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NPTEL – Electrical & Electronics Engineering – Semiconductor Nanodevices

Introduction to Materials and


Classification of Low Dimensional Materials

R. John Bosco Balaguru


Professor
School of Electrical & Electronics Engineering
SASTRA University

B. G. Jeyaprakash
Assistant Professor
School of Electrical & Electronics Engineering
SASTRA University
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Table of Content
1. INTRODUCTION TO MATERIALS................................................................3

1.1 HISTORICAL OUTLOOK........................................................................................................3


1.2 GENERAL CLASSIFICATION OF MATERIALS..................................................................3
1.3 STRUCTURE OF MATERIALS...............................................................................................4
1.4 AMORPHOUS SOLIDS……………………………………………………………………....5
1.5 CRYSTALLINE SOLIDS……………………………………………………………………..6
1.6 SOLIDIFICATION………………………………………………………………………….…6

2. CLASSIFICATION OF LOW DIMENSIONAL MATERIALS....................7

2.1 BASIC PROPERTIES OF LOW DIMENSIONAL


SEMICONDUCTOR NANOSTRUCTURES............................................................................9
2.2 WHY PROPERTIES OF NANOMATERIALS ARE DIFFERENT.......................................10

2.2.1 Increase in surface area to volume………………………………………………….10


2.2.2 Quantum confinement……………………………………………………………….10

2.3 INFLUENCE OF PHYSICAL DIMENSION ON DIFFERENT PROPERTIES....................11

3.3.1 Structural properties………………………………………………………………..11


3.3.2 Thermal properties…………………………………………………………………..12
3.3.3 Chemical properties…………………………………………………………………12
3.3.4 Mechanical properties………………………………………………………………12
3.3.5 Magnetic properties…………………………………………………………………12
3.3.6 Optical properties…………………………………………………………………...13
3.3.7 Electronic properties………………………………………………………………..14

2.4 COMPARISION OF BULK AND NANOSTRUCURED


SEMICONDUCTING MATERIAL........................................................................................15

3. QUIZ AND ASSIGNMENT..............................................................................17

3.1 SOLUTIONS............................................................................................................................17

4. REFERENCES..................................................................................................18

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1 Introduction to Materials
This lecture provides you about the fundamentals of solid materials, its
classification and general properties

1.1 Historical Outlook


Materials are more
important in our everyday
lives. Different materials in
various forms were used in
transportation, housing,
clothing, communication,
recreation, and food
production.Historically, the
development and advancement
of societies have been intimately
tied to the member’s ability to
produce and deploy materials to
fill their needs. In fact, early
civilizations have been designated
by the level of their materials
development as Stone Age, Bronze
Age and Iron Age.
The earliest humans
utilized stone, wood, clay, skins
that occur naturally for their needs.
With time they discovered
techniques for producing materials
that had properties superior to
those of the natural ones; these
new materials included pottery and various metals. Furthermore, it was discovered that
the properties of a material could be altered by heat treatments and by the addition of
other substances.

1.2 General classification of Materials


There are thousands of materials available for various applications. Most of the
materials fall into one of three classes such as metallic, ceramic and polymer. This
classification is based on the atomic bonding forces of a particular material. Also, these
materials can be combined to form a composite material to have unique properties than
its constituent. Within each of these classifications, materials are usually organized into

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groups based on their chemical composition or certain physical or mechanical properties.


Composite materials are often grouped by the types of materials combined or the way the
materials are arranged together. Table 1 shows a common classification of materials.

Metals Polymer
• Ferrous metals and alloys (irons, • Thermoplastics
carbon steels, alloys steels, stainless • Thermoset plastics
steels) • Elastomers

• Nonferrous metals and alloys (Al,


Cu, Ni, Mg, Ti, super alloys
Ceramics Composites
• Glass • Reinforced plastics
• Graphite • Metal-matrix composites
• Diamond • Concrete

Table 1 General Classification of materials

1.3 Structure of Materials


We know all the
matter is made up of
atoms. From the periodic
table, it can be seen that
there are about 114
different kinds of atoms.
These 114 atoms form
thousands of different
substances ranging from
the air we breathe to the
metal used to support all
buildings. Metals behave
differently than ceramics,
and ceramics behave
differently than polymers.
The properties of matter
depend on the type of atoms and how they are bonded together. The three most common
major classification of structural, listed generally in increasing size, are:

• Atomic structure, which includes features that cannot be seen, such as the types
of bonding between the atoms, and the way the atoms are arranged.

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• Microstructure, which includes features that can be seen using a microscope, but
seldom with the naked eye.

• Macrostructure, which includes features that can be seen with the naked eye)

The atomic structure primarily affects the chemical, physical, thermal, electrical,
magnetic, and optical properties. The microstructure and macrostructure can also affect
these properties but they generally have a larger effect on mechanical properties and on
the rate of chemical reaction. The properties of a material offer clues as to the structure of
the material. The strength of metals suggests that these atoms are held together by strong
bonds. In solids, the way the atoms or molecules arrange themselves contributes to the
appearance and the properties of the materials.

Atoms can be gathered together as an aggregate through a number of different


processes, including condensation, pressurization, chemical reaction, electrodeposition,
and melting.

1.4 Amorphous Solids


A solid substance with
its atoms held apart at
equilibrium spacing, but with
no long-range periodicity in
atom location in its structure is
an amorphous solid. Examples
of amorphous solids are glass
and some types of plastic. They
are sometimes described as
supercooled liquids because
their molecules are arranged in
a random manner somewhat as
in the liquid state. For example,
glass is commonly made from
silicon dioxide or quartz sand,
which has a crystalline
structure. When the sand is
melted and the liquid is cooled
rapidly enough to avoid crystallization, an amorphous solid called a glass is formed.
Amorphous solids do not show a sharp phase change from solid to liquid at a definite
melting point, but rather soften gradually when they are heated. The physical properties
of amorphous solids are identical in all directions along any axis so they are said to have
isotropic properties, which will be discussed in more detail later

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1.5 Crystalline Solids


More than 90% of naturally occurring and artificially prepared solids are
crystalline. Minerals, sand, clay, limestone, metals, carbon (diamond and graphite), salts
(NaCl, KCl etc.), all have crystalline structures. A crystal is a regular, repeating
arrangement of atoms or molecules. The majority of solids, including all metals, adopt a
crystalline arrangement because the amount of stabilization achieved by anchoring
interactions between neighbouring particles is at its greatest when the particles adopt
regular (rather than random) arrangements. In the crystalline arrangement, the particles
pack efficiently together to minimize the total intermolecular energy.
The regular repeating pattern that the atoms arrange in is called the crystalline
lattice. The scanning tunnelling microscope (STM) makes it possible to image the
electron cloud associated individual atoms at the surface of a material.

1.6 Solidification
The crystallization of a large amount of material from a single point of nucleation
results in a single crystal. The moment a crystal begins to grow is known as nucleation
and the point where it occurs is the nucleation point. At the solidification temperature,
atoms of a liquid, such as melted metal, begin to bond together at the nucleation points
and start to form crystals. The final sizes of the individual crystals depend on the number
of nucleation points.

Fig. 1. a) Nucleation of crystals, b) crystal growth, c) irregular grains form as crystals grow together, d) grain boundaries
as seen in a microscope
In engineering materials, a crystal is usually referred to as a grain. A grain is
merely a crystal without smooth faces because its growth was impeded by contact with
another grain or a boundary surface. The interface formed between grains is called a

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grain boundary. The atoms between the grains (at the grain boundaries) have no
crystalline structure and are said to be disordered and are shown in Fig. 1.
Grains are sometimes large enough to be visible under an ordinary light
microscope or even to the unaided eye. The spangles that are seen on newly galvanized
metals are grains. Rapid cooling generally results in more nucleation points and smaller
grains (a fine grain structure). Slow cooling generally results in larger grains which will
have lower strength, hardness and ductility.

2 Classification of Low Dimensional Materials


This lecture provides you about the classification of low dimensional materials
(nanomaterials) and its properties

Anything made up of matter with one or more substances is termed as material. A


material’s state can be solid, liquid or gas and thus the building blocks may be atoms,
ions or molecules and its basic properties is shown in Table 2. Also the materials from
one state to other state can be changed by changing temperature or pressure, and is shown
in Fig. 2.

• Solids can hold their own shape unless something happens to them.
• Liquid flow and take the shape of their container.
• Gases are usually invisible and spread out to fill up spaces.
• Plasma are invisible and spread out to fill up space

Materials can be classified according to their state, size, shape, texture, colours,
flexibility, strength, hardness, malleable and whether they are a good conductor or bad
conductor of heat/electricity.

Table 2 Various states of a materials

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Fig. 2.Change in materials state and its basic properties

Solid state materials with reduced dimension in one or two or three directions are
recognized as low dimensional materials. Based on reduced dimension, the low
dimensional materials are in generally classified as 2D, 1D and 0D, and are shown in Fig.
3. Bulk materials is called as 3D materials, Due to reduced dimension, electron motion in
the materials is restricted either in one or two or three directions.

Fig. 3. Schematic representation of various forms of low dimensional materials

2.1. Basic Properties of Low Dimensional Semiconductor


Nanostructures

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The properties of any solids materials depend on the chemical composition, atomic
structure and the size of a solid in one, two or three dimensions. For example, Hardness
and optical reflection of carbon changes when it transform from diamond to graphite
(Fig. 4 (a&b)). Both are made up of carbon atoms, but the atom arrangements and bond
between them differs.

Fig. 4. (a) Diamond (b) Graphite

Also the change in microstructure (i.e. arrangement of atoms / molecules / ions) size
equivalent to a few inter-atomic spacing in one, two or three dimensions forming building
blocks of solid materials makes change in the properties. For example, colour changes of
gold at nanoscale. The materials synthesis with new properties by means of the controlled
microstructure size and shape on the atomic level has become important to achieve new
properties with enhanced device performance.

The materials microstructure with well-defined boundaries having a


characteristics length scale of the order of 1-10nm, where quantum size effect can be
expected are termed as nanostructured materials or simply nanomaterials. It should be
noted that, the material need not be so small; it can be a large surface whose thickness is
in the scale of nanometers or a long wire whose diameter is in the scale of nanometers or
a particle whose diameter is in the scale of nanometers. The microstructure of nanometer-
size crystallites with different crystallographic orientations are always far away from
thermodynamic equilibrium, because the boundary atom and the grain atoms both have
different nature. However nanostructured materials synthesized from supramolecular
chemistry are in thermodynamic equilibrium state.

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2.2 Why properties of nanomaterials are different?


The following two factors make the nanomaterials to have considerably different
properties that its bulk one.

1. Increase in relative surface area


2. Quantum confinement effect

2.2.1 Increase in surface area to volume

Nanomaterials have a relatively greater surface area when compared to the same
volume or mass of the same material in bulk form. For example, consider cube of 1m3
volume (Fig. 5), it has surface area of 6m2. If this cube of same volume is divided into
eight small cubes, then the total surface area increases to 12m2. Further dividing cube
leads to increase in surface area. This is illustrated in the following figure. Also if the
size of nanomaterials decreases, a greater proportion of atoms are found at the surface
compared to those inside. This makes materials more chemically reactive.

Fig.5. Increase in surface area of cube

2.2.2 Quantum Confinement


In nanomaterials, the electronic energy levels are not continuous as in the bulk but are
discrete. This is due to the confinement of the electronic wave function in one, two or
three physical dimensions of the materials and accordingly it can be classified as

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1. 1D confinement – Thin film, Quantum well


2. 2D confinement – Nanotubes, Nanorod, Quantum wire
3. 3D confinement - Precipitates, Colloids, quantum dots

2.3 Influence of phyical dimension on different properties ?

As seen in the previous topics, due to reduced physical size in one, two or three
dimension of a materials, leads to change in surface area and electron confinment, makes
the change in materials properties. The following section deals about different properties
of nanomaterials which differs from its bulk one.

2.3.1 Structural properties

Crystal structure of nanomaterials may or maynot same as its bulk one, but has
different lattice parameters. For example, gold and aluminium nanoparticles of size with
few nanometers are icosahedral rather than face-centered cubic in bulk (fig.6). Indium of
size less than 6.5nm is face-centered cubic rather than face-centered tetrahedral for size
greater than 6.5nm. Also, the inter atomic spacing in nanomaterials decreases than bulk
due to long range electrostatic forces and the short range core-core repulsion. For
example, decrease in aluminum separation to 2.81Å from 2.86Å and the binding energy
also decreases to 2.77eV from 3.39v.

Fig. 6. Crystal structure of (a) bulk (FCC) (b) nano (Icosahedral) Gold

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2.3.2 Thermal properties


The large increase in surface energy and the change in inter atomic spacing as a function
of size has marked effect on melting properties of nanomaterials. For example, the
melting point of gold nanoparticle shown in Fig.7 decreases rapidly as size reduces.

Fig. 7. Schematic diagram of the variation in melting point of gold nanoparticle as a


function of particle size.

2.3.3 Chemical properties


The ionisation energy is generally higher for small atomic cluster than for the
corresponding bulk one. Nanoscale structures have very high surface area to volume ratio
and potentially different crystallographic structures which may be lead to a radical
alteration in chemical reactivity. Catalysis using finely divided nanoscale system can
increase the rate, selectivity and effeciency of chemical reactions.

2.3.4 Mechanical properties


The presence of defects in any materials will alters the mechanical proeprties of it. In
nanomaterials, defects are high and increases due to non-thermal equilibrium and hence
mechanical properties changes. Some novel nanostructures which are very different from
bulk structure in terms of atomic structural arrangement, will show very different
mechanical properties. For examples single and multiwalled carbon nanotube show high
mechanical strength and high elastic limit which inturn lead to considerable flexibility.

2.3.5 Magnetic properties


Magnetic nanomaterials has multifunction applications, including ferrofluids, colour
imaging, bioprocessing, refrigeration as well as high storage density magnetic memory

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media. Due to large proportion of surface atoms which have a different local environment
leads different magnetic coupling with neighbouring atoms and in turns differs in
magnetic properties than its bulk one. Ferromagnetic materials in bulk form has multiple
magnetic domains, whereas nanoparticle often has one domain as shown in Fig.8 and
exhibit superparamagnetism phenomena. Also Giant magnetoresistance (GMR shown in
Fig. 9) is a phenomenon observed in nanoscale multilayer consisting of a strong
ferromagnet(e.g, Fe , Co) and a weaker magnetic or non-magnetic buffer(e.g, Cr,Cu). It is
usually employed in data storage and sensing.

Fig. 8. Superparmagnetism in nanomaterials

Fig. 9. GMR materials are made from alternating layers of magnetic and non- magnetic metals that are nanometers in
thickness.

2.3.6 Optical properties


In bulk materials, optical emission and absorption depends on transition between
valence band and conduction band. Large changes in optical properties such as colour is
seen in low dimensional semiconductor and metal. For example, Colloidal solutions of
gold nanoparticle have deep red colour which progressively more yellow as a particle
size increases (Fig.10) as a result of surface plasmon resonance occuring in low
dimensional materials. Semiconductor nanoparticles in the form of quantum dots shows
size dependent behaviour in the frequency and intensity of light emission as well as

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modified non linear optical properties and enhanced gain for certain emission energy or
wavelength. Other properties which may affected by reduced dimensionality include
photocatalysis, photoconductivity, photoemission and electroluminescence.

Fig. 10. The diameter of gold nanoparticle determines the colour

2.3.7 Electronic properties

The electonic properties changes occurs in the low dimensional material are related
to the wave like property of the electron and scaracity of the scattering centres. As the
size of the system becomes comparable with the de Broglie wavelength of the electrons,
the discrete nature of the energy states becomes occur as shown in Fig. 11. In certain
cases, conduction material become insulator below the critical length scale.

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Fig. 10. Density of states low dimensional materials

In macroscopic system , electronic trsnsport is determined by scattering with phonons ,


impurities or other carriers . However, if the system become sufficiently small, all
scattering centres will disappears and the electronic transport become purely ballastic
transport. Conduction in highly confined structure such as quantum dot is very sensitive
to the presence of other charge carriers and hence the charge state of the dot known as
coulomb blockade effect. This results in conduction processes involving single electrons
which in turn require a minimum amount of energy to operate the switch, transisitor, or
memeory element.

2.4 Comparison of bulk and nanostructured Semiconducting


material

Property/ Specific Bulk state Nano scale


Phenomenon properties
Structure confinement No confinement Confine in zero, one ,two
and three dimension
Surface area It is small as compare to Collective surface area can
its volume be enormous
Surface to (S/V) is small. Because Approaches 1, when all
volume it become insignificant atoms are surface atoms
ratio(S/V) as object becomes
larger.
Lattice Constant and Lattice spacing is altered.
spacing characteristics of bulk spacing near surface
contracts due to
rearrangement and ion
vacancies are larger
Atom co- Co-ordination saturated Co-ordination is unsaturated
ordination except at surface where at surface and volume
it is negligible
Electron Continuous over the It is not continuous
orbitals breadth of the material
Quantum Quantum mechanics Nanomaterial exist at
mechanics applies at the bulk level Quantum – classical
and it is called “ bath interface
tub waves “
Electromagnetic Radiation : Black body radiation. Influenced by the Bohr
property Absorption Absorption Emission radius

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Emission bands are broader


Optical 1. Metal reflects with 1. Size dependent
response partial absorption of absorption and
light emission
2. Micron size particle 2. Environmental
scatter the light dependent
3. High order Plasmon 3. Localized surface
resonance is Plasmon resonance
delocalized
Optical Bulk values are valid in Bulk optical constants no
constant micron size particles longer valid below 10 to 20
(n,k,α) nm
Band gap Bulk values are valid Band gap is size dependent.
Ex: Gold behaves as a
semiconductor in nano
particle form (<5nm)
Electrical Electrical conduction Electrical conduction are
conduction are continuous and not continuous and not obey
obeys ohms law the ohms law.
Thermodynamic Melting point Metal have high melting Metal nanoparticle have low
properties point melting point
Surface Independent of size Dependent of size
tension
Chemical Most of the bulk Intermolecular forces are
bond material ionic , covalent important. Hydrogen bond
and metallic bonds are and van der walls force
predominant dominant rather than ionic or
covalent or metallic bond
Entropy In bulk state , it links In nanoscale , the entropy is
between macro and very high and it cannot be
micro scale measured as that of bulk one
.
Solubility Large particle have In smaller particle have
limited solubility enhanced solubility . It is
important in targeted drug
delivery system
Magnetic Magnetic Bulk ferromagnetic Small magnetic nanoparticle
properties effect material usually forms consist of only one domain
multiple magnetic and exhibit a super
domains. paramagnetism
GMR Not possible in bulk It is observed in nanoscale
Electronic Energy level Continuous energy level Discrete energy level

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properties Density of Directly proportional to 2D=constant


states the E1/2 1D α E-1/2
0D- different for individual
energy levels .
Electronic Diffusive type of Ballistic Transport
transport transport
Coulomb It is never occurs in It is occurs in nanoscale
blockade bulk material material
effect

3 Quiz and Assignment


1. Materials can be classified into three types. They are metal, _________ and
ceramic
2. Ceramic are _______ and metals are ductile
3. The _______________ microscope makes it possible to image the electron cloud
associated individual atoms at the surface of a material
4. The moment a crystal begins to grow is known as _________
5. Rapid cooling generally results in more nucleation points and ________ grains.
Slow cooling generally results in _________ grains which will have lower
strength, hardness and ductility
6. Hardness and optical reflection of carbon changes when it transform from
_______to graphite
7. Colour of gold can be changed at ______ scale
8. The microstructure of nanometer-size crystallites with different crystallographic
orientations are always far away from _______________ equilibrium
9. The two factors make the nanomaterials to have considerably different properties
that its bulk is: (1). Increase in relative surface area and (2). _________
10. If the size of nanomaterials ________, a greater proportion of atoms are found at
the surface compared to those inside. This makes materials more chemically
reactive.
11. 1D confinement materials can be called either quantum well or _______
12. In general, the inter atomic spacing in nanomaterials ________ than bulk due to
long range electrostatic forces and the short range core-core repulsion
13. The ionisation energy is generally ______ for nanoparticles than for the
corresponding bulk one
14. Ferromagnetic materials in bulk form has multiple magnetic domains, whereas
nanoparticle often has one domain as shown in figure and exhibit _________
phenomena.
15. In nanomaterials, all scattering centres will disappears and the electronic transport
become purely _________transport.

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3.1 Solutions
1. Polymer
2. brittle
3. Scanning Tunneling
4. nucleation
5. smaller, larger
6. diamond
7. nano
8. thermodynamic
9. Quantum confinement effect
10. decreases
11. Thin films
12. decreases
13. higher
14. superparamagnetism
15. Ballastic

4 References
[1] William D. Callister, Jr. , Fundamentals of Materials Science and Engineering-An
Interactive e-text, John Wiley & Sons, Inc. , 2001.
[2] H. Hosono, Y. Mishima, H. Takezoe, K.J.D. Mackenzie, Nanomaterials from
Research to Applications, Elsevier Inc., 2006.
[3] Guozhong Cao, Nanostructures & Nanomaterials Synthesis, Properties &
Applications, Imperial College Press, 2004.

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