Unit 2: Band theory of solids, Conductivity of metals .

Conductors, Insulators, Semiconductors,

Intrinsic and extrinsic semiconductors, Band theory of semiconductors. Super Conductors. Type I
and II super conductors. Applications of Superconductors.

(1) Band theory of solids (What is band energy?)

Let us now make an extrapolation of some of these concepts to solid materials. A solid may
be thought of as consisting of a large number, say, N, of atoms initially separated from one
another, which are subsequently brought together and bonded to form the ordered atomic
arrangement found in the crystalline material. At relatively large separation distances, each
atom is independent of all the others and will have the atomic energy levels and electron
configuration as if isolated. However, as the atoms come within close proximity of one
another, electrons are acted upon, or perturbed, by the electrons and nuclei of adjacent atoms.
This influence is such that each distinct atomic state may split into a series of closely spaced
electron states in the solid, to form what is termed an electron energy band.
The extent of splitting depends on interatomic separation (Figure 12.2) and begins with the
outermost electron shells, since they are the first to be perturbed as the atoms coalesce.Within
each band, the energy states are discrete, yet the difference between adjacent states is
exceedingly small. At the equilibrium spacing, band formation may not occur for the electron
subshells nearest the nucleus, as illustrated in Figure 12.3b. Furthermore, gaps may exist
between adjacent bands, as also indicated in the figure; normally, energies lying within these
band gaps are not available for electron occupancy. The conventional way of representing
electron band structures in solids is shown in Figure 12.3a.

The number of states within each band will equal the total of all states contributed by the N
atoms. For example, an s band will consist of N states, and a p band of 3N states.With regard
to occupancy, each energy state may accommodate two electrons, which must have
oppositely directed spins. Furthermore, bands will contain the electrons that resided in the
corresponding levels of the isolated atoms; for example, a 4s energy band in the solid will
contain those isolated atom’s 4s electrons. Of course, there will be empty bands and,
possibly, bands that are only partially filled. The electrical properties of a solid material are a
consequence of its electron band structure—that is, the arrangement of the outermost electron
bands and the way in which they are filled with electrons.

(2) Fermi Energy

Four different types of band structures are possible at 0 K. In the first (Figure12.4a), one
outermost band is only partially filled with electrons. The energy corre-sponding to the
highest filled state at 0 K is called the Fermi energy Ef , as indicated. This energy band
structure is typified by some metals, in particular those that have a single s valence electron
(e.g., copper). Each copper atom has one 4s electron; however, for a solid comprised of N
atoms, the 4s band is capable of accommodating 2N electrons. Thus only half the available
electron positions within this 4s band are filled.

For the second band structure, also found in metals (Figure 12.4b), there is an overlap of an
empty band and a filled band. Magnesium has this band structure. Each isolated Mg atom has
two 3s electrons. However, when a solid is formed, the 3s and 3p bands overlap. In this
instance and at 0 K, the Fermi energy is taken as that energy below which, for N atoms, N
states are filled, two electrons per state.

(3) Valence Band, Conduction band, and Energy band

The final two band structures are similar: one band (the valence band) that is completely
filled with electrons is separated from an empty conduction band, and an energy band gap
lies between them. For very pure materials, electrons may not have energies within this gap.
The difference between the two band structures lies in the magnitude of the energy gap; for
materials that are insulators, the band gap is relatively wide (Figure 12.4c), whereas for
semiconductors it is narrow (Figure 12.4d).
(4) CONDUCTION IN TERMS OF BAND AND ATOMIC BONDING MODELS

(4.1) Free electron hole

At this point in the discussion, it is vital that another concept be understood—namely, that
only electrons with energies greater than the Fermi energy may be acted on and accelerated in
the presence of an electric field. These are the electrons that participate in the conduction
process, which are termed free electrons. Another charged hole electronic entity called a
hole is found in semiconductors and insulators. Holes have energies less than Ef and also
participate in electronic conduction. As the ensuing discussion reveals, the electrical
conductivity is a direct function of the numbers of free electrons and holes. In addition, the
distinction between conductors and nonconductors (insulators and semiconductors) lies in the
numbers of these free electron and hole charge carriers.

(4.1.1) Metals
For an electron to become free, it must be excited or promoted into one of the empty and
available energy states above Ef. For metals having either of the band structures shown in
Figures 12.4a and 12.4b, there are vacant energy states adjacent to the highest filled state at
Ef. Thus, very little energy is required to promote electrons into the low-lying empty states, as
shown in Figure 12.5. Generally, the energy provided by an electric field is sufficient to
excite large numbers of electrons into these conducting states.
(4.1.2) Insulators and Semiconductors

For insulators and semiconductors, empty states adjacent to the top of the filled valence band
are not available. To become free, therefore, electrons must be promoted across the energy
band gap and into empty states at the bottom of the conduction band. This is possible only by
supplying to an electron the difference in energy between these two states, which is
approximately equal to the band gap energy Eg. This excitation process is demonstrated in
Figure 12.6. For many materials this band gap is several electron volts wide. Most often the
excitation energy is from a nonelectrical source such as heat or light, usually the former.
The number of electrons excited thermally (by heat energy) into the conduction band depends
on the energy band gap width as well as temperature. At a given temperature, the larger the
Eg, the lower is the probability that a valence electron will be promoted into an energy state
within the conduction band; this results in fewer conduction electrons. In other words, the
larger the band gap, the lower is the electrical conductivity at a given temperature. Thus, the
distinction between semiconductors and insulators lies in the width of the band gap; for
semiconductors it is narrow, whereas for insulating materials it is relatively wide.
Increasing the temperature of either a semiconductor or an insulator results in an increase in
the thermal energy that is available for electron excitation. Thus, more electrons are promoted
into the conduction band, which gives rise to an enhanced conductivity.

(4.2) Electron mobility

The scattering phenomenon is manifested as a resistance to the passage of an electric current.

Several parameters are used to describe the extent of this scattering; these include the drift
velocity and the mobility of an electron. The drift velocity vd represents the average electron
velocity in the direction of the force imposed by the applied field. It is directly proportional to
the electric field as follows:

The constant of proportionality μe is called the electron mobility, and is an indication of the
frequency of scattering events; its units are square meters per volt-second (m2/V-s).
where n is the number of free or conducting electrons per unit volume (e.g., per cubic meter),
and |e| is the absolute magnitude of the electrical charge on an electron (1.6 × 10−19 C). Thus,
the electrical conductivity is proportional to both the number of free electrons and the
electron mobility.

(4.3) ELECTRICAL RESISTIVITY OF METALS

Since crystalline defects serve as scattering centers for conduction electrons in metals,
increasing their number raises the resistivity (or lowers the conductivity). The concentration
of these imperfections depends on temperature, composition, and the degree of cold work of a
metal specimen. In fact, it has been observed experimentally that the total resistivity of a
metal is the sum of the contributions from thermal vibrations, impurities, and plastic
deformation; that is, the scattering mechanisms act independently of one another. This may
be represented in mathematical form as follows:

in which ρt, ρi, and ρd represent the individual thermal, impurity, and deformation resistivity
contributions, respectively.

where ρ0 and a are constants for each particular metal. This dependence of the thermal
resistivity component on temperature is due to the increase with temperature in thermal
vibrations and other lattice irregularities (e.g., vacancies), which serve as electron-scattering
centers.
Influence of Impurities

For additions of a single impurity that forms a solid solution, the impurity resistivity ρi is
related to the impurity concentration ci in terms of the atom fraction (at%/100) as follows:

Where A is a composition-independent constant that is a function of both the impurity and

host metals. The influence of nickel impurity additions on the room-temperature resistivity of
copper is demonstrated in Figure 12.9, up to 50 wt% Ni; over this composition range nickel is
completely soluble in copper (Figure 10.3a). Again, nickel atoms in copper act as scattering
centers, and increasing the concentration of nickel in copper results in an enhancement of
resistivity.

For a two-phase alloy consisting of α and β phases, a rule-of-mixtures expression may be

utilized to approximate the resistivity as follows:
(5) Intrinsic semisemiconductor
The electrical conductivity of the semiconducting materials is not as high as that of the
metals; nevertheless, they have some unique electrical characteristics that render them
especially useful. The electrical properties of these materials are extremely sensitive to the
presence of even minute concentrations of impurities. Intrinsic semisemiconductor
conductors are those in which the electrical behavior is based on the electronic structure
inherent in the pure material. When the electrical characteristics are dictated by impurity
atoms, the semiconductor is said to be extrinsic.

TYPES OF SUPERCONDUCTORS
• Depending upon the behavior in an external magnetic field, superconductors are divided
into two categories:
1. Type-I superconductor or soft superconductor
2. Type-II superconductor or hard superconductor

(6) What is Type-I Superconductor?

Type-I superconductor acts as a perfect diamagnetic material and obeys Meissnar effect.
Type-II Superconductor

Type-II superconductors do not obey perfect Meissner effect.

(a) Meissner effect - The Meissner effect is the expulsion of a magnetic field from
a superconductor during its transition to the superconducting state when it is cooled below the
critical temperature. This expulsion will repel a nearby magnet.

•As value of magnetic field field (H) increases, magnetisation of superconductor increases.
Upto Hc1 it shows perfect superconducting behavior.
•Above Hc1 force of external magnetic field lines increases and it starts penetrating
superconducting material. At Hc2 material losts its superconductivity completely.

•The state between Hc1 and Hc2 is known as “Vortex state” or “Mixed state”.

•As to destroy superconductivity of type-II superconductor is difficult than type-I

superconductor due to its high value of Hc, it is known as “Hard superconductor”.

•Mostly alloys and ceramics like NbN (Hc = 8 x 106 Tesla), Babi3 (Hc = 59 x 103 Tesla) are
examples of hard superconductors.