MOLECULES AND SOLIDS

OBJECTIVES:

• To understand the energy states and spectra of molecules

• To understand the cohesion of solid metals using bonding in solids
• To comprehend the electrical properties of metals, semiconductors and
insulators
• To understand the effect of doping on electrical properties of semiconductors
• To understand superconductivity and its engineering applications

4.1 ENERGY STATES AND SPECTRA OF MOLECULES

Consider an individual molecule in the gaseous phase of a substance. The energy E of the
molecule can be divided into four categories: (1) electronic energy, due to the interactions
between the molecule’s electrons and nuclei; (2) translational energy, due to the motion of the
molecule’s center of mass through space; (3) rotational energy, due to the rotation of the
molecule about its center of mass; and (4) vibrational energy, due to the vibration of the
molecule’s constituent atoms:
E = Eel + Etrans + Erot + Evib (4.1)

Because the translational energy is unrelated to internal structure, this molecular energy is
unimportant in interpreting molecular spectra. Although the electronic energies can be studied,
significant information about a molecule can be determined by analyzing its quantized
rotational and vibrational energy states. Transitions between these states give spectral lines in
the microwave and infrared regions of the electromagnetic spectrum, respectively.

ROTATIONAL MOTION OF MOLECULES

Let’s consider the rotation of a diatomic molecule around its center of mass (Figure 6.4a). A
diatomic molecule aligned along a y axis has only two rotational degrees of freedom,
corresponding to rotations about the x and z axes passing through the molecule’s center of
mass. If  is the angular frequency of rotation about one of these axes, the rotational kinetic
energy of the molecule about that axis can be expressed as
1 2
Erot = I
2 (4.2)
In this equation, I is the moment of inertia of the molecule about its center of mass, given by
 mm 
I =  1 2  r2 =  r2 (4.3)
 m1 + m2 

where m1 and m2 are the masses of the atoms that form the molecule, r is the atomic separation,
and  is the reduced mass of the molecule
m1m2
=
m1 + m2 (4.4)

Figure 4.1: Rotation of a diatomic molecule around its center of mass. (a) A diatomic
molecule oriented along the y axis. (b) Allowed rotational energies of a diatomic molecule
expressed as multiples of E1 = ℏ2/I.
The magnitude of the molecule’s angular momentum about its center of mass is L=Iω, which
can attain quantized values given by,

L = J ( J + 1) J = 0, 1, 2, ... (4.5)

where J is an integer called the rotational quantum number. Combining Equations 4.5 and
4.2, we obtain an expression for the allowed values of the rotational kinetic energy of the
molecule:
2
Erot = EJ = J ( J + 1) J = 0, 1, 2, ... (4.6)
2I
The allowed rotational energies of a diatomic molecule are plotted in Figure 4.1b. The allowed
rotational transitions of linear molecules are regulated by the selection rule ΔJ =±1. From
Equation 4.6, the energies of the absorbed photons are given by,
2
h2
Ephoton = J= J J = 1, 2, 3, ... (4.7)
I 4 2 I
where J is the rotational quantum number of the higher energy state.

VIBRATIONAL MOTION OF MOLECULES

If we consider a molecule to be a flexible structure in which the atoms are bonded together by
“effective springs” as shown in Figure 4.2a, we can model the molecule as a simple harmonic
oscillator as long as the atoms in the molecule are not too far from their equilibrium positions.
Figure 4.2b shows a plot of potential energy versus atomic separation for a diatomic molecule,
where r0 is the equilibrium atomic separation. For separations close to r0, the shape of the
potential energy curve closely resembles a parabola. According to classical mechanics, the
frequency of vibration for the system is given by
1 k
f = (4.8)
2 

where k is the effective spring constant and  is the reduced mass given by Equation 4.4. The
vibrational motion and quantized vibrational energy can be altered if the molecule acquires
energy of the proper value to cause a transition between quantized vibrational states. The
allowed vibrational energies are
 1
Evib =  v +  hf v = 0, 1, 2, ... (4.9)
 2

where v is an integer called the vibrational quantum number.

Figure 4.2 (a) Effective-spring model of a diatomic molecule. (b) Plot of the potential energy
of a diatomic molecule versus atomic separation distance.
 Figure 4.3 Allowed vibrational energies of a diatomic molecule, where f is the frequency of
vibration of the molecule
Substituting Equation 4.8 into Equation 4.9 gives the following expression for the allowed
vibrational energies:

 1 h k
Evib =  v +  v = 0, 1, 2, ... (4.10)
 2  2 

The selection rule for the allowed vibrational transitions is Δv = ±1. The photon energy for
transition is given by,
h k
Ephoton = Evib = (4.11)
2 

The vibrational energies of a diatomic molecule are plotted in Figure 4.3. At ordinary
temperatures, most molecules have vibrational energies corresponding to the v = 0 state
because the spacing between vibrational states is much greater than kBT, where kB is
Boltzmann’s constant and T is the temperature.

4.2 MOLECULAR SPECTRA

In general, a molecule vibrates and rotates simultaneously. To a first approximation, these
motions are independent of each other, so the total energy of the molecule is the sum of
Equations 4.6 and 4.9:
 1 2
E =  v +  hf + J ( J + 1)
 2 2I (4.12)

The energy levels of any molecule can be calculated from this expression, and each level is
indexed by the two quantum numbers v and J. From these calculations, an energy-level diagram
like the one shown in Figure 4.4a can be constructed. For each allowed value of the vibrational
quantum number v, there is a complete set of rotational levels corresponding to J = 0, 1, 2, . . .
. The energy separation between successive rotational levels is much smaller than the
separation between successive vibrational levels. The molecular absorption spectrum in Figure
4.4b consists of two groups of lines: one group to the right of center and satisfying the selection
rules ΔJ = +1 and Δv = +1, and the other group to the left of center and satisfying the selection
rules ΔJ = -1 and Δv = +1. The energies of the absorbed photons can be calculated from
Equation 4.12:
2
Ephoton = E = hf + ( J + 1) J = 0, 1, 2, ... ( J = +1) (4.13)
I

2
Ephoton = E = hf − J J = 1, 2, 3, ... ( J = −1) (4.14)
I

where J is the rotational quantum number of the initial state.

Figure 4.4: (a) Absorptive transitions between the v = 0 and v = 1 vibrational states of a
diatomic molecule. (b) Expected lines in the absorption spectrum of a molecule.
The experimental absorption spectrum of the HCl molecule shown in Figure 4.5. One
peculiarity is apparent, however: each line is split into a doublet. This doubling occurs because
two chlorine isotopes were present in the sample used to obtain this spectrum. Because the
isotopes have different masses, the two HCl molecules have different values of I.
 Figure 4.5: Experimental absorption spectrum of the HCl molecule
The second function determining the envelope of the intensity of the spectral lines is the
Boltzmann factor. The number of molecules in an excited rotational state is given by
−ℏ2 𝐽(𝐽+1)
𝑛 = 𝑛0 𝑒 2𝐼𝑘𝐵 𝑇
where n0 is the number of molecules in the J = 0 state.
Multiplying these factors together indicates that the intensity of spectral lines should be
described by a function of J as follows:
−ℏ2 𝐽(𝐽+1)
𝐼𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦 ∝ (2𝐽 + 1)𝑒 2𝐼𝑘𝐵 𝑇
(4.15)

4.3 BONDING IN SOLIDS

A crystalline solid consists of a large number of atoms arranged in a regular array, forming a
periodic structure.
Ionic Solids: Many crystals are formed by ionic bonding, in which the dominant interaction
between ions is the Coulomb force. Consider a portion of the NaCl crystal shown in Figure
4.6a. The red spheres are sodium ions, and the blue spheres are chlorine ions. As shown in
Figure 4.6b, each Na+ ion has six nearest-neighbor Cl- ions. Similarly, in Figure 4.6c, each Cl-
ion has six nearest-neighbor Na+ ions. Each Na+ ion is attracted to its six Cl- neighbors. The
corresponding potential energy is -6kee2/r, where ke is the Coulomb constant and r is the
separation distance between each Na+ and Cl-. In addition, there are 12 next-nearest-neighbor
Na+ ions at a distance of √2r from the Na+ ion, and these 12 positive ions exert weaker repulsive
forces on the central Na+. Furthermore, beyond these 12 Na+ ions are more Cl2 ions that exert
an attractive force, and so on. The net effect of all these interactions is a resultant negative
electric potential energy

e2
U attractive = − ke (4.16)
r
where α is a dimensionless number known as the Madelung constant. The value of α depends
only on the particular crystalline structure of the solid (α = 1.747 for the NaCl structure). When
the constituent ions of a crystal are brought close together, a repulsive force exists because of
electrostatic forces and the exclusion principle. The potential energy term B/rm in Equation
4.17 accounts for this repulsive force. The repulsive forces occur only for ions that are very
close together.
Therefore, we can express the total potential energy of the crystal as
e2 B
U total = − ke + (4.17)
r rm

where m in this expression is some small integer.

Figure 4.6: (a) Crystalline structure of NaCl. (b) Each positive sodium ion is surrounded by
six negative chlorine ions. (c) Each chlorine ion is surrounded by six sodium ions

Figure 4.7: Total potential energy versus ion separation distance for an ionic solid, where U0
is the ionic cohesive energy and r0 is the equilibrium separation distance between ions
A plot of total potential energy versus ion separation distance is shown in Figure 4.7. The
potential energy has its minimum value U0 at the equilibrium separation, when r = r0.
 e2  1 
U 0 = − ke 1 − 
r0  m  (4.18)

This minimum energy U0 is called the ionic cohesive energy of the solid, and its absolute value
represents the energy required to separate the solid into a collection of isolated positive and
negative ions.

Covalent Solids: Solid carbon, in the form of diamond, is a crystal whose atoms are covalently
bonded. In the diamond structure, each carbon atom is covalently bonded to four other carbon
atoms located at four corners of a cube as shown in Figure 4.8(a). The crystalline structure of
diamond is shown in Figure 4.8 (b). The basic structure of diamond is called tetrahedral (each
carbon atom is at the center of a regular tetrahedron), and the angle between the bonds is 109.5°.
Other crystals such as silicon and germanium have the same structure. Covalently bonded
solids are usually very hard, have high bond energies and high melting points, and are good
electrical insulators.

Figure 4.8: (a) Each carbon atom in a diamond crystal is covalently bonded to four other
carbon atoms so that a tetrahedral structure is formed. (b) The crystal structure of diamond,
showing the tetrahedral bond arrangement
Metallic Solids: Metallic bonds are generally weaker than ionic or covalent bonds. The outer
electrons in the atoms of a metal are relatively free to move throughout the material, and the
number of such mobile electrons in a metal is large. The metallic structure can be viewed as a
“sea” or a “gas” of nearly free electrons surrounding a lattice of positive ions (Figure 4.9). The
bonding mechanism in a metal is the attractive force between the entire collection of positive
ions and the electron gas.

Light interacts strongly with the free electrons in metals. Hence, visible light is absorbed and
re-emitted quite close to the surface of a metal, which accounts for the shiny nature of metal
surfaces. Because the bonding in metals is between all the electrons and all the positive ions,
metals tend to bend when stressed.

Figure 4.9: Highly schematic diagram of a metal

4.4 FREE-ELECTRON THEORY OF METALS

Quantum based free electron theory of metals is centered on wave nature of electrons. In this
model, one imagines that the outer-shell electrons are free to move through the metal but
are trapped within a three-dimensional box formed by the metal surfaces. Therefore,
each electron is represented as a particle in a box and is restricted to quantized energy
levels. Each energy state can be occupied by only two electrons (one with spin up & the
other with spin down) as a consequence of exclusion principle. In quantum statistics, it is
shown that the probability of a particular energy state E being occupied by an electrons is
given by

1
f (E) = (4.19)
 E − EF 
exp   + 1
 kT 

where f(E) is called the Fermi-Dirac distribution function and EF is called the Fermi
energy. Plot of f(E) versus E is shown in figure 4.10.
Figure. 4.10: Plot of Fermi-Dirac distribution function f(E) Vs energy E at (a) T = 0K and (b)
T > 0K
At zero kelvin (0 K), all states having energies less than the Fermi energy are occupied, and
all states having energies greater than the Fermi energy are vacant. i.e. Fermi energy is the
highest energy possessed by an electron at 0 K (Figure 4.10a). As temperature increases (T >
0K), the distribution rounds off slightly due to thermal excitation and probability of Fermi level
being occupied by an electron becomes half (Figure 4.10b). In other words, Fermi energy is
that energy state at which probability of electron occupation is half. The Fermi energy EF also
depends on temperature, but the dependence is weak in metals.

Density of states: From particle in a box problem, for a particle of mass m is confined to move
in a one-dimensional box of length L, the allowed states have quantized energy levels given
by,

h2 
2 2
En = 2
n 2
= 2
n2 n = 1, 2, 3 . . . (4.20)
8mL 2mL

An electron moving freely in a metal cube of side L, can be modeled as particle in a three-
dimensional box. It can be shown that the energy for such an electron is

2
2
E=
2mL 2 (n
2
x + ny2 + nz2 ) (4.21)

where m is mass of the electron and nx, ny, nz are quantum numbers(positive integers). Each
allowed energy value is characterized by a set of three quantum numbers (nx, ny, nz - one
for each degree of freedom). Imagine a three-dimensional quantum number space
whose axes represent nx, ny, nz. The allowed energy states in this space can be represented
as dots located at positive integral values of the three quantum numbers as shown in the
Figure 4.11.
 Figure 4.11: Representation of the allowed energy states in a quantum number space (dots
represent the allowed states)
Eq. 5.21 can be written as

E
nx2 + n y2 + nz2 = = n2 (4.22)
Eo

2
2 E
where Eo = 2
and n =
2mL Eo

Eq. 4.22 represents a sphere of radius n. Thus, the number of allowed energy states
having energies between E and E+dE is equal to the number of points in a spherical
shell of radius n and thickness dn. In this quantum number space each point is at the corners
of a unit cube and each corner point is shared by eight unit cubes and as such the contribution
of each point to the cube is 1/8 th. Because a cube has eight corners, the effective point per unit
cube and hence unit volume is one. In other words, number of points is equal to the volume
of the shell. The “volume” of this shell, denoted by G(E)dE.

1 1
G(E) dE =   ( 4 n 2 dn ) =    n dn
2

8 2

 E   E  1 2  E
G ( E ) dE = 12    d    using the relation n =
 o   o  
E  E Eo
  E  − 12 −1 −3 1
G ( E ) dE = 1
2   Eo
1
2 E 2
dE = 1
4  Eo 2
E 2
dE
 Eo 

−3
 2 2  2
1
G ( E ) dE = 1
4  2 
E 2
dE
 2mL 

3
2 m 2 L3 1 2
G ( E ) dE = E dE , L3 = V
2 2 3

Number of states per unit volume per unit energy range, called density of states, g(E) is
given by

g(E) = G(E)/V

3
2
G(E ) 2 m 1
g ( E ) dE = dE = E 2
dE
V 2 2 3

3
4 2 m 2 1 h
g ( E ) dE = E 2
dE =
h3 2

Finally, we multiply by 2 for the two possible spin states of each particle.

3
8 2 m 2 1
g ( E ) dE = E 2
dE (4.23)
h3

g(E) is called the density-of-states function.

Electron density: For a metal in thermal equilibrium, the number of electrons N(E) dE,
per unit volume, that have energy between E and E+dE is equal to the product of the
density of states and the probability that a state is occupied. that is,

N(E)dE = [ g(E)dE ] f(E)

3 1
8 2 m 2
E 2 dE
N ( E ) dE = (4.24)
h3  E − EF 
exp   + 1
 kT 

Plots of N(E) versus E for two temperatures are given in figure 4.12.
 Figure 4.12: Plots of N(E) versus E for (a) T = 0K (b) T = 300K
If ne is the total number of electrons per unit volume, we require that

 3  1
8 2 m 2
E 2 dE
ne =  N ( E ) dE =  (4.25)
h3  E − EF 
 + 1
0 0
exp 
 kT 

At T = 0K, the Fermi-Dirac distribution function f(E) = 1 for E <EF and f(E) = 0 for E >EF.
Therefore, at T = 0K,

3 3 3
8 2 m 8 2 m 16 2  m
2 EF 2 2

 ( ) EF
1 3 3
ne = E 2
dE = 2
3
2
= EF 2 (4.26)
h3 0
h3 3 h3

Solving for Fermi energy at 0K, we obtain

2
h 2  3 ne  3
EF ( 0 ) =   (4.27)
2 m  8 

The average energy of a free electron in a metal at 0K is Eav = (3/5)EF.

4.5 BAND THEORY OF SOLIDS

When a quantum system is represented by wave function, probability density ||2 for that
system is physically significant while the probability amplitude  not. Consider an atom such

as sodium that has a single s electron outside of a closed shell. Both the wave functions  S ( r )
+

and  S ( r ) are valid for such an atom [ S ( r ) and  S ( r ) are symmetric and anti symmetric
− + −

wave functions]. As the two sodium atoms are brought closer together, their wave functions
begin to overlap. Figure 4.13 represents two possible combinations : i) symmetric - symmetric
and ii) symmetric – antisymmetric . These two possible combinations of wave functions
represent two possible states of the two-atom system. Thus, the states are split into two
energy levels. The energy difference between these states is relatively small, so the two states
are close together on an energy scale.
When two atoms are brought together, each energy level will split into 2 energy levels. (In
general, when N atoms are brought together N split levels will occur which can hold 2N
electrons). The split levels are so close that they may be regarded as a continuous band of
energy levels. Figure 4.14 shows the splitting of 1s and 2s levels of sodium atom when :
(a) two sodium atoms are brought together (b)five sodium atoms are brought together (c)
a large number of sodium atoms are assembled to form a solid. The close energy levels
forming a band are seen clearly in (c).

Figure. 4.13: The wave functions of two atoms combine to form a composite wave function :
a) symmetric-symmetric b) symmetric-antisymmetric

Figure 4.14: Splitting of 1s and 2s levels of sodium atoms due to interaction between them
Some bands may be wide enough in energy so that there is an overlap between the
adjacent bands. Some other bands are narrow so that a gap may occur between the allowed
bands, and is known as forbidden energy gap. The 1s, 2s, and 2p bands of solid sodium
are filled completely with electrons. The 3s band (2N states) of solid sodium has only
N electrons and is partially full; The 3p band, which is the higher region of the overlapping
bands, is completely empty as shown in Figure 4.15
 Figure 5.15: Energy bands of a sodium crystal

4.6 ELECTRICAL CONDUCTION IN METALS, INSULATORS AND

SEMICONDUCTORS
Good electrical conductors contain high density of free charge carriers, and the density
of free charge carriers in insulators is nearly zero. In semiconductors free-charge-carrier
densities are intermediate between those of insulators and those of conductors.
Metals: Metal has a partially filled energy band (Figure 4.16 (a)). At 0K Fermi level is
the highest electron-occupied energy level. If a potential difference is applied to the
metal, electrons having energies near the Fermi energy require only a small amount of
additional energy to reach nearby empty energy states above the Fermi-level. Therefore,
electrons in a metal experiencing a small force (from a weak applied electric field) are free to
move because many empty levels are available close to the occupied energy levels. The model
of metals based on band theory demonstrates that metals are excellent electrical conductors.
Insulators: Consider the two outermost energy bands of a material in which the lower band is
filled with electrons and the higher band is empty at 0 K (Figure 4.16 (b)). The lower, filled
band is called the valence band, and the upper, empty band is the conduction band. The energy
separation between the valence and conduction band, called energy gap Eg, is large for
insulating materials. The Fermi level lies somewhere in the energy gap. Due to larger energy
gap compare to thermal energy kT (26meV) at room temperature, excitation of electrons from
valence band to conduction band is hardly possible. Since the free-electron density is nearly
zero, these materials are bad conductors of electricity.
Semiconductors: Semiconductors have the same type of band structure as an insulator, but the
energy gap is much smaller, of the order of 1 eV. The band structure of a semiconductor is
shown in Figure 4.16c. Because the Fermi level is located near the middle of the gap for a
semiconductor and Eg is small, appreciable numbers of electrons are thermally excited from
the valence band to the conduction band. Because of the many empty levels above the thermally
filled levels in the conduction band, a small applied potential difference can easily raise the
energy of the electrons in the conduction band, resulting in a moderate conduction. At T = 0
K, all electrons in these materials are in the valence band and no energy is available to excite
them across the energy gap. Therefore, semiconductors are poor conductors at very low
temperatures. Because the thermal excitation of electrons across the narrow gap is more
probable at higher temperatures, the conductivity of semiconductors increases rapidly with
temperature. This is in sharp contrast with the conductivity of metals, where it decreases with
increasing temperature. Charge carriers in a semiconductor can be negative, positive, or both.
When an electron moves from the valence band into the conduction band, it leaves behind a
vacant site, called a hole, in the otherwise filled valence band.

Figure 4.16: Band structure of (a) Metals (b) Insulators (c) Semiconductors
In an intrinsic semiconductor (pure semiconductor) there are equal number of conduction
electrons and holes. In the presence of an external electric field, the holes move in
the direction of field and the conduction electrons move opposite to the direction of
the field. Both these motions correspond to the current in the same direction (Figure
4.17).

Figure 4.17: Movement of electrons and holes in an intrinsic semiconductor

Doped Semiconductors (Extrinsic semiconductors): Semiconductors in their pure form are
called intrinsic semiconductors while doped semiconductors are called extrinsic
semiconductors. Doping is the process of adding impurities to a semiconductor. By doping
both the band structure of the semiconductor and its resistivity are modified. If a
tetravalent semiconductor (Si or Ge) is doped with a pentavalent impurity atom (donor
atom), four of the electrons form covalent bonds with atoms of the semiconductor and
one is left over (Figure 4.18). At zero K, this extra electron resides in the donor-levels,
that lie in the energy gap, just below the conduction band. Since the energy Ed between
the donor levels and the bottom of the conduction band is small, at room temperature,
the extra electron is thermally excited to the conduction band. This type of
semiconductors are called n-type semiconductors because the majority of charge carriers
are electrons (negatively charged).
If a tetravalent semiconductor is doped with a trivalent impurity atom (acceptor atom),
the three electrons form covalent bonds with neighboring semiconductor atoms, leaving
an electron deficiency (a hole) at the site of fourth bond (Figure 4.19). At zero K, this
hole resides in the acceptor levels that lie in the energy gap just above the valence
band. Since the energy Ea between the acceptor levels and the top of the valence band
is small, at room temperature, an electron from the valence band is thermally excited
to the acceptor levels leaving behind a hole in the valence band. This type of
semiconductors are called p-type semiconductors because the majority of charge carriers
are holes (positively charged).

Figure 4.18: n-type semiconductor – two dimensional representation and band structure
When conduction in a semiconductor is the result of acceptor or donor impurities, the material
is called an extrinsic semiconductor. The typical range of doping densities for extrinsic
semiconductors is 1013 to 1019 cm-3, whereas the electron density in a typical semiconductor is
about 1021 cm-3.
 Figure 4.19: p-type semiconductor: two-dimensional representation and band structure

4.7 HALL EFFECT

Hall effect is a process in which a transverse electric field is developed in a solid material when
the material carrying an electric current is placed in a magnetic field that is perpendicular to
the current. The Hall effect was discovered by Edwin Herbert Hall in 1879. When a current-
carrying conductor or a semiconductor is introduced to a perpendicular magnetic field, a
voltage can be measured at the right angle to the current path. This effect of obtaining a
measurable voltage is known as the Hall effect.

Consider a semiconductor (assumed to be n-type) in the form of a rectangular strip of width w,

thickness t and electron density n. Let a current  flow along its length in X direction and a
transverse magnetic field B be applied across its thickness t along the Y direction (Figure 4.20).

Figure 4.20 : Hall Effect in n-type semiconductor

The moving electrons experience a force 𝐹𝑀 due to the magnetic field. Due to 𝐹𝑀 , the electrons
tend to move in the Z direction leaving behind the positive charges.

𝐹𝑀 = 𝑒 𝑣𝐷 𝐵

where, 𝑣𝐷 is the drift speed of the electrons and 𝑒 is the charge on the electron.

This separation of charges results in an electric field EH across the width of the specimen (in Z
direction). EH exerts a force on the electrons given by

𝐹𝐸 = − 𝑒 𝐸𝐻

Under equilibrium conditions 𝑒 𝐸𝐻 = 𝑒 𝑣𝐷 𝐵  𝐸𝐻 = 𝑣𝐷 𝐵

VH I
We have EH = and vD =
w ne wt

Substituting these values, we get

B RH  B
VH = or VH =
net t

1
Where, the quantity = RH is called the Hall coefficient of the specimen.
ne

 V  t 
 RH =  H   (4.29)
 B   

The hall coefficient is positive if the number of positive charges is more than the negative
charges. Similarly, it is negative when electrons are more than holes.

Applications of Hall Effect:

1. Magnetic field sensing equipment (Gauss Meter)

2. For the measurement of direct current, Hall effect Tong Tester is used.
3. It is used in phase angle measurement.
4. Proximity detectors
5. Hall effect Sensors and Probes
6. For detecting wheel speed and accordingly assist the anti-lock braking system.
4.8. RESISTIVITY MEASUREMENT BY FOUR PROBE METHOD

A material's electrical resistivity is a measure of how strongly it opposes the flow of current.
The Ω-m is the SI unit of electrical resistivity. The electric resistance (R) of a material is given
by R = V/I where V is electrical potential difference across the material and I is the current
through the material. The resistance depends on the dimension of the material. For a wire R =
L/A, where L is the length of the area, A is the cross sectional area of the wire and  is the
electrical resistivity of the material of the wire. Thus, for a wire, the resistivity,

𝑅×𝐴
𝜌= 𝐿

When two probes are used for measurement of voltage and current, and hence for the
calculation of resistance in the case of a semiconductor, the probe resistance, the contact
resistance, the spreading resistance, and the sheet resistance (resistance of a square piece of a
thin material with contacts made to two opposite sides of the square) due to the semiconductor
will come into effect. Using four probes one can eliminate the probe resistance, contact
resistance (the electrical resistance that arises at the contact point when components are
connected) and the spread resistance (refers to the phenomenon in which current spreads
through a material or device, resulting in a decrease in resistance. in the measurement).

The current is passed through the outer probes and the voltage is measured across the inner
probes. The resistivity measured using the four probes may vary with the geometry (thickness
and shape) of the semiconductor sample and placement of the probes on the surface of the
sample. It may also vary with the probe gap, nature of the surface of the sample, the size of the
sample.

Figure 4.21: Experimental setup for resistivity measurement.

Mathematical calculations show that the resistivity of a semi-infinite sample is given by

𝑉
𝜌0 = × 2𝜋𝑆
𝐼

where I is the current through the outer probes, V is the voltage across the inner probes, S is the
distance between the probes (which is taken to be the same here) and 2πS is the geometric
factor of the semi-infinite sample.

For a finite rectangular sample of thickness W, a dimension correction function f (W/S) is

introduced in the resistivity expression as,

𝜌0
𝜌=
𝑓(𝑊 ⁄𝑆)

2𝜋𝑆 𝑉
i.e., 𝜌 = 𝑓(𝑊⁄𝑆) × (4.30)
𝐼

The resistivity is estimated form the above expression.

4.9 PHOTOVOLTAIC EFFECT AND SOLAR CELLS

Solar cells, also referred to as photovoltaic cells, are pivotal in the realm of renewable energy.
Their functionality hinges on the photovoltaic effect, where semiconductor materials within
the cell absorb photons from sunlight. These absorbed photons energize electrons, enabling
them to flow as an electric current. This process occurs without moving parts, noise, or
greenhouse gas emissions, rendering solar cells an environmentally friendly and sustainable
energy source. The significance of solar cells lies in their contribution to mitigating climate
change and reducing dependence on finite fossil fuels. By harnessing the virtually infinite
energy of the sun, solar cells offer a clean alternative to traditional energy sources. They aid in
shrinking carbon footprints, thereby combating global warming and environmental
degradation. Moreover, solar cells have versatile applications, ranging from powering
residential homes and commercial buildings to providing electricity in remote locations
without access to the grid. They also find use in spacecraft, satellites, and portable electronic
devices, showcasing their adaptability and reliability in various settings.

Solar spectrum and Air Mass (AM)

The solar spectrum and air mass are crucial concepts in understanding how sunlight interacts
with the Earth's atmosphere and influences the performance of solar energy systems. The solar
spectrum refers to the distribution of electromagnetic radiation emitted by the sun across
different wavelengths. Sunlight contains a broad range of wavelengths, from ultraviolet (UV)
to infrared (IR), with visible light occupying the middle portion of the spectrum. Each
wavelength carries a specific amount of energy, and the distribution of this energy determines
the spectral composition of sunlight. However, as sunlight travels through the Earth's
atmosphere, it encounters various molecules and particles that can scatter and absorb certain
wavelengths. This interaction alters the solar spectrum reaching the Earth's surface. For
instance, shorter wavelengths like UV are more prone to scattering by molecules such as
oxygen and nitrogen, while longer wavelengths like IR can be absorbed by greenhouse gases
like water vapor and carbon dioxide.

Air mass (AM) quantifies the path length of sunlight through the Earth's atmosphere before
reaching the surface. It is expressed numerically as the ratio of the actual path length to the
shortest possible path length through the atmosphere (when the sun is directly overhead). Air
mass values vary depending on the angle of the sun relative to the observer's location. For
example, AM1 corresponds to solar radiation perpendicular to the Earth's surface at sea level,
while higher AM values represent sunlight traveling through a thicker atmospheric layer at
greater angles. Understanding the solar spectrum and air mass is crucial for designing and
optimizing solar energy systems. The standard spectrum for space applications is referred to as
AM0. It has an integrated power of 1366.1 W/m2. The AM1.5 Global spectrum is designed for
flat plate modules and has an integrated power of 1000 W/m2.

(Source: [Link]
 Figure 4.22. Solar spectrum (Red: AM1.5)
Solar Cell: p-n junction under illumination

Figure 4.23: Schematic of a solar cell

At the heart of a solar cell is a semiconductor material, often silicon, with additional elements
added to create either a positive (p-type) or negative (n-type) charge. When sunlight strikes the
solar cell, it excites electrons in the semiconductor material, causing them to break free from
their atoms. This process generates electron-hole pairs. However, for these electron-hole pairs
to produce an electric current, they need to be separated and directed towards an external
circuit. This separation occurs at the junction between the p-type and n-type regions of the solar
cell, known as the p-n junction. At this junction, the free electrons from the n-type region are
attracted to the positive charge in the p-type region, while the holes from the p-type region are
attracted to the negative charge in the n-type region. This movement of charge creates an
electric field across the junction.

When an external circuit is connected to the solar cell, the separated electrons and holes can
flow in opposite directions through the circuit, generating an electric current. This flow of
electrons constitutes electricity, which can be harnessed to power electrical devices or stored
in batteries for later use.

Figure 4.24: Solar cell under illumination

 Figure 4.25: Energy level diagram showing carrier transport under illumination of a p-n
junction
Solar Cell Parameters
(i) Maximum Power Point Power (PMPP): The semiconductor material of the solar cell has its
internal resistance. This resistance varies with the light intensity and attains a minimum value
at maximum intensity. At this saturation value the power output is maximum. This maximum
power output is termed as maximum power point power and denoted as PMPP. At this point
maximum power transfer takes from the solar cell to the load, and it is given by,
PMPP = I × V
PMPP is measured by finding the product of voltage and current at the maximum power point.
(ii) Short Circuit Current (ISC) : When the solar cell terminals are shorted (RL = 0) together
maximum current flows through the terminals. This maximum current is called short-circuited
current and denoted as ISC.
(iii) Open Circuit Voltage (VOC) : The voltage measured at the terminals of the solar cell without
load (RL = ) is called open circuit voltage and denoted as VOC. At both the cases of open
circuit or short circuit the power dissipated by the solar cell is zero.
(iv) Conversion Efficiency (η) : In a solar cell light energy is converted in to electrical energy.
In this process of conversion not all input solar radiation is converted in to electric current. The
conversion efficiency denoted in percentage and it is given by,
𝑂𝑢𝑡𝑝𝑢𝑡 𝑃𝑜𝑤𝑒𝑟
𝜂=
𝐼𝑛𝑝𝑢𝑡 𝑝𝑜𝑤𝑒𝑟
𝑃𝑀𝑃𝑃
𝜂=
𝐴𝐶 𝐸
where AC is the surface area of the solar cell, E is the light intensity in watts/cm2.
(v) Fill Factor: The fill factor (FF) of a solar cell is a parameter used to quantify its efficiency
in converting sunlight into electrical energy. It represents the ratio of the maximum power
output of the solar cell to the product of its open-circuit voltage (Voc) and short-circuit current
(Isc). Mathematically, the fill factor (FF) is defined as:
𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑝𝑜𝑤𝑒𝑟 𝑜𝑢𝑡𝑝𝑢𝑡
𝐹𝐹 =
𝑉𝑂𝐶 𝐼𝑆𝐶
The fill factor essentially measures how effectively a solar cell can utilize the available sunlight
to produce electricity. It takes into account losses within the solar cell, including those due to
recombination of charge carriers, series resistance, and shunt resistance.
Ideally, a solar cell would have a fill factor of 1, indicating perfect efficiency. However, in
practice, fill factors for commercial solar cells typically range from 0.5 to 0.8, depending on
various factors such as the materials used, manufacturing processes, and operating conditions.

(Source: [Link]

Figure 4.26: I-V and P-V curve for a typical solar cell
Solar cell materials
The Shockley-Queisser limit, named after scientists William Shockley and Hans-Joachim
Queisser, is a theoretical maximum efficiency limit for a single-junction solar cell. It
establishes the maximum efficiency a solar cell can achieve based on fundamental principles
of thermodynamics and semiconductor physics. It takes into account factors such as the
bandgap energy of the semiconductor material used in the solar cell, the energy of photons in
sunlight, and the loss mechanisms within the cell. According to the Shockley-Queisser limit,
the maximum efficiency of a single-junction solar cell operating under one sun illumination
(AM1.5G spectrum) at room temperature is approximately 33.7%. For single-junction solar
cells, the bandgap energy should be such that it matches the solar spectrum to achieve
maximum absorption of photons. Typically, bandgap energies in the range of 1.1 to 1.7 electron
volts (eV) are considered suitable for solar cells.

(Source: [Link]

Figure 4.27: Shockley-Queisser limit

Choosing the right material for solar cells involves a strategic approach that considers several
factors to optimize performance, cost-effectiveness, and sustainability.
Efficiency: Prioritize materials with high conversion efficiency to maximize electricity
generation per unit area. Silicon-based solar cells offer proven high efficiency, but emerging
materials like perovskites show potential for even greater efficiency gains.
Cost-effectiveness: Balance efficiency with cost to ensure affordability and scalability. Silicon
remains a popular choice due to its abundance, but thin-film technologies like cadmium
telluride (CdTe) and copper indium gallium selenide (CIGS) offer lower manufacturing costs
per watt.
Availability: Consider the availability and accessibility of raw materials to ensure long-term
sustainability and reduce supply chain risks. Choose materials with ample global reserves and
minimal geopolitical constraints.
Stability and Reliability: Select materials with proven long-term stability and reliability under
various environmental conditions to ensure consistent performance over the solar cell's
lifetime.
Toxicity and Environmental Impact: Assess the environmental impact and toxicity of
materials throughout their lifecycle, from extraction and manufacturing to disposal or
recycling. Choose materials with minimal environmental footprint and recyclability to promote
sustainability.
Technological Feasibility: Evaluate the technological readiness and scalability of materials
for large-scale manufacturing. Consider factors such as ease of fabrication, compatibility with
existing infrastructure, and potential for integration into commercial production processes.

4.10 SUPERCONDUCTIVITY-PROPERTIES AND APPLICATIONS

Superconductor is a class of metals and compounds whose electrical resistance decreases to
virtually zero below a certain temperature Tc called the critical temperature. The critical
temperature is different for different superconductors. Mercury loses its resistance completely
and turns into a superconductor at 4.2K. Critical temperatures for some important
elements/compounds are listed below.

Element/Compound Tc (K)
La 6.0
NbNi 10.0
Nb3Ga 23.8

Figure 4.28: Plot of Resistance Vs Temperature for normal metal and a superconductor

Meissner Effect: In the presence of magnetic field, as the temperature of superconducting

material is lowered below Tc, the field lines are spontaneously expelled from the interior of the
superconductor(B = 0, Figure 6.24). Therefore, a superconductor is more than a perfect
conductor; it is also a perfect diamagnet. The property that B = 0 in the interior of a
superconductor is as fundamental as the property of zero resistance. If the magnitude of the
applied magnetic field exceeds a critical value Bc, defined as the value of B that destroys a
material’s superconducting properties, the field again penetrates the sample. Meissner effect
can be explained in the following way.
 Figure 4.29: A superconductor in the form of a long cylinder in the presence of an external
magnetic field.

A good conductor expels static electric fields by moving charges to its surface. In effect, the
surface charges produce an electric field that exactly cancels the externally applied field inside
the conductor. In a similar manner, a superconductor expels magnetic fields by forming surface
currents. Consider the superconductor shown in Figure 5.24. Let’s assume the sample is
initially at a temperature T>Tc so that the magnetic field penetrates the cylinder. As the cylinder
is cooled to a temperature T<Tc, the field is expelled. Surface currents induced on the
superconductor’s surface produce a magnetic field that exactly cancels the externally applied
field inside the superconductor. As expected, the surface currents disappear when the external
magnetic field is removed.

BCS Theory: In 1957, Bardeen, Cooper and Schrieffer gave a successful theory to explain the
phenomenon of superconductivity, which is known as BCS theory. According to this theory,
two electrons can interact via distortions in the array of lattice ions so that there is a net
attractive force between the electrons. As a result, the two electrons are bound into an entity
called a Cooper pair, which behaves like a single particle with integral spin. Particles with
integral spin are called bosons. An important feature of bosons is that they do not obey the
Pauli exclusion principle. Consequently, at very low temperatures, it is possible for all bosons
in a collection of such particles to be in the lowest quantum state and as such the entire
collection of Cooper pairs in the metal is described by a single wave function. There is an
energy gap equal to the binding energy of a Cooper pair between this lowest state and the next
higher state. Under the action of an applied electric field, the Cooper pairs experience an
electric force and move through the metal. A random scattering event of a Cooper pair from a
lattice ion would represent resistance to the electric current. Such a collision would change the
energy of the Cooper pair because some energy would be transferred to the lattice ion. There
are no available energy levels below that of the Cooper pair (it is already in the lowest state),
however, and none available above because of the energy gap. As a result, collisions do not
occur and there is no resistance to the movement of Cooper pairs.

Types of Superconductors

Type - I Superconductors: Type I superconductors are those superconductors that lose their
superconductivity very easily or abruptly when placed in the external magnetic field. As you
can see from the graph of the intensity of magnetization (M) versus applied magnetic field (H),
when the Type I superconductor is placed in the magnetic field, it suddenly or easily loses its
superconductivity at the critical magnetic field (Hc) (point A).

Figure 4.30: Graph of the intensity of magnetization (M) versus applied magnetic field (H)

After Hc, the Type I superconductor will become a conductor. Type I superconductors are also
known as soft superconductors because they lose their superconductivity easily. Type I
superconductors are perfectly diamagnetic in nature and obey the Meissner effect. Lead (Pb)
at 7.196 K, Lanthanum (La) at 4.88 K and Tantalum (Ta) at 4.47 K are Type-I superconductors.

Type-II Superconductors: Type II superconductors are those superconductors that lose their
superconductivity gradually but not easily or abruptly when placed in the external magnetic
field. As seen from the graph of the intensity of magnetization (M) versus applied magnetic
field (H), when the Type II superconductor is placed in the magnetic field, it gradually loses
its superconductivity. Type II superconductors start to lose their superconductivity at the lower
critical magnetic field (Hc1) and completely lose their superconductivity at the upper critical
magnetic field (Hc2).
 Figure 4.31: Graph of the intensity of magnetization (M) versus applied magnetic field (H)

The state between the lower critical magnetic field (Hc1) and upper critical magnetic field (Hc2)
is known as vortex state or intermediate state. After Hc2, the Type II superconductor will
become a conductor.
Type II superconductors are also known as hard superconductors because they lose their
superconductivity gradually but not easily. Type II superconductors obey the Meissner effect
but not completely. Example of Type II superconductors: YBCO (Yttrium barium copper
oxide), niobium nitride (NbN), Barium bismuth (BaBi3). Type II superconductors are used for
strong field superconducting magnets.
Applications: Most important and basic application of superconductors is in high field
solenoids which can be used to produce intense magnetic field. Superconducting magnets are
used in magnetic resonance imaging (MRI) technique. Magnetic levitation, based on Meissner
effect, is another important application of superconductors. This principle is used in maglev
vehicles. Detection of a weak magnetic field and lossless power transmission are some other
important applications of superconductors.

QUESTIONS

1. Obtain an expression for rotational energy of a diatomic molecule. Sketch schematically

these rotational energy levels.
2. Obtain expressions for rotational transition photon energies and frequencies.
3. Obtain an expression for vibrational energy of a diatomic molecule. Sketch schematically
these vibrational energy levels. Obtain expression for vibrational transition photon
energies.
4. Write expression for total energy (vibrational and rotational) of a molecule. Sketch
schematically these energy levels of a diatomic molecule for the lowest two
vibrational energy values, indicating the possible transitions. Write the expressions
 for the energy of the photon in the molecular energy transitions. Write the
expression for the frequency separation of adjacent spectral lines.
5. Explain the expression for the total potential energy of a crystal. Sketch
schematically the plot of the same.
6. Define (a) ionic cohesive energy (b) atomic cohesive energy, of a solid.
7. Write the expression for Fermi-Dirac distribution function. Sketch schematically the
plots of this function for zero kelvin and for temperature above zero kelvin.
8. Derive an expression for density-of-states.
9. Assuming the Fermi-Dirac distribution function , obtain an expression for the density
of free-electrons in a metal with Fermi energy EF, at zero K and, hence obtain
expression for Fermi energy EF in a metal at zero K. [ Given: density-of-states
3
8 2  m 2 12
function g( E ) dE = E dE ]
h3
10. Explain the formation of energy bands in solids with necessary diagrams.
11. Distinguish between conductors, insulators and semiconductors on the basis of band
theory
12. Indicate the position of (a) donor levels (b) acceptor levels, in the energy band
diagram of a semiconductor.
13. What is the difference between p-type and n-type semiconductors? Explain with band
diagram.
14. With necessary diagrams, explain doping in semiconductors.
15. Why the electrical conductivity of an intrinsic semiconductor increases with increasing
temperature?
16. Explain Hall effect and derive an expression for Hall coefficient.
17. Explain measurement of resistivity of a semiconductor by four-probe method.
18. What are the advantages of four-probe method?
19. Define (i) Fill factor, (ii) Open circuit voltage, (iii) Short circuit current, (iv) Efficiency of
a solar cell.
20. Give representative I-V plot of a solar cell under illumination and indicate Voc, Isc,
maximum power point.
21. What are superconductors? Draw a representative graph of Resistance Vs Temperature for
a superconductor.
22. Explain Meissner effect.
23. Explain briefly the BCS theory of superconductivity in metals.
24. Classify and explain types of superconductors.

PROBLEMS
1. An HCl molecule is excited to its first rotational energy level, corresponding
to J = 1. If the distance between its nuclei is ro = 0.1275 nm, what is the angular
speed of the molecule about its center of mass ?
Ans: 5.691012 rad/s
 2. The rotational spectrum of the HCl molecule contains lines with wavelengths of
0.0604, 0.0690, 0.0804, 0.0964, and 0.1204 mm. What is the moment of inertia of the
molecule?
Ans: 2.72x10-47 kg.m2
3. The frequency of photon that causes v = 0 to v = 1 transition in the CO molecule
is 6.42 x 1013 Hz. Ignore any changes in the rotational energy. (A) Calculate the force
constant k for this molecule. (B) What is the maximum classical amplitude of
vibration for this molecule in the v = 0 vibrational state ?
Ans: A) 1.85103 N/m B) 0.00479 nm
4. Consider a one-dimensional chain of alternating positive and negative ions. Show that
the potential energy associated with one of the ions and its interactions with the
rest of this hypothetical crystal is

e2
U(r ) = − k e 
r
where the Madelung constant is  = 2 ln 2 and r is the inter-ionic spacing.
Hint: Use the series expansion
x2 x3 x4
ln (1 + x ) = x − + − + ...
2 3 4
5. Each atom of gold (Au) contributes one free-electron to the metal. The concentration of free-
electron in gold is 5.90 x 1028/m3. Compute the Fermi Energy of gold.
Ans: 5.53 eV
6. Sodium is a monovalent metal having a density of 971 kg/m3 and a molar mass of
0.023 kg/mol. Use this information to calculate (a) the density of charge carriers
and (b) the Fermi energy.
Ans: 2.54 x 1028/m3, 3.15 eV
7. Calculate the energy of a conduction electron in silver at 800 K, assuming the probability
of finding an electron in that state is 0.950. The Fermi energy is 5.48 eV at this
temperature.
Ans: 5.28 eV
8. Show that the average kinetic energy of a conduction electron in a metal at zero
K is (3/5) EF
Suggestion: In general, the average kinetic energy is
1
ne 
E AV = E N( E ) dE

where the density of particles


ne =  N( E ) dE
0
3 1
8 2 m 2
E dE
2
N( E ) dE =
h3  E − EF 
exp   + 1
 kT 
9. (a) Consider a system of electrons confined to a three-dimensional box. Calculate the
ratio of the number of allowed energy levels at 8.50 eV to the number at 7.00 eV. (b)
Copper has a Fermi energy of 7.0 eV at 300 K. Calculate the ratio of the number of
occupied levels at an energy of 8.50 eV to the number at Fermi energy. Compare
your answer with that obtained in part (a).
Ans: (a) 1.10 (b) 1.4610-25
10. Most solar radiation has a wavelength of 1 μm or less. What energy gap should the material
in solar cell have in order to absorb this radiation ? Is silicon (Eg= 1.14 eV) appropriate?
Ans: 1.24 eV or less; yes
11. The energy gap for silicon at 300 K is 1.14 eV. (a) Find the lowest-frequency photon that can
promote an electron from the valence band to the conduction band. (b) What is the wavelength
of this photon?
Ans: 2.7x1014 Hz, 1090 nm
12. A light-emitting diode (LED) made of the semiconductor GaAsP emits red light ( λ=
650nm). Determine the energy-band gap in the semiconductor.
Ans: 1.91 eV

13. Consider a semiconductor in the form of a rectangular strip of thickness 10 µm. Let
a current of 1 mA flow along its length and a transverse magnetic field of strength 1T
be applied across its thickness. If Hall voltage is 2mV, then calculate charge carrier
density.
Ans: 3.1 x 1023m-3
14. The Hall coefficient of certain Silicon specimen was found to be -7.35 x 105 m3C-1.
Calculate the charge carrier density. Mention type of the charge carrier.
Ans: 8.455 x 1022 m-3; electrons