MM1201: Material Science (3-0-0)
Dr. Anushree Dutta, Assistant Professor
Dept. of Metallurgical and Materials Engineering
Email Id: [Link]@[Link]
UNIT-III
NIT Jamshedpur
1
UNIT-III:
Electron theory of Metals: Bond theory, Uncertainty principle, Free electron theory, Zone theory, The dependence of
the energies on the wave number, The density of state curves, Conductors and insulators, Semiconductors, Dielectric
behavior, Ferroelectricity, Piezoelectricity, Magnetism.
2
Assumptions in classical free electron theory
• In metals, there are large number of free electrons moving freely and randomly in all possible
directions.
• These free electrons behave like gas molecules in a container and obeying the laws of kinetic theory
of gases (free electron gas).
3
• In the absence of field, the energy associated with each electron at a temperature T is given by kT. It
2
3 12
is related to kinetic energy as kT = 𝑚𝑣𝑡ℎ , where vth is the thermal velocity and k is Boltzmann
2 2
constant.
• In metals, the positive ion cores are at fixed positions and the free electrons move randomly and
collide either with positive ion cores or with other free electrons or with boundaries.
• These collisions are elastic. The electric conduction is due to free electrons only.
• Electron velocities in a metal obey Maxwell-Boltzmann distribution law.
• The free electrons move in a constant potential field. Hence the potential energy of the electrons is
constant.
• When an electric field is applied to a metal, free electrons are accelerated in the direction opposite to
the direction of applied electric field with a velocity called drift velocity represented as vd.
3
Success of classical free electron theory (Drude-
Lorentz theory)
• Verifies Ohm’s law.
• Explains electrical conductivity and thermal conductivities of metals.
• Can explains ductility and malleability of metals.
• Can explains optical properties of metals.
• Can explains Widemann-Franz law in metals to some extent.
4
Drude theory (in 1900) assumption was based on
• Knew about electron as charge carrier (discovered by J.J. Thomson in 1897)
• Kinetic theory of gases
• Atomic structure was not known (Discovery of atomic nucleus by Rutherford in 1911
and model of hydrogen atom by Neils Bohr)
• Assumed as there is –ve charge there must be compensating +ve charge for electrical
neutrality and named as ions
• Applied kinetic theory of gases in case of electrons
• Ions are heavier so immobile and not taking part in conduction
• Ions are shielded by so many inner shell electrons. So interaction was neglected
• Drude measured the distance between two collision is 1-10 Å (interatomic distance )
elegant theory at that time
5
Limitations/failure of classical free electron theory
• Fails to explain the electrical conductivity of semiconductors and insulators.
• Fails to explain the temperature variation of electrical conductivity at low temperature.
• Fails to explain the concept of specific heat of metals.
• Fails to explain the mean free path of the electrons.
• Fails to explain temperature dependence of paramagnetic susceptibility and
ferromagnetism.
6
Brief overview Quantum mechanics
• Behavior of matter and energy is different in subatomic level (electron, proton, neutron, etc.)
• Quantum theory is helpful for describing that behavior.
• Evolution and Development of quantum mechanics happened over a long period of time
• Rutherford explained that most of the space in atom is free. Heavy positive charge as
nucleus is at the center and –ve charge electron orbit around the nucleus
• As per classical Maxwell theory of electromagnetism, any accelerate electric charge radiate
• Accordingly, electron should loose its energy and fall on nucleus
• Thus, No atomic stability
• Neils Bohr improved the existing Rutherford model and told that electron cannot move
arbitrarily in any orbit, but it can rotate only those orbits where its energy is fixed.
• So, electron in a particular orbit has fixed quantum of energy. Which was the origin of
quantum mechanics.
7
Brief overview Quantum mechanics
• Energies of electrons are quantized that is electrons are permitted to have only
specific values of energy.
• Energy states do not vary continuously with energy, that is adjacent states are
separated by finite energies.
• Newtonian mechanics – position, velocity and momentum of particle can be measured
accurately and simultaneously same time
• As per quantum mechanics, it is impossible to measure accurately same time both
the position and the momentum of an object ( ) - Heisenberg Uncertainty
Principle
8
Energy (Classical VS Quantum)
9
• Electron are quantum particles and called fermions
• They follow Fermi-Dirac statistics
• In quantum mechanical system, energy level are discrete
• Electron occupy in the energy states following Pauli's exclusion principle and Hund’s rule
• Fermi-Dirac distribution function: The probability of finding the particles in energy level
• Probability function is a mathematical representation of the probability distribution of the
energies of the quantum states that electrons can exist in at some given temperature
• Fermi level: The highest energy level that an electron can occupy at the absolute zero
temperature.
• The energy level above which probability of finding particle is zero at absolute zero
• Fermi level is the energy level at which the probability of finding particle at any
temperature is 1/2 .
10
Sommerfeld free electron theory
Sommerfeld proposed Quantum free electron theory in 1928. It overcomes many of the drawbacks of
classical theory. Sommerfeld explained theory by applying Fermi-Dirac statistics instead of Maxwell-
Boltzmann statistics. And developed the theory by applying the principles of quantum mechanics.
Assumptions of Quantum Free Electron Theory
• Valence electrons move freely in a constant potential within the boundaries of metal and is prevented
from escaping the metal at the boundaries (high potential). Hence the electron is trapped in a potential
well.
• The distribution of electrons in various allowed energy levels occurs as per Pauli Exclusion Principle
and Hund’s rule.
• The attraction between the free electrons and lattice ions and the repulsion between electrons were
ignored.
• The distribution of energy among the free electrons obey Fermi-Dirac statistics.
• The energy values of free electrons are quantized.
• To find the possible energy values of electron Schrodinger time independent wave equation is applied.
The problem is similar to that of particle present in a potential box.
11
Success of Sommerfeld quantum free electron theory
• Successfully explains the electrical and thermal conductivity of metals.
• Can explain the Thermionic phenomenon.
• Explains temperature dependence of conductivity of metals.
• Can explain the specific heat of metals.
• Explains magnetic susceptibility of metals.
• Can explain photo electric effect, Compton Effect and black body radiation etc.
• Gives the correct mathematical expression for the thermal conductivity of metals.
12
Failure of quantum free electron theory
• Fails to explains why some crystals have metallic properties other do not have
• Unable to explain why the atomic arrays in metallic crystals should prefer certain
structures only.
• Fails to distinguish between metal, semiconductor and Insulator.
• Fails to explain the positive value of Hall Co-efficient.
13
Fermi Dirac Distribution
• A metal piece contains very large number of electrons. Each electron possesses quantized energy
states and obeys Pauli’s exclusion principle. Hence they satisfy Fermi-Dirac statistics. The
probability F(E) of an electron occupying energy level Ei is given by
• Where F(Ei) is called Fermi function which is defined as the probability of electron occupation in the
given energy state (Ei) at thermal equilibrium. Ef is Fermi energy, Ei is energy of ith state and k is
Boltzmann constant.
Pauli's Exclusion Principle: No two electrons in the same atom can have identical values for all four of their
quantum numbers.
14
Plot of f(E) Vs E
• Collective behavior of electron gas obey Fermi Dirac statistics.
• Distribution function f(E) describes us how electrons are distributed in various energy states.
• This system of electrons have different energy level. Therefore, electron occupy these energy states.
• Fermi energy (EF) is characteristics properties of metals. Collective behavior depend on how electron are
distributed in the energy states.
15
Effect of temperature on Fermi Dirac distribution
Conclusions: At T=0K, the Fermi Dirac distribution of electrons can be understood mathematically from the
following two cases.
𝐸𝑖 −𝐸𝐹
Case -1: If Ei>EF, 𝑒 𝑘𝑇 =∞
Therefore, F(Ei)= 1/∞ then F(Ei)=0. It indicates that energy levels above Fermi level are empty.
𝐸𝑖 −𝐸𝐹
Case -2: If Ei< EF, 𝑒 𝑘𝑇 =0 then F(Ei)=1. It indicates that energy levels below Fermi levels are full of electrons.
The Fermi level is a boundary energy level which separates the filled energy state and empty states at 0K. The
energy of the highest filled state at 0K is called Fermi Energy E F and the energy level is known as Fermi Level.
16
Case-3: At T>0K (any finite temperature),
1) if Ei= EF then F(Ei)=1/2. i.e 50%. Therefore, Fermi level is the energy level for which the probability of
filled states is 50% at any temperature.
2) When T>0, F(EF)<1 for Ei< EF
3. F(Ei)>0 for Ei> EF
As temperature increases more and more electrons jump to the levels above EF leaving vacancies as
shown in the fig.
3. The electrons in the levels above EF and vacancies in the levels below EF are responsible for
conduction in semiconductors.
4. If the temperature is raised further, the resistance of the metals increases due to decrease of mobility.
5. At T>0K, the Fermi energy level decreases.
6. According to classical theory, all the free electrons below EF gain energy when temperature is
increased. This deviates theoretical and experimental values.
7. According to quantum theory only few electrons below EF gain energy from external source. Thus
theoretical values are closer to the experimental values.
17
Electrons in a periodic potential - Bloch theorem:
• A crystalline solid consists of a lattice, which is composed of a large number of ion cores at
regular intervals,
• And the conduction electrons that can move freely throughout the lattice.
• The conduction electrons move inside periodic positive ion cores.
• Hence instead of considering uniform constant potential as we have done in the Classical as well
as Sommerfeld electron theory, we have to consider the variation of potential inside the metallic
crystal with the periodicity of the lattice as shown fig.
18
Zone theory or Band theory of solids
• Assuming electrons as quantum particle, Sommerfeld successfully explained many
properties of materials including electrical conductivity, thermal conductivity, temperature
dependence resistance, specific heat of solids, magnetic properties, para magnetism of
metals etc.
• However, quantum mechanical theory could not explain why some materials are conductor,
semi conductor and some are insulator
• Unable to distinguish between these materials
• In some phenomenon quantum theory also fail and why fails
• How zone theory or band theory corrected the areas and the assumptions
• Failure was mainly due to the assumption that electrons move under constant potential
(zero)
• In real crystal electrons move in periodic potential
19
Zone theory
• Zone theory was proposed by Bloch in 1928 and developed by Kronig – Penny and others
• Potential is a periodic function with the periodicity in the lattice
• Electrons experience varying potential
20
• According to free electron theory, conduction electron moves under constant potential
inside crystal, but restrained by the surface of the crystal.
• In quantum free electron, only constraint on the particle is that it is confined in a
boundary. The boundary has infinite potential where wave function does not exist.
• This theory could explain many phenomena but fails to explain why some solids are
good conductor of electricity, some are semi conductors and others are insulator.
• Physical properties of semiconductor and insulator can not be explained by quantum free
electron theory.
• In real crystal, electrons move in periodic potential.
• This potential arises due to periodic distribution of the positive charge associated with
ions cores situated on the lattice sites inside the crystal plus the constant contribution due
to all other free electrons of the crystal.
21
22
23
• Bloch solved Schrodinger equation one dimensional crystal lattice problem
• In quantum free electron theory, the wave function does not exist at boundary
• Solution of Bloch periodic potential model was very complex as potential is
continuously varying
• In order get rid of complexity, Kronig and Penny (two scientists) simplified the
model with rectangular potential model (potential is changing like step function)
24
Material Science (MM1101) UNIT-III : Dr. Anushree Dutta
Kronig-Penny model
Kronig-Penny potential one dimensional potential where V0 is the height of the potential
barrier. a is Lattice distance and b is width of the potential barrier.
25
The dependence of the energies on the wave number
Ref: Robert E. Reed-Hill - Physical metallurgy principles-Van Nostrand (1973)
26
The dependence of the energies on the wave number
In this region Schrodinger
wave equation does not
have any solutions.
𝜋 𝜋
At the value of - 𝑎𝑛𝑑 wave function is discontinuous (stationary wave formed)
𝑑 𝑑
In this region Schrodinger wave equation does not have any solutions that gives rise to
forbidden energy gap
Ref: Robert E. Reed-Hill - Physical metallurgy principles-Van Nostrand (1973)
27
Origin of Energy gap
28
Band theory
• In 1928-1931, Bloch, Kronig-Penny, Willson, and Peierls invented Band theory.
• They gave convincing explanation of metallic (conducting) semiconducting and
insulating behaviors of solids.
• A solid is made up of enormous number of closely packed atoms. When these
atoms are isolated they have discrete sets of energy levels as 1s,2s,2p,3s,…so on
• To form a solid large number of isolated atoms (order of 1023) are brought
together, then a continuously increasing interaction occurs between them so that
the split energy levels form essentially continuous bands of energy.
29
Band theory
• The energy bands in solids corresponds to the energy level in atoms, Generally lower
levels are splitted less than higher levels or almost unsplitted because these levels
contain mostly inner electrons which are not affected by nearest atoms
• An electron can have only energies that can fall with in these energy bands. The
energy bands in a solids may be overlapped or not depending on structure of solids. If,
they do not overlap then the interval between them represents energies which the
electrons in the solids cannot have.
• These intervals are called Forbidden Energy Gap
30
Band theory
31
32
33
Conductor, Semiconductor and Insulator
• Conductor: The conductor are those in which plenty of free electron are available for electric
conduction. In terms of energy bands, conductor are those which have overlapping valence
band and conduction band. E.g. Cu, Ag, Al, etc
• Semiconductor: These are characterized by a very narrow energy band gap (~1 eV) between
the valence and conduction band. These are solids whose electrical conductivity lies between
conductor and insulator. Ex. Ge, Si, GaAs.
• Insulator: Solids having wide energy gap (~6 eV) between the filled valence band and empty
conduction band. Valence electrons cannot acquire that much of high energy from an applied
field that they could cross the energy gap and enter the conduction band. Hence conduction is
impossible for insulator.
34
Classification of Materials
35
Classification of Materials
36
Classification of Materials
37
Density of States (DOS)
The density of states (DOS) is essentially the number of different states at a particular energy level
that electrons are allowed to occupy, i.e. the number of electron states per unit volume per unit
energy. Bulk properties such as specific heat, paramagnetic susceptibility, and other transport
phenomena of conductive solids depend on this function. DOS calculations allow one to determine
the general distribution of states as a function of energy and can also determine the spacing between
energy bands in semi-conductors.
38
39
The Heisenberg’s Uncertainty Principle
• The Heisenberg’s uncertainty principle states that the more precisely the position of some
particle is determined, the less precisely its momentum can be known, and vice versa.
• As per quantum mechanics, it is impossible to measure accurately same time both the
position and the momentum of an object.
40
Magnetism
Material Science (MM1101) UNIT-III : Dr. Anushree Dutta 41
• Dielectric material is one that is electrically insulating (nonmetallic) and exhibits or may be made to
exhibit an electric dipole structure; that is, there is a separation of positive and negative electrically
charged entities on a molecular or atomic level. As a result of dipole interactions with electric fields,
dielectric materials are used in capacitors.
• Piezoelectric: A dielectric material in which polarization is induced by the application of external
forces. Piezoelectric refers to the property of certain solid materials which can accumulate the
electric charge upon the application of mechanical stress.
• Ferroelectrics: The group of dielectric materials called ferroelectrics exhibit spontaneous
polarization—that is, polarization in the absence of an electric field. They are the dielectric analogue
of ferromagnetic materials, which may display permanent magnetic behavior. There must exist in
ferroelectric materials permanent electric dipoles, the origin of which is explained for barium
titanate, one of the most common ferroelectrics.
42
Ionic bond, Covalent bond and Metallic bond
• Ionic bonding It is always found in compounds that are composed of both metallic and nonmetallic
elements, elements that are situated at the horizontal extremities of the periodic table. Atoms of a
metallic element easily give up their valence electrons to the nonmetallic atoms. In the process all
the atoms acquire stable or inert gas configurations and, in addition, an electrical charge; that is, they
become ions. Sodium chloride (NaCl) is the classic ionic material. A sodium atom can assume the
electron structure of neon (and a net single positive charge) by a transfer of its one valence 3s
electron to a chlorine atom. After such a transfer, the chlorine ion has a net negative charge and an
electron configuration identical to that of argon. In sodium chloride, all the sodium and chlorine
exist as ions.
43
• In covalent bonding, stable electron configurations are assumed by the sharing of electrons between
adjacent atoms. Two atoms that are covalently bonded will each contribute at least one electron to the
bond, and the shared electrons may be considered to belong to both atoms. Covalent bonding is
schematically illustrated in Figure 2.10 for a molecule of methane (CH4). The carbon atom has four
valence electrons, whereas each of the four hydrogen atoms has a single valence electron. Each
hydrogen atom can acquire a helium electron configuration (two 1s valence electrons) when the
carbon atom shares with it one electron. The carbon now has four additional shared electrons, one
from each hydrogen, for a total of eight valence electrons, and the electron structure of neon. The
covalent bond is directional; that is, it is between specific atoms and may exist only in the direction
between one atom and another that participates in the electron sharing.
44
• Metallic bonding, the final primary bonding type, is found in metals and their alloys. A relatively
simple model has been proposed that very nearly approximates the bonding scheme. Metallic
materials have one, two, or at most, three valence electrons. With this model, these valence electrons
are not bound to any particular atom in the solid and are more or less free to drift throughout the
entire metal. They may be thought of as belonging to the metal as a whole, or forming a “sea of
electrons” or an “electron cloud.” The remaining nonvalence electrons and atomic nuclei form what
are called ion cores, which possess a net positive charge equal in magnitude to the total valence
electron charge per atom. Figure 2.11 is a schematic illustration of metallic bonding. The free
electrons shield the positively charged ion cores from mutually repulsive electrostatic forces, which
they would otherwise exert upon one another; consequently the metallic bond is nondirectional in
character. In addition, these free electrons act as a “glue” to hold the ion cores together .
45