of using nanoparticles as very small probes that would

allow us to spy at the cellular machinery without introducing too much interference [5].
Understanding of biological processes on the nanoscale level is a strong driving force behind

development of nanotechnology [6].

Out of plethora of size-dependant physical properties available to someone who is interested in

the practical side of nanomaterials, optical [7] and magnetic [8] effects are the most used for

biological applications.

The aim of this review is firstly to give reader a historic prospective of nanomaterial application

to biology and medicine, secondly to try to overview the most recent developments in this field,

and finally to discuss the hard road to commercialisation. Hybrid bionanomaterials can also be

applied to build novel electronic, optoelectronics and memory devices (see for example [9, 10]).

Nevertheless, this will not be discussed here and will be a subject of a separate article.

A list of some of the applications of nanomaterials to biology or medicine is given below:

 Fluorescent biological labels [11–13]

 Drug and gene delivery [14, 15]

 Bio detection of pathogens [16]

 Detection of proteins [17]

 Probing of DNA structure [18]

 Tissue engineering [19, 20]

 Tumour destruction via heating (hyperthermia)[21]

 Separation and purification of biological molecules and cells [22]

  MRI contrast enhancement [23]

 Phagokinetic studies [24]

As mentioned above, the fact that nanoparticles exist in the same size domain as proteins makes

nanomaterials suitable for bio tagging or labelling. However, size is just one of many

characteristics of nanoparticles that itself is rarely sufficient if one is to use nanoparticles as

biological tags. In order to interact with biological target, a biological or molecular coating or

layer acting as a bioinorganic interface should be attached to the nanoparticle. Examples of

biological coatings may include antibodies, biopolymers like collagen [25], or monolayers of

small molecules that make the nanoparticles biocompatible. In addition, as optical detection

techniques are wide spread in biological research, nanoparticles should either fluoresce or

change their optical properties.

Cancer therapy

Photodynamic cancer therapy is based on the destruction of the cancer cells by laser generated

atomic oxygen, which is cytotoxic. A greater quantity of a special dye that is used to generate the

atomic oxygen is taken in by the cancer cells when compared with a healthy tissue. Hence, only

the cancer cells are destroyed then exposed to a laser radiation. Unfortunately, the remaining dye

molecules migrate to the skin and the eyes and make the patient very sensitive to the daylight

exposure. This effect can last for up to six weeks.

To avoid this side effect, the hydrophobic version of the dye molecule was enclosed inside a

porous nanoparticle [28]. The dye stayed trapped inside the Ormosil nanoparticle and did not
spread to the other parts of the body. At the same time, its oxygen generating ability has not been

affected and the pore size of about 1 nm freely allowed for the oxygen to diffuse out.

***

6.2. Applications of Quantum Dots

Quantum dots (QDs) are often referred to very tiny man-made semiconductor particles, whose

size are normally no more than 10 nanometers. Their extremely small size renders their optical

and electronic properties different from those of bulk materials. A majority of QDs have the

ability to emit light of specific wavelengths if excited by light or electricity. According to

existing literature, the electronic characteristics of QDs are determined by their size and shape,

which means we can control their emission wavelengths by tuning their size

Applications

1. Bioimaging

Various kinds of organic dyes have been used in bioimaging for decades. However, most of the

organic dyes suffer from low quantum yield and photostability. However, with the advancement

of nanotechnology, QDs have been considered to be superior to traditional organic dyes in many

respects. For example, it has been found that QDs are 20 times brighter and 100 times more

stable more than traditional fluorescent reporters. With well-established inorganic synthetic

techniques now are available for generating QDs with high brightness. For bioimaging

applications, the fluorescent probes have to remain well-dispersed and stable in the aqueous

medium with a wide range of pH and ionic strengths. Fortunately, numerous approaches have

been developed to make the QDs water-dispersible. Up until now, great efforts have been

devoted to employing QDs for in vitro and in vivo imaging, which are expected to be important
to the diagnoses of many diseases, the understanding of embryogenesis, and lymphocyte

immunology.

2. Photovoltaic devices

Because of the tunable of the absorption spectrum and high extinction coefficient, QDs are

desirable for light harvesting, is beneficial for photovoltaic devices. QDs have the potential to

boost the efficiency of silicon photovoltaic cells and lead to reduced costs.

3. Light emitting devices

QDs are promising for light emitting devices and may improve the performance of light-emitting

diode (LED), leading to the new design of “Quantum Dot light Emitting Diode”. QDs are very

useful for display devices considering their unique optical properties. They are capable of

presenting visibly more accurate and outstanding colors. A proof-of-concept QDs display has

been successfully achieved from technical perspective years ago, and shows a good performance

and bright emission in the region of visible and near infrared spectrum.

Nanowire

A nanowire is a nanostructure, with the diameter of the order of a nanometer (10−9 meters). It can

also be defined as the ratio of the length to width being greater than 1000. Alternatively,

nanowires can be defined as structures that have a thickness or diameter constrained to tens

of nanometers or less and an unconstrained length. At these scales, quantum mechanical effects

are important—which coined the term "quantum wires".

The nanowire geometry provides potential advantages over planar wafer-based or thin-film solar

cells in every step of the photoconversion process. These advantages include reduced reflection,

extreme light trapping, im-proved band gap tuning, facile strain relaxation, and increased defect
toler-ance. These benefits are not expected to increase the maximum efficiency above standard

limits; instead, they reduce the quantity and quality of mate-rial necessary to approach those

limits, allowing for substantial cost reduc-tions. Additionally, nanowires provide opportunities to

fabricate complex single-crystalline semiconductor devices directly on low-cost substrates and

electrodes such as aluminum foil, stainless steel, and conductive glass, ad-dressing another major

cost in current photovoltaic technology. This review describes nanowire solar cell synthesis and

fabrication, important charac-terization techniques unique to nanowire systems, and advantages

of the nanowire geometry.

Several physical reasons predict that the conductivity of a nanowire will be much less than that

of the corresponding bulk material. First, there is scattering from the wire boundaries, whose

effect will be very significant whenever the wire width is below the free electron mean free path

of the bulk material. In copper, for example, the mean free path is 40 nm. Copper nanowires less

than 40 nm wide will shorten the mean free path to the wire width.

Nanowires also show other peculiar electrical properties due to their size. Unlike single wall

carbon nanotubes, whose motion of electrons can fall under the regime of ballistic

transport (meaning the electrons can travel freely from one electrode to the other), nanowire

conductivity is strongly influenced by edge effects. The edge effects come from atoms that lay at

the nanowire surface and are not fully bonded to neighboring atoms like the atoms within the

bulk of the nanowire. The unbonded atoms are often a source of defects within the nanowire, and

may cause the nanowire to conduct electricity more poorly than the bulk material. As a nanowire

shrinks in size, the surface atoms become more numerous compared to the atoms within the

nanowire, and edge effects become more important.

Furthermore, the conductivity can undergo a quantization in energy: i.e. the energy of the

electrons going through a nanowire can assume only discrete values, which are multiples of

the conductance quantum G = 2e2/h (where e is the charge of the electron and h is the Planck

constant. See also the Quantum Hall effect).

Nanowires can be used for MOSFETs (MOS field-effect transistors). MOS transistors are used

widely as fundamental building elements in today's electronic circuits.[32][33] As predicted

by Moore's law, the dimension of MOS transistors is shrinking smaller and smaller into

nanoscale. One of the key challenges of building future nanoscale MOS transistors is ensuring

good gate control over the channel. Due to the high aspect ratio, if the gate dielectric is wrapped

around the nanowire channel, we can get good control of channel electrostatic potential, thereby

turning the transistor on and off efficiently.

Due to the unique one-dimensional structure with remarkable optical properties, the nanowire

also opens new opportunities for realizing high efficiency photovoltaic devices.[34] Compared

with its bulk counterparts, the nanowire solar cells are less sensitive to impurities due to bulk

recombination, and thus silicon wafers with lower purity can be used to achieve acceptable

efficiency, leading to the a reduction on material consumption.[35]

To create active electronic elements, the first key step was to chemically dope a semiconductor

nanowire. This has already been done to individual nanowires to create p-type and n-type

semiconductors.

The next step was to find a way to create a p–n junction, one of the simplest electronic devices.

This was achieved in two ways. The first way was to physically cross a p-type wire over an n-

type wire. The second method involved chemically doping a single wire with different dopants

along the length. This method created a p-n junction with only one wire.
After p-n junctions were built with nanowires, the next logical step was to build logic gates. By

connecting several p-n junctions together, researchers have been able to create the basis of all

logic circuits: the AND, OR, and NOT gates have all been built from semiconductor nanowire

crossings.

In August 2012, researchers reported constructing the first NAND gate from undoped silicon

nanowires. This avoids the problem of how to achieve precision doping of complementary

nanocircuits, which is unsolved. They were able to control the Schottky barrier to achieve low-

resistance contacts by placing a silicide layer in the metal-silicon interface.[36]

It is possible that semiconductor nanowire crossings will be important to the future of digital

computing. Though there are other uses for nanowires beyond these, the only ones that actually

take advantage of physics in the nanometer regime are electronic.[37]

In addition, nanowires are also being studied for use as photon ballistic waveguides as

interconnects in quantum dot/quantum effect well photon logic arrays. Photons travel inside the

tube, electrons travel on the outside shell.

When two nanowires acting as photon waveguides cross each other the juncture acts as

a quantum dot.

Conducting nanowires offer the possibility of connecting molecular-scale entities in a molecular

computer. Dispersions of conducting nanowires in different polymers are being investigated for

use as transparent electrodes for flexible flat-screen displays.

Because of their high Young's moduli, their use in mechanically enhancing composites is being

investigated. Because nanowires appear in bundles, they may be used as tribological additives to

improve friction characteristics and reliability of electronic transducers and actuators.

Because of their high aspect ratio, nanowires are also uniquely suited

to dielectrophoretic manipulation,[38][39][40] which offers a low-cost, bottom-up approach to

integrating suspended dielectric metal oxide nanowires in electronic devices such as UV, water

vapor, and ethanol sensors.[41]

***

The Physics of Single Electron Transistor

The single electron transistor is made of an island connected through two tunneling junctions to

a drain and a source electrode, and through a capacitor to a gate electrode (Figure 1). When

there is no bias on any electrode, electrons in the system do not have enough energy to tunnel

through the junctions.

A conventional field-effect transistor, the kind that makes all modern electronics work, is a

switch that turns on when electrons are added to a semiconductor and turns off when they are

removed. These on and off states give the ones and zeros that digital computers need for

calculation. Interestingly, these transistors are almost completely classical in their physics. Only

a few numbers that characterize their behavior are affected by quantum mechanics. However, if

one makes a new kind of transistor, in which the electrons are confined within a small volume

and communicate with the electrical leads by tunneling, all this changes. One then has a

transistor that turns on

and off again every time one electron is added to it, we call it a single electron transistor

(SET).
 There are a variety of materials chosen for single electron transistors based on the

particular properties desired in the system. Relevant properties include the capacitance of the

material, the ease of fabrication, crystalline structure, electron mobility, and ease of growing

oxide layers. There are two classes of single electron transistors used today, “metallic " and

“semiconducting”. This refers to the material they are commonly fabricated from as opposed

to describing in any way their operation. Both function through the process of tunneling

junctions.

1. Applications of Set

Charge Sensor

The Single-electron transistors (SETs) are efficient charge sensors for reading out spin or

charge qubits confined in quantum dots (QDs). To investigate their capacitive parameters,

which are related to the signal-to-noise ratio (SNR) during qubit readout, twin silicon single

QDs were fabricated using a lithographic process on a silicon-on- insulator substrate. Since

the configuration and dimensions of the QDs could be determined by direct imaging, the

theoretical capacitive parameters could be compared to the measured values. Good agreement

was found between the calculated and measured value, which confirms the validity of the

calculation method. The results indicated that decreasing the SET diameter reduces the

capacitive coupling between qubits but increases the signal-to-noise ratio for both dc and radio

frequency single- shot measurements. Since these results are independent of the device

materials, they are useful for establishing guidelines for the design of SET charge sensors in

lateral QD-SET structures based on a two-dimensional electron gas.

Detection of Infrared Radiation

The single-electron transistor can also be used to detect infrared signals at room temperature.

By exciting electrons over an electrically induced energy barrier, both the range of detectable

wavelengths and the sensitivity of the device can be controlled. The sensor works when an

infrared signal excites conduction-band electrons in a 25-nm- deep electron reservoir. A silicon

insulator channel measuring 40 × 400 nm is placed next to the reservoir to increase the number

of excited electrons. A poly-silicon lower gate then turns off the transistor and electrically

forms an energy barrier, creating a storage node on the other side. Electrons with energy greater

than the height of the barrier are injected into the storage node, where they are read as changes

in current flowing through the transistor.

Detection of Infrared Radiation

The single-electron transistor can also be used to detect infrared signals at room temperature.

By exciting electrons over an electrically induced energy barrier, both the range of detectable

wavelengths and the sensitivity of the device can be controlled. The sensor works when an

infrared signal excites conduction-band electrons in a 25-nm- deep electron reservoir. A

silicon insulator channel measuring 40 × 400 nm is placed next to the reservoir to increase the

number of excited electrons. A poly-silicon lower gate then turns off the transistor and

electrically forms an energy barrier, creating a storage node on the other side. Electrons with

energy greater than the height of the barrier are injected into the storage node, where they are

read as changes in current flowing through the transistor.

Ultrasensitive Microwave Detector

Another application of Single Electron Transistor can be as an Ultrasensitive Microwave

Detector; island is weakly coupled to a bias circuit through two small- capacitance tunnel
 junctions and a capacitive gate. At low bias voltages and temperatures, a single quasiparticle

may only be introduced to the island through photon-assisted tunneling. Once this occurs, the

quasiparticle is trapped on the island because it takes a relatively long time for this specific

quasiparticle to tunnel off. While it is trapped, charge is transported through the system two

electrons at a time. Since the photon-assisted transition merely switches the detector current on,

this device is not limited to one electron tunneled through the system per absorbed photon.

This makes the device an extremely sensitive and potentially useful detector of microwave

radiation.

Temperature Standards

Theoretical analysis based on the orthodox theory has shown that ∆V= 5.44NkBT/e is

surprisingly stable with respect to almost any variations of the array parameters (with the

important exception of a substantial spread in the junctions’ resistances), providing a

remarkable opportunity to use the arrays for absolute thermometry, since the fundamental

constants are known with high accuracy. Each particular array may give high (1%) accuracy

of within less than one decade of temperature variations, but for arrays with different island

size (and hence different), these ranges may be shifted and overlap. Thus, it is possible to have

an absolute standard of temperature with a very broad (say, two-decade) total range from

several circuits fabricated on a single chip.

This development is very encouraging, but since all this work is recent, some time is

needed to see whether these new devices will be able to compete with (or even replace) the

established temperature standards.

Supersensitive Electrometer
 The technology of fabrication of tunnel barriers for single-electron devices is still in its

infancy, they apparently contain many electron trapping centers and other two-level systems

capable of producing “telegraph noise”- random low-frequency variations of the barrier

conductance.

The high sensitivity of single-electron transistors have enabled to use them as

electrometers in unique physical experiments. For example, they have made possible

unambiguous observations of the parity effects in superconductors. Absolute measurements of

extremely low dc currents (~10-20 A) have been demonstrated. The transistors have also been

used in the first measurements of single-electron effects in single-electron boxes and traps. A

modified version of the transistor has been used for the first proof of the existence of

fractional-charge excitations in the fractional quantum hall effect.

Single-Electron Spectroscopy

Another application of single-electron electrometry is the possibility of measuring the electron

addition energies (and hence the energy level distribution) in quantum dots and other

nanoscale objects. There are two natural ways to carry out such measurements. The first is to

use the quantum dot as the island of the single-electron box, capacitively coupled to the single

electron transistor or other sensitive electrometer. The second is to use the quantum dot

directly as the island of a weakly biased single-electron transistor and measure the gate

voltages providing the sharp increase of the source-drain conductance.

2. Limitations in Set Implementations

Back Ground Charge

 The first major problem with the single electron logic circuits is the infamous randomness of

the background charge. A single charged impurity trapped in the insulating environment

polarizes the island, creating on its surface an image charge Q0 of the order of e. This charge

is effectively subtracted from the external charge Qe.

Room Temperature

The another big problem with all the known types of single electron logic devices is the

requirement Ec~100kB T, which in practice means sub-nanometer island size for room

temperature operation. In such small conductors the quantum kinetic energy gives a dominant

contribution to the electron additional energy even small variations in island shape will lead to

unpredictable and rather substantial variations in the spectrum of energy levels and hence in the

device switching threshold.

Out Side Environment Linking with SETs

The individual structures patterns which function as logic circuits must be arranged in to larger

2D patterns. There are two ideas, first is to integrate SET as well as related equipments with the

existing MOSFET, this is attractive because it can increase the integrating density. The second

option is to give up linking by wire, instead utilizing the static electronic force between the

basic clusters to form a circuit linked by cluster, which is called quantum cellular automata

(QCA). The advantage of QCA is its first information transfer velocity between cells via

electrostatic interaction only, no wire is needed between arrays and the size of each cell can be

as small as 2.5 nm, this made them very suitable for high density memory and next generation

quantum computer.

Lithography Technique
Another major problem with single electron devices is the requirement Ec~100kB T, which in

practice means sub-nanometer island size for room temperature operation. In VLSI circuits, this

fabrication technology level is very difficult. Moreover, even if these islands are fabricated by

any sort of nanolithography, their shape will hardly be absolutely regular.

Co-tunneling

The pressure essence of the effect is that the tunneling of several electrons through different

barriers at the same time is possible as a single coherent quantam mechanical process. The rate

of the process is crudely less than that for the single electron tunneling.

***

Quantum dot laser

A quantum dot laser is a semiconductor laser that uses quantum dots as the active laser

medium in its light emitting region. Due to the tight confinement of charge carriers in quantum

dots, they exhibit an electronic structure similar to atoms. Lasers fabricated from such an active

media exhibit device performance that is closer to gas lasers, and avoid some of the negative

aspects of device performance associated with traditional semiconductor lasers based on bulk

or quantum well active media. Improvements in modulation bandwidth, lasing threshold, relative

intensity noise, linewidth enhancement factor and temperature insensitivity have all been

observed. The quantum dot active region may also be engineered to operate at different

wavelengths by varying dot size and composition. This allows quantum dot lasers to be

fabricated to operate at wavelengths previously not possible using semiconductor laser

technology.
Recently, devices based on quantum dot active media are finding commercial application in

medicine (laser scalpel, optical coherence tomography), display technologies (projection, laser

TV), spectroscopy and telecommunications. A 10 Gbit/s quantum dot laser that is insensitive to

temperature fluctuation for use in optical data communications and optical networks has been

developed using this technology

Optical storage

Optical storage is the storage of data on an optically readable medium. Data is recorded by

making marks in a pattern that can be read back with the aid of light, usually a beam

of laser light precisely focused on a spinning optical disc. An older example of optical

storage that does not require the use of computers, is microform. There are other means of

optically storing data and new methods are in development. An optical disc drive is a device

in a computer that can read CD-ROMs or other optical discs, such as DVDs and Blu-

ray discs. Optical storage differs from other data storage techniques that make use of other

technologies such as magnetism, such as floppy disks and hard disks, or semiconductors,

such as flash memory and RAM.

Optical switch

An optical switch is a device that selectively switches optical signals on or off or from one

channel to another. The former is known as an optical (time-domain) switch or an optical

modulator, while the latter is called an optical space switch or an optical router. Since the

switching can be temporal or spatial, such switches are analogous to one-way or two-way

switches in electrical circuits. In general, optical modulators and routers can be made from

each other.
An optical switch may operate by mechanical means, such as physically shifting an optical

fiber to drive one or more alternative fibers, or by electro-optic effects, magneto-optic

effects, or other methods. Slow optical switches, such as those using moving fibers, may be

used for alternate routing of an optical switch transmission path, such as routing around

a fault. Fast optical switches, such as those using electro-optic or magneto-optic effects, may

be used to perform logic operations; also included in this category are semiconductor optical

amplifiers, which are optoelectronic devices that can be used as optical switches and be

integrated with discrete or integrated microelectronic circuits.

Optical switching technology is driven by the need to provide flexibility in optical network

connectivity. Prime applications are optical protection, test systems, remotely reconfigurable

add-drop multiplexers, and sensing. Possible future applications include remote optical

provisioning and restoration.

Current switching applications include passive protection switching for service restoration

following a disruption, such as a fiber cut. One common application for switches is in Remote

Fiber Test Systems (RFTSs) that can monitor and locate a fault on a fiber transmission line.[3] An

emerging application of optical switches is optical cross-connection. Optical cross-connects

utilize optical switching fabrics to establish an interconnection between multiple optical inputs

and outputs.

Magnetic storage or magnetic recording

Magnetic storage or magnetic recording is the storage of data on a magnetized medium.

Magnetic storage uses different patterns of magnetisation in a magnetisable material to store

data and is a form of non-volatile memory. The information is accessed using one or

more read/write heads.

magnetic storage is the storage on a magnetized medium. Magnetic storage utilizes different

patterns of magnetization in a magnet sable material to store data in non-volatile memory.

The information is retrieved using one or more read/write heads. The first magnetic data

stores used information stored on the surface of drums than disks. Drums are easy to design

with the required acceptances and read/write heads could be provided for each track,

staggered around the circumference. There was no head movement to control which made

the extreme access time quite short one revolution of the drum. With multiple heads, data

could be transported “word parallel” so data transmission rates might be quite high,

compensating for the slow, non-random access.

Data are stored in hard drives in the form of ‘bits’, tiny magnetic domains with a North and a

South pole. Conventionally, the switching occurs when an external magnetic field is applied,

which would force the direction of the poles either up or down. Alternatively, switching can be

achieved via the application of a short femtosecond laser pulse in an all-optical switching, and

results in a more efficient and much faster storage of data. Mark Lalieu, PhD candidate at the

Applied Physics Department, says: “All-optical switching for data storage has been known for

about a decade. When all-optical switching was first observed in ferromagnetic materials –

amongst the most promising materials for magnetic memory devices – this research field gained

a great boost”. However, the switching of the magnetization in these materials requires multiple

laser pulses and, thus, long data writing times.

Microelectromechanical systems (MEMS), also written as micro-electro-mechanical systems (or

microelectronic and microelectromechanical systems) and the

related micromechatronics and microsystems is the technology of microscopic devices,

particularly those with moving parts. It merges at the nanoscale into nanoelectromechanical

systems (NEMS) and nanotechnology. MEMS are also referred to as micromachines in Japan

and microsystem technology (MST) in Europe.

What is MEMS Technology?

Micro-Electro-Mechanical Systems, or MEMS, is a technology that in its most general form

can be defined as miniaturized mechanical and electro-mechanical elements (i.e., devices and

structures) that are made using the techniques of microfabrication. The critical physical

dimensions of MEMS devices can vary from well below one micron on the lower end of the

dimensional spectrum, all the way to several millimeters. Likewise, the types of MEMS devices

can vary from relatively simple structures having no moving elements, to extremely complex

electromechanical systems with multiple moving elements under the control of integrated

microelectronics. The one main criterion of MEMS is that there are at least some elements

having some sort of mechanical functionality whether or not these elements can move. The term

used to define MEMS varies in different parts of the world. In the United States they are

predominantly called MEMS, while in some other parts of the world they are called

“Microsystems Technology” or “micromachined devices”.

While the functional elements of MEMS are miniaturized structures, sensors, actuators, and

microelectronics, the most notable (and perhaps most interesting) elements are the microsensors

and microactuators. Microsensors and microactuators are appropriately categorized as

“transducers”, which are defined as devices that convert energy from one form to another. In the

case of microsensors, the device typically converts a measured mechanical signal into an

electrical signal.

Some common commercial applications of MEMS include:

 Inkjet printers, which use piezoelectrics or thermal bubble ejection to deposit ink on paper.

 Accelerometers in modern cars for a large number of purposes including airbag deployment

and electronic stability control.

 Inertial Measurement Units (IMUs): MEMS Accelerometers and MEMS gyroscopes in

remote controlled, or autonomous, helicopters, planes and multirotors (also known as

drones), used for automatically sensing and balancing flying characteristics of roll, pitch and

yaw. MEMS magnetic field sensor (magnetometer) may also be incorporated in such devices

to provide directional heading. MEMS are also used in Inertial navigation systems (INSs) of

modern cars, airplanes, submarines and other vehicles to detect yaw, pitch, and roll; for

example, the autopilot of an airplane.[27]

 Accelerometers in consumer electronics devices such as game controllers (Nintendo Wii),

personal media players / cell phones (virtually all smartphones, various HTC PDA

models)[28] and a number of Digital Cameras (various Canon Digital IXUS models). Also

used in PCs to park the hard disk head when free-fall is detected, to prevent damage and data

loss.
 MEMS microphones in portable devices, e.g., mobile phones, head sets and laptops. The

market for smart microphones includes smartphones, wearable devices, smart home and

automotive applications.[29]

 Precision temperature-compensated resonators in real-time clocks.[30]

 Silicon pressure sensors e.g., car tire pressure sensors, and disposable blood pressure sensors

 Displays e.g., the digital micromirror device (DMD) chip in a projector based

on DLP technology, which has a surface with several hundred thousand micromirrors or

single micro-scanning-mirrors also called microscanners

 Optical switching technology, which is used for switching technology and alignment for data

communications

 Bio-MEMS applications in medical and health related technologies from Lab-On-Chip to

MicroTotalAnalysis (biosensor, chemosensor), or embedded in medical devices e.g.

stents.[31]

 Interferometric modulator display (IMOD) applications in consumer electronics (primarily

displays for mobile devices), used to create interferometric modulation − reflective display

technology as found in mirasol displays

 Fluid acceleration such as for micro-cooling

 Micro-scale energy harvesting including piezoelectric,[32] electrostatic and electromagnetic

micro harvesters.

 Micromachined ultrasound transducers.[33][34]

***

Nanoelectromechanical systems (NEMS)

Nanoelectromechanical systems (NEMS) are a class of devices integrating electrical and

mechanical functionality on the nanoscale. NEMS form the next logical miniaturization step

from so-called microelectromechanical systems, or MEMS devices. NEMS typically integrate

transistor-like nanoelectronics with mechanical actuators, pumps, or motors, and may thereby

form physical, biological, and chemical sensors.

Applications

 Nanoelectromechanical relay

 Nanoelectromechanical systems mass spectrometer

A nanoelectromechanical (NEM) relay is an electrically actuated switch that is built on

the nanometer scale using semiconductor fabrication techniques. They are designed to operate in

replacement, or in conjunction, with traditional semiconductor logic. While the mechanical

nature of NEM relays makes them switch much slower than solid-state relays, they have many

advantageous properties, such as zero current leakage and low power consumption, which make

them potentially useful in next generation computing.

A nanoelectromechanical systems mass spectrometer (NEMS-MS) is an instrument

measuring the mass of analyte particles by detecting the frequency shift caused by the adsorption

of the particles on a NEMS resonator.

6.1. Unique properties conducting transparentnano films and possible application:

Highly conducting transparent CdO thin films may find many applications such as a low

resistance contact to the junction, gas sensors etc. Metallic CdO coating onto glass container may

also reduce appreciably the coefficient of friction of the glass surfaces and thereby facilitate the

movement of the containers through high-speed fitting lines. Apart from these, highly conducting

CdO coating may be used for the production of heating layers for protecting vehicle windscreens

from freezing and misting over; light transmitting electrodes for development of optoelectronic

devices; antistatic surface layers on temperature control coatings in orbiting satellites and surface

layers in electroluminescent applications. Again in nanostructured form, it will not be used as

high conducting materials. But as surface area increases in nanostructured form, the material

become more reactive and hence sensing activity (in gas sensor) and photocatalytic activity

enhances.

It is well known that the mobility of charge carriers in a TCO thin film affects both the

electrical and the optical properties. To obtain high conductance and transmittance, a high

mobility material required to minimize the free-carrier absorption of nearinfrared radiation. Both

high mobility and carrier concentration lead to reductions in the resistivity of TCO materials.

However, simply increasing the carrier concentration increases the free carrier absorption and

moves the absorption band toward the short-wavelength portion of the visible spectrum i.e.

Burstein–Moss (BM) shift take place. At excessively high concentrations, this causes the familiar

visual browning of the films. Therefore, increasing the mobility is the only useful option for

increasing the conductivity and reducing the free-carrier absorption. The mobility of a

semiconductor is directly proportional to the carrier relaxation time and inversely proportional to

the effective mass of the carriers; so the only options available are to increase the former or to
decrease the latter. Defects in the film can cause charge scattering that reduces the relaxation

time.

6.2. Applications of Nano materials Ozone Layer Recovery

Though the ozone layer has been repairing itself spontaneously, in spite of this, it has been

observed that there is a constantly decreasing of the ozone in the ozone layer of the stratosphere,

as the process of recovering has been taking place very slowly and also the man-made ozone

depleting compounds increasing more and more. As a result the possibility of ozone hole

recovery remain uncertain. By modern nanoscience research, there is a finite prospect of ozone

recovery by developing nanostructure titanium oxide (TiO2) materials [21-24] that can cause

photodriven remediation reaction to control the offensive order in the atmosphere and recover

the ozone layer to make the environment clean.

Nanostructure titanium oxide (TiO2) materials can be used as oxygen generator and ozone hole

compensator. The nanostructured TiO2 can convert the different oxides of nitrogen such as NO,

NO2 etc and the different oxides of sulpher such as SO, SO2 etc and CO2 into O2 and N, S, C

respectively in presence of visible light. Even nanostructured TiO2 can convert the water vapour

into O2 and H2 in presence of visible light. When these O2 are reached at upper atmosphere over

the equatorial belt, in presence of UV photon O2 is converted into O3 in this way ozone hole

may be compensated.

Different types of offensive ordered in the atmosphere such as CO2, different oxides of sulpher

and nitrogen, chlorofluorocarbon etc are the potential ozone depletors. Due to decrease of ozone

layer increase in the amounts of ultraviolet radiation received at the earth surface and it affects

the living part of the environment. As civilization advances, industrialization also increases, as
results different types of offensive orders in the atmosphere also increases. To control it, our

approach has to be changed that can be done by developing nanostructure materials such as

titanium oxide (TiO2) that can cause photo driven remediation reaction to control the offensive

order and make the environment clean. We also must have to be aware about the cause of

production of O3 hole and we have to minimize the use of such materials that produces offensive

orders in the atmosphere.

The impact of nanotechnology

The impact of nanotechnology extends from its medical, ethical, mental, legal and

environmental applications, to fields such as engineering, biology, chemistry, computing,

materials science, and communications. Major benefits of nanotechnology include improved

manufacturing methods, water purification systems, energy systems, physical

enhancement, nanomedicine, better food production methods, nutrition and large-scale

infrastructure auto-fabrication

Energy Advantages

Nanotechnology may transform the ways in which we obtain and use energy. In particular, it's

likely that nanotechnology will make solar power more economical by reducing the cost of

constructing solar panels and related equipment. Energy storage devices will become more

efficient as a result. Nanotechnology will also open up new methods of generating and storing

energy.

Advantages in Electronics and Computing

The field of electronics is set to be revolutionized by nanotechnology. Quantum dots, for

example, are tiny light-producing cells that could be used for illumination or for purposes such as
display screens. Silicon chips can already contain millions of components, but the technology is

reaching its limit; at a certain point, circuits become so small that if a molecule is out of place the

circuit won't work properly. Nanotechnology will allow circuits to be constructed very accurately

on an atomic level.

Medical Advantages

Nanotechnology has the potential to bring major advances in medicine. Nanobots could be sent

into a patient's arteries to clear away blockages. Surgeries could become much faster and more

accurate. Injuries could be repaired cell-by-cell. It may even become possible to heal genetic

conditions by fixing the damaged genes. Nanotechnology could also be used to refine drug

production, tailoring drugs at a molecular level to make them more effective and reduce side

effects.

Environmental Effects

Some of the more extravagant negative future scenarios have been debunked by experts in

nanotechnology. For example: the so-called "gray goo" scenario, where self-replicating nanobots

consume everything around them to make copies of themselves, was once widely discussed but

is no longer considered to be a credible threat. It is possible, however, that there will be some

negative effects on the environment as potential new toxins and pollutants may be created by

nanotechnology.

Privacy and Security

Nanotechnology raises the possibility of microscopic recording devices, which would be

virtually undetectable. More seriously, it is possible that nanotechnology could be weaponized.

Atomic weapons would be easier to create and novel weapons might also be developed. One
possibility is the so-called "smart bullet," a computerized bullet that could be controlled and

aimed very accurately. These developments may prove a boon for the military; but if they fell

into the wrong hands, the consequences would be dire.

In different industries, there are a number of advantages of nanotechnology, such as in cancer

treatments, nanotechnology is proving to be more effective than the conventional treatment

therapies as it targets the affected area without harming the surrounding parts of the body.

How different food companies are implementing nanotechnology?

Smart Packaging- These special packages contain nanosensors and anti-microbial activators

which will signal the decaying of food. Smart packs can also induce calcium molecules for

people who are suffering from osteoporosis.

Nanocapsules- Nanocapsules induced in food make them a healthy food options, future may see

chocolate chips or tomato sauce as healthy food options.

Smart food- Companies like Nestle are manufacturing smart food which will have the ability to

interact with the consumers. Smart food allows the user to customize the food in their own way

by changing its color or flavor. Infact, a smart food can detect if a person is allergic to certain

ingredients or not.

Nano-robot food production- Companies are also willing to invest in nanorobot who are able to

make food by assembling atoms and molecules of different nutrients. “Instead of harvesting
grain and cattle for carbohydrates and protein, nanobots could assemble the desired steak or

flour from carbon, hydrogen and oxygen atoms present in the air as water and carbon dioxide”.

Nanotechnology has a significant impact and it literally evolved a technological world as we

know it today. It has impressive applications in almost every area whether it is medical science,

ro

botics, manufacturing etc.

Having said that, it also has some major disadvantages and limitations that cannot be neglected.

Since Nanotech has its role to play in most of the industries, we have seen its diversified

limitations in all the industries.

Here are some of the potential disadvantages of Nanotechnology

Disadvantages of Nanotechnology

 One of the biggest disadvantages that the world is facing because of nanotechnology is

the lack of employment in the fields of traditional farming, manufacturing, and industrial

sector and that is because of the vast development of the nanotechnology. Nanotech

devices and machines have taken place of humans to work faster and efficiently, which

has lessened the importance of men power in the field of practical work.

 Increasing development and instant performance have also increased the fall of certain

commodities like diamond and oil. The presence of alternative( Nanotech ) has decreased

the demand because alternates are more efficient and do not require the use of fossil

fuels.
 Diamonds have lost its value because it is now mass produced with the help of

nanotechnology. A manufacturer can now produce the bulk of these products at

molecular scale and decomposition is done to create new components.

 Another big threat, which is born with the advent of nanotechnology, is the easy

accessibility of atomic weapons. Nanotechnology has made these weapons more

powerful and more destructive. Unauthorized, criminal bodies can reach nuclear weapons

easily, and its formulation could be stolen.

 Nanotechnology has increased the chance of the health issues. Due to microscopic size of

nanoparticles, it increases the risk of inhalation that can severely damage lungs and could

also lead to fatal health issues. It increases the risk of damaging the lungs if nanoparticles

are inhaled for 60 seconds.

 At present nanotechnology is on the most expensive technologies and its cost is

increasing day by day. The main reason for not being cost efficient is the molecular

structure and processing of the product. It is difficult for the manufacturers to randomly

produce dynamic products using nanotechnology. Huge pricing of nanotech machines

makes it unaffordable currently.

 Nanotechnology comes with financial risks also, manufacturers have to invest huge

money for starting nanotech plants and if produced products fail to satisfy the customer

then manufacturer bear a lot of loss. The original product cannot be recovered because it

will cost twice as much. Maintenance cost of the product is also very high.
  Nanotechnology also raised some practical commercial problems. Practical problems can

include everything which is to be produced from masses like coal, petroleum.

Nanotechnology does not leave single nanoparticle unused which crashed the small

industries of sub-products of the massive materials, this is the main reason for low

quantity of sub-products of coal and petroleum in the market.

 There are some ethical issues which include the poisoning of mass material which has

been processed at a nanoscale. It may leave negative impacts on the health and industry.

Mass poisoning could happen only if the coatings on the products that nanotechnology

has to produce include poisonous microparticles that can penetrate into the brain when it

comes in contact with humans.

 While nanotechnology can help produce all kinds of goods and improved products, but

the particles that are created are so small that they may cause eventual health problems in

the bodies of consumers.

 Nanotechnology has raised the standard of living but at the same time, it has increased

the pollution in water and air. The pollution caused by nanotechnology is known as Nano

Pollution. Such kind of pollution is very dangerous for living organisms under water &

on earth.

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