Energy Bands for Electrons

in Crystals (Kittel Ch. 7)

Recall nature of free electron gas

Free electrons in box of size L x L x L
(artificial but useful)
Solved Schrodinger Equation
States classified by k with E(k) = (h2/2m) k2
Periodic boundary conditions convenient:
Leads to kx = 2n/L, etc.
Pauli Exclusion Principle, Fermi Statistics
Simplest model for metals
Why are some materials insulators, some metals?

Energy

Energy
Gap

/a

/a

Understanding Electrons in Crystals

Recall nature of free electron gas

Free electrons in box of size L x L x L
(artificial but useful)
Solved Schrodinger Equation
States classified by k with E(k) = (h2/2m) k2
Periodic boundary conditions convenient:
Leads to kx = 2n/L, etc.
Pauli Exclusion Principle, Fermi Statistics
Simplest model for metals
Why are some materials insulators, some metals?

First step - NEARLY free electrons in a crystal

Simple picture of how Bragg diffraction leads to
standing waves at the Brillouin Zone Boundary and to
energy gaps

Electron Gas
Simplest possible model
for a metal - electrons are
completely free of the
nuclei - nuclei are replaced
by a smooth background -Electrons in a box
Real Crystal Potential variation with
the periodicity of the crystal
Attractive (negative) potential
around each nucleus

Schrodinger Equation

Schrodinger Equation

Basic equation of Quantum Mechanics

How can we solve the Schrodinger Eq.

[ - ( h2/2m ) 2 + V(r ) ] (r ) = E (r )

[ - ( h2/2m ) 2 + V( r ) ] ( r ) = E (r )
where V( r ) has the periodicity of the crystal?

where
m = mass of particle
V(r ) = potential energy at point r
2 = (d2/dx2 + d2/dy2 + d2/dz2)
E = eigenvalue = energy of quantum state
(r ) = wavefunction
n (r ) = | (r ) |2 = probability density

Difficult problem - This is the basis of current research

in the theory of electrons in crystals
We will consider simple cases as an introduction
Nearly Free Electrons
Kronig-Penney Model

Key Point for electrons in a crystal: The potential

V(r ) has the periodicity of the crystal

Next Step for Understanding

Electrons in Crystals

Consider 1 dimensional example

If the electrons can move freely on a line from 0 to L
0 (with no potential),
L

Simplest extension of the

Electron Gas model

we have seen before that :

Schrodinger Eq. In 1D with V = 0
- ( h2/2m ) d2/dx2 (x) = E (x)
Solution with (x) = 0 at x = 0,L
(x) = 21/2 L-1/2 sin(kx) , k = n /L, n = 1,2, ...

Nearly Free electron Gas Very small potential variation

with the periodicity of the
crystal
Very weak potentials
with crystal periodicity

or

We will first consider

electrons in one dimension

Fixed Boundary Condition

(x) =

L-1/2

exp( ikx), k = n (2/L), n = 0,1,..

E (k) = ( h2/2m ) k 2

Periodic Boundary Condition

Electrons on a line

Electrons on a line with potential V(x)

For electrons in a box, the energy is just the kinetic

energy
E (k) = ( h2/2m ) k 2
Values of k fixed by the box, k = n (2/L), n = 0,1,..
Crystal: L = Ncell a

What happens if there is a potential V(x) that has the

periodicity a of the crystal?
An electron wave with wavevector k can suffer Bragg
diffraction to k G, with G any reciprocal lattice vector

The maximum (Fermi) wavevector is determined by

the number of free electrons
Nelec/2=2nF+1, thus nF~ Nelec/4
k = n (2/Ncella), n=0,1,.. Nelec/4
define number of electrons per cell N
kF= N/2 (/a)

/a

Result:
Standing wave at zone boundary
Energy gap where there are no waves that can travel
in crystal

Bragg scattering at k = /a leads to two possible

combinations of the right and left going waves:
(+)=(2L)-1/2[exp(ix/a)+exp(-ix/a)] = 21/2 L-1/2cos(x/a)
(-)=(2L)-1/2 [exp(ix/a)-exp(-ix/a)] = 21/2 i L-1/2 sin(x/a)

Energy

Energy
Gap

with density n(+) = 2/L cos2(x/a); n(-) = 2/L sin2(x/a)

n(+) - high density at atoms

Energy Bands Allowed energies for

electrons in the crystal
(more later)

/a

State with k = /a
diffracts to k = - /a
and vice versa
k
/a

Interpretation of Standing waves at

Brillouin Zone boundary

Electrons on a line with potential V(x)

/a

Bragg Diffraction
occurs at
BZ boundary

Atoms

n(-) - low density at atoms

Energy difference between solutions

Electrons on a line with potential

V(x)= Vcos(2x/a)

n(+) = 2/L cos2(x/a); n(-) = 2/L sin2(x/a)

for n(+) the electrons are piled up on the positive ions,
the magnitude of the negative potential energy is
higher, so the energy is lower

n(-) - low density at atoms

high energy

n(-) - low density at atoms

high energy

Energy
Gap

Energy

n(+) - high density at atoms

low energy

Energy gap -- energies at which no waves can travel

L
through crystal E g = dxV ( x )(n( + ) n( )) = V

Atoms - attractive
(negative) potential

n(+) - high density at atoms

low energy

/a

/a

Representing V as a periodic function

Understanding Electrons in Crystals

We have seen (Kittel Ch 2) that any periodic function

can be written as Fourier series
f(r) = G fG exp( i G . r)
where the G s are reciprocal lattice vectors
G(m1,m2,) = m1 b1 + m2 b2 + m3 b3
Check: A periodic function satisfies
f(r) = f(r + T) where T is any translation
T(n1,n2,) = n1 a1 + n2 a2 + n3 a3
the ns are integers

Real Crystal Potential variation with

the periodicity of the crystal
Attractive (negative) potential
around each nucleus
Potential leads to:
Electron bands - E(k) different from free
electron bands
Band Gaps

Thus V(r) = G VG exp( i G . r)

And V(r) = real VG = V*-G or if the crystal is
symmetric VG = V-G

Ex. In a 1D crystal kF= N/2 (/a), where N= # of electrons per cell.

How many electron bands are expected for N=1,2,3,?

Schrodinger Equation - Again

Schrodinger Equation - Continued

In a periodic crystal
[ - ( h2/2m ) 2 + G VG exp( i G . r) ] ( r ) = E ( r )

Then the Schrodinger Eq. becomes:

k ck k exp( i k . r) + k ck G VG exp( i (k + G). r) ]
= E k ck exp( i k . r)
where k = ( h/2m ) | k |2

Now assume ( r ) = k ck exp( i k . r)

Introduce k = k+G then relabel k as k

k { [ k - E ] ck + G VG ck-G } exp( i k . r) = 0
Equating terms with the same r dependence on the
two sides on the equation, we find the Central
Equation

Note we do NOT assume has the periodicity of the

lattice! It is a superposition of waves!
What is k?
Just as before for electrons in a box, we assume
( r ) is periodic in a large box (L x L x L) which leads
to
kx = nx (2/L), n = 0,1,.. | k |= n (2/L)

[ k - E ] ck + G VG ck-G = 0

Central Equation for electron bands

Bloch Theorem

What is the interpretation of the equation:

One of the most important equations of the course!

In a general crystal, the wave function for an electron
has the form:
k ( r ) = G ck-G exp( i (k - G). r)

[ k - E ] ck + G VG ck-G = 0
If VG = 0 (no potential - free electrons) then each k is
independent and each wavefunction is
k ( r ) = ck exp( i k . r) ; E = k = ( h/2m ) | k |2

which can be written

k ( r ) = exp( i k . r) uk ( r )

If VG 0, then each k is mixed with k - G where G is

any reciprocal lattice vector -- the solution is
k ( r ) = G ck-G exp( i (k - G). r)

where uk ( r ) is the periodic function

with the periodicity of the crystal lattice
uk ( r ) = G ck-G exp( - i G . r)

Yet to be determined

Kronig-Penney model

Kronig-Penney model
A exp( iKx ) + B exp( iKx ) for 0 < x < a
C exp( Qx ) + D exp( Qx ) for a < x < a + b

square well potential

( x)=

0 for n( a + b ) < x < ( n + 1 )a + nb

U( x ) =
U 0 for (n + 1 )a + nb < x < ( n + 1 )( a + b )

( a) = exp (ik(a+b)) (-b)

- ( h2/2m ) d2/dx2 (x)+ U(x) (x) = E (x)

Combination of traveling waves where U=0, exponential penetration
into the U=U0 region
A exp( iKx ) + B exp( iKx ) for 0 < x < a
( x)=
C exp( Qx ) + D exp( Qx ) for a < x < a + b

boundary conditions: (x), d (x)/dx continuous

x=0: A+B = C+D, iK(A-B) = Q(C-D)
x=a: A exp(iKa) +B exp(-iKa) = [C exp(-Qb) +D exp(Qb)]exp (ik(a+b))
iK[A exp(iKa) -B exp(-iKa)] = Q [C exp(-Qb) -D exp(Qb)]exp (ik(a+b))

The solution must satisfy the Bloch theorem

k ( x) = exp (ik(a+b)) k ( x-a-b)

Solution if determinant vanishes relationship between a, b,

Q, K, k

Periodicity of the lattice, k is like a reciprocal vector

Kronig-Penney model - limiting case

Bloch Theorem - II
The general form is
kn ( r ) = exp( i k . r) ukn ( r )

Assume b=0, U0~, Q2ba/2=P

(P/Ka) sin Ka + cos Ka = cos ka

where ukn ( r ) is a periodic function. Here n labels

different bands

Solution only when l.h.s.<1

energy gaps at k=0, +- /a, ..
E (k) = ( h2/2m ) K 2

Key Points:
1) Each state is labeled by a wave vector k
2) k can be restricted to the first Brillouin Zone
This may be seen since
k+G ( r ) = exp( i (k + G). r) u k+G ( r )
= exp( i k . r) uk( r )
where uk ( r ) = exp( i G. r) u k+G ( r ) is just another
periodic function

E
bands

Since K depends on P
E is plotted vs. ka
E is not ~k2

2 3

ka

Bloch Theorem - III

The total number of k values

We can use the idea of periodic boundary conditions
on a box of size L x L x L - same as for phonons,
electrons in a box,...
Volume per k point = (2/L)3
Total number of k points in Brillouin zone
Nk-point = VBZ /(2 /L)3 = (2/a)3(L/2)3 = (L/a)3 = Ncell

Thus a wavefunction in a crystal can always be written

kn ( r ) = exp( i k . r) ukn ( r )
where:

ukn ( r ) is a periodic function

n labels different bands
k is restricted to the first Brillouin Zone

Each primitive cell contributes exactly one independent

value of k to each energy band.
Taking the two spin orientations into account, there are
2Ncell independent orbitals in each energy band.

In the limit of a large system

k becomes continuous
n is discrete index: n = 1,2,3, .

Solving the Central Equation

Solving the Central Equation

Simple cases where we can solve

Leads to two coupled equations

[ k - E ] ck + G VG ck-G = 0

[ k - E ] ck + V ck-G = 0

If VG is weak, then we can solve the nearly free

electron problem (and find the solution we saw earlier
in the chapter).

[ k-G - E ] ck-G + V ck = 0
or

For k near BZ boundary, the wave exp( i k . r) is

mixed strongly with exp( i (k - G). r), where G is the
single vector that leads to | k | ~ | k - G |

[ k - E ]
V

=0

[ k-G - E ]

Solution
E = (1/2) ( k + k-G ) +- [(1/4) ( k - k-G )2 + V 2] 1/2
and
ck-G = [( - k + E)/V ] ck

Let V = VG = V-G for that G

Nearly Free Electrons on a line

Solutions in 1D

E = (1/2) ( k + k-G ) +- [(1/4) ( k - k-G )2 + V 2] 1/2

Bands changed greatly only at zone boundary

Energy gap -- energies at which no waves can travel
through crystal
Energies corresponding

ck-G = [( - k + E)/V ] ck

to next BZs are translated

into first BZ

k-G= -/a i (unit vector)

Energy
Gap

Energy

BZ boundary: k= /a i,
k= k-G = ,
= V, += +V
ck-G = +- ck

(+) = ck [exp( i x/a) + exp(-i x/a)]

(-) = ck [exp( i x/a) - exp(-i x/a)]

Far from BZ boundary

wavefunctions and energies
approach free electron values

/a

/a

Free Electrons, 1D, no gaps

How to apply this idea in general

(k + 4/a)2

First find free electron bands plotted in BZ

E
The energy is ALWAYS E (K) = ( h2/2m ) K 2
but now we reduce K to first BZ, i.e., we find G such
that K = k + G , and k is in the first BZ
G(m1,m2,) = m1 b1 + m2 b2 + m3 b3
biaj= 2ij

2
h2
h2
E(k) =
k +G =
( k x + Gx )2 + ( k y + G y )2 + ( k z + Gz )2
2m
2m

(k + 2/a)2

K2
(k + 2/a)2

G= 2/a

Then add effects of potential energy gaps

3/a 2/a /a

/a

2/a 3/a

Free Electrons, 3D, simple cubic, K=(Kx,0,0)

Nearly Free Electrons, 3D, schematic

(kx )2 + 2(2/a)2

(kx )2 + (2/a)2

K2=Kx2

(kx+2/a)2+(2/a)2

E
(kx +

2/a /a

(kx + 2/a)2

(kx )2 + (2/a)2
Gx
Gy or Gz

2/a)2

/a

2/a

kx

/a

/a

kx

Qualitative Picture of Electron Energy

Bands and Gaps in Solids
Allowed Energies for Electrons

Understanding Electrons in Crystals

Real Crystal Potential variation with
the periodicity of the crystal
Attractive (negative) potential
around each nucleus
The nearly free electron cases show the general
form of bands:
Continuous bands of allowed states
Gaps where the are no states for the particular
k points

Forbidden Gap
in Energies for
Valence Electrons
Atomic-like Core States
Distance Between Atoms

Metals vs Insulators

Metals vs Insulators

A band holds two electrons per each cell

Therefore a crystal with an odd number of electrons
per cell MUST* be a metal!
Partially filled bands lead to Fermi energy and
Fermi surface in k space
Conductivity because states can change and
scatter when electric field is applied

In 1d an even number of electrons per cell always

leads to an insulator!
In higher d, it depends on size of gaps
Different direction of k

Semi-metal

A crystal with an even number of electrons per cell

MAY be an insulator!
Electrons frozen
Gap in energy for any excitations of electrons

E
Fermi Energy

/a

Summary
Solving the Central Equation in Fourier space
Bloch Theorem
Bloch states for electrons in crystals
Nearly Free Electrons
General Rules
First Free electron bands
Then add effects of small potential
Energy Bands and Band Gaps -- basis for
understanding metals vs. insulators
Read Kittel Ch 7

10

0 kx

/a

|k|