Engineering Physics

Dr. Rajesh Cheruku

​ ssistant Professor
A
Department of Physics
Central University of Karnataka
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Origin of Energy Bands

➢Consider a free Lithium atom and the electron

moves in a free potential well as shown in figure.
➢If we can solve the Schrodinger wave equations
we will get the discreate series of discreate energy
level, as shown in the figure.
➢In Lithium atom contains three electrons, two of
which occupy the 1s shell (completely) and the
third the 2s subshell.

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➢Now consider the situation in which two lithium atoms assemble to form lithium molecule Li2.
➢The potential seen by the electron is now the double well shown in Figure.

➢The energy spectrum here is comprised of a set of discrete doublets: Each of atomic levels-that
is, the 1s, 2s, 2p ..etc.-has split into two closed spaced levels.
➢Because of the close generic relation between atoms and molecular levels, we may also speak
of 1s,2s, 2p,.. etc, molecular energy levels.
➢Each molecular level can accommodate at most two electrons of opposite spins, according to
exclusion principle.
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➢The amount of splitting depends strongly on the internuclear distance of the two atoms in the
molecule. The closer the two nuclei, the stronger the perturbation and the larger the splitting.
➢The splitting also depends on the atomic orbital: The splitting of the 2p level is larger than that
of the 2s level, which is larger still than that of the 1s level.
➢The above considerations may be generalized to a polyatomic Li molecule of an arbitrary
number of atoms.
➢Thus in a 3-atom molecule, each atomic level is split into a triplet, in a 4-atom molecule into a
quadruplet, and so forth. The lithium solid may then be viewed as the limiting case in which the
number of atoms has become very large, resulting in a gigantic lithium molecule.

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➢Each of the atomic levels is split into N closely spaced sublevels, where N is the
number of atoms in the solid. But since N is so very large, about 1023, the sublevels are
so extremely close to each other that they coalesce, and form an energy band.
➢Thus the ls,2s, 2p levels give rise, respectively, to the ls, 2s, and 2p bands, as shown
in figure.
➢To illustrate how close to each other the sublevels lie within the bands, consider the
following numerical example.
➢Suppose that the width of the band is 5 eV (a typical value). The energy interval
between two adjacent levels is therefore of the order 5/1023:5 x 10-23 eV.
➢Since this is an extremely small value, the individual sublevels are indistinguishable,
so we can consider their distribution as a continuous energy band.

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➢The width of the band varies, but in general the higher the band the greater its width, because,
as we recall from the case of molecules, a high energy state corresponds to a large atomic radius,
and hence a strong perturbation, which is the cause of the level broadening in the first place.
➢By contrast, low energy states correspond to tightly bound orbitals, which are affected but
slightly by the perturbation.
➢Figure shows 2s and 2p bands for metallic lithium plotted as functions of the lattice constants
a.
➢ Note that the band widths increase as a decreases, as is to be expected, since the smaller the
interatomic distance the greater the perturbation.
➢Note also that, for a < 6a, the 2s and 2p bands broaden to the point at which they begin to
overlap, and the gap between them vanishes entirely.

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The Bloch Theorem
➢ The behavior of the electron in a crystalline solid is determined by studying the
appropriate Schrodinger equation.

ħ 𝜵𝟐 + 𝑽(𝒓) Ψ(r) = E Ψ(r)

−𝟐𝒎
𝟐

➢ V(r) crystalline potential seen by the electron, and Ψ(r) and E are, respectively, the
state function and energy of this electron.

➢ The potential V(r) includes the interaction of the electron with all atoms in the solid,
as well as its interaction with other electrons.

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➢At this point we make the important observation that the potential V(r) is periodic.
➢It has the same translational symmetry as the lattice, that is
V(r+R)= V(r)
➢where R is a lattice vector. Such a potential is shown schematically in figure.

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➢According to the Bloch theorem, the solution for a periodic potential V(r) has the
form
Ψk(r)= eik.r uk(r)
➢Where the function uk(r) has the same translational symmetry as the lattice, that is
uk(r+R) = uk(r)
➢The vector k is a quantity related to the momentum of the particle.

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Properties of Bloch function
(a)
It has the form of a traveling plane wave, as represented by the factor eik.r, which implies that
the electron propagates through the crystal like a free particle.
The effect of the function uk(r) is to modulate this wave so that the amplitude oscillates
periodically from one cell to the next, as shown in figure.

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But this does not affect the basic character of the state function, which is that of a traveling
wave.
If the electron were indeed entirely free, the state function Ψk(r) would be given by
𝟏 ik.r
e
√𝑽
that is, the function u(r) is a constant. But the electron is not free, since it interacts with the
lattice, and this interaction determines the special character of the periodic function u(r).
(b)
Because the electron behaves as a wave of vector k, it has a de-Broglie wavelength λ=2π/k
and hence a momentum
P= ħ k
according to the de-Broglie relation. We shall call the vector the crystal momentum of the
electron.

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(c)
The Bloch function Ψk(r) is a crystal orbital, as it is delocalized throughout the
solid, and not localized around any particular atom.
Thus the electron is shared by the whole crystal. This is, of course, consistent
with property (a) above, in which we described the electron as a traveling wave.

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Kronig Penny Model

➢According to the quantum free electron theory of metals, a conduction electron in a metal
experiences constant (or zero) potential and free to move inside the crystal but will not come out
of the metal because an infinite potential exists at the surface.
➢This theory successfully explains electrical conductivity, specific heat, thermionic emission,
and Paramagnetism.
➢The free electron theory fails to explain many other physical properties, for example:
➢(i) it fails to explain the difference between conductors, insulators and semiconductors,
➢(ii) positive Hall coefficient of metals, and
➢(iii) lower conductivity of divalent metals than monovalent metals.

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To overcome the above problems, the periodic
potentials due to the positive ions in metal have been
considered. shown in Figure, if an electron moves
through these ions, it experiences varying potentials.

The potential of an electron at the

positive ion site is zero and is maximum
in between two ions. The potential
experienced by an electron, when it
passes along a line through the positive
ions is as shown in Figure.

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 It is not easy to solve Schrödinger’s equation with these potentials. So, Kronig and Penney
approximated these potentials inside the crystal to the shape of rectangular steps as shown
in Figure. This model is called the Kronig-Penney model of potentials.

The energies of electrons can be known by solving Schrödinger’s wave equation in such a
lattice. The Schrödinger time-independent wave equation for the motion of an electron
along X-direction is given by

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The energies and wave functions of electrons associated with this model can be calculated by
solving time-independent one-dimensional Schrödinger’s wave equations for the two regions I
and II as shown in Figure.
The Schrödinger’s equations are

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According to Bloch’s theorem, the wave function solution of the Schrödinger equation when
the potential is periodic and to make sure the function u(x) is also continuous and smooth,
can be written as Ψ (r)= eik.r u (r)
k k

Where u(x) is a periodic function which satisfies u (x + a) = u(x). Using Bloch theorem and
all the boundary conditions for the continuity of the wave function the solution of
Schrodinger wave equation obtained as

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This equation shows the relation between the energy (through α) and the wave-vector, k, and as
you can see, since the left-hand side of the equation can only range from −1 to 1 then there are
some limits on the values that α (and thus, the energy) can take, that is, at some ranges of values
of the energy, there is no solution according to these equations, and thus, the system will not
have those energies: energy gaps.
These are the so-called band-gaps, which can be shown to exist in any shape of periodic
potential (not just delta or square barriers). This has been plotted in Fig.

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lies between +1 to -1. By varying αa, a wave mechanical nature could be plotted as shown
in Figure, the shaded portion of the wave shows the bands of allowed energy with the
forbidden region as an unshaded portion.

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Metals, Insulators and Semiconductors

Metal Insulator Semi-conductor Semi-metal

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