Solid State Theory Physics 545

Kronnig Penney Kronnig-Penney Model

Band theory Periodic Potential Approach

We have seen that the periodic potential in crystals can give rise to energy bands. But to calculate the energy bands by solving the Schrodinger equation can be a difficult task. Here we will consider a simplified potential, periodic square potential to potential potential, represent the actual potential in a real crystal. This model is called Kronig-Penny. Although it is not Kronig-Penny realistic, it allows us to calculate exactly the energy bands as a function of k that appear in Blochs Bloch s theorem.

Weak vs. Strong Crystal Potentials g y

Previously we used the NEARLY-FREE ELECTRON model to discuss the propagation of electrons in the presence of a PERIODIC crystal potential * In this model we assume that the only effect of the crystal potential is to DIFFRACT electrons whenever the Bragg condition is satisfied * The effect of this diffraction was found to be to open forbidden GAPS in the energy spectrum of the electrons p The SIZE of these gaps was also shown to be proportional to the STRENGTH of the crystal potential
E

O i of an energy gap i the nearly-free electron Opening f in th l f l t model gaps open at wavenumbers for which the electron wavelength is commensurate with the inter-atomic spacing (l = 2a in the case shown here) in this model the gap is understood to result from bragg diffraction of electrons by the crystal structure

ENERGY GAP

/ /a

/ /a

Energy Levels and Bands

Isolated atoms have precise allowed energy levels. In the presence of the periodic lattice potential bands of allowed states are separated by energy gaps for which there are no allowed energy states. The ll Th allowed states in conductors can be constructed from d t t i d t b t t df combinations of free electron states (the nearly free electron model) or from linear combinations of the states of the isolated atoms (the tight binding model).

position

Bound States in atoms

Electrons in isolated atoms occupy discrete allowed energy levels E0, E1, E2 etc. .
0 0 -1

-2

The potential energy of an electron a distance r from a positively charge nucleus of charge q is g

Increasing g Binding E1 Energy E0

E2

V(r)

-3

qe V(r) = 4 o r
2

-4

-5 -8 -6 -4 -2 0 2 4 6 8

r r

Bound and free states in solids

The 1D potential energy of an electron due to an 0 0 array of nuclei of charge y g q separated by a distance -1 a is 2

V (r) =
n

qe q 4 o r na

E2 E1 E0

V(r)

-2

Where n = 0, +/-1, +/-2 etc. -3

-3

This is shown as the black line in the figure. figure V(r) lower in solid (work function).

V(r) V( ) Solid

-4

-5 0 0

-8 -6 -4 -2 Naive picture: lowest binding energy states can + + become free to move Nuclear positions throughout crystal

r2

r +

+ a

Influence of the lattice periodicity p y

In the free electron model, the allowed energy states are

E=

2m

2 (k x2 + k y + k z2 )

where for periodic boundary conditions 2n y 2nx 2nz kx = ; ky = ; kz = L L L nx , ny and ny positive or negative integers.

0 k

Periodic potential
Exact form of potential is complicated Has property V(r+ R) = V(r) where R = m1a + m2b + m3c where m1, m2, m3 are i t h integers and a ,b ,c d b are the primitive lattice vectors. E

0 -1 -2 -3 -4 -5 r

 The formation of forbidden gaps is NOT unique to the nearly-free electron problem however * We demonstrate this here by considering the formation of energy gaps in the so-called KRONIG-PENNEY MODEL * Unlike the nearly-free electron model in this problem we consider the case where the electrons move in a STRONG b PERIODICALLY VARYING crystal potential l i but PERIODICALLY-VARYING l i l The model potential considered in the kronigpenney model the periodic potential of the crystal is crudely modeled as a square-well superlattice q p each potential well can be considered to represent the potential associated with a x particular atom in the crystal a in this model the amplitude of the potential modulation vo is taken to be large compared to the electron energy

Vo

V=0 b

The Kronig-Penney Model g y

The problem that we consider here is a ONE-DIMENSIONAL one in which we assume that the potential variation occurs only in the x-direction * We start from the SCHRDINGER EQUATION for motion in this direction

d 2 ( x ) + V ( x ) ( x ) = E ( x ) 2 2m dx
2

( 4.20)

* Since the electron moves in a PERIODIC potential its wavefunction must satisfy BLOCHS THEOREM which for the superlattice of interest here may be expressed as

( x + d ) = e ik d ( x )
x

( 4.21)

In the above equation d is the PERIOD of the superlattice potential while kx is the value of the wavenumber associated with the motion in the direction

 To solve this problem we must RECALL the solutions for electron motion in the presence of a CONSTANT potential barrier * For a constant barrier of height V the GENERAL wavefunction and energy solutions are F b i fh i h h f i d l i given as

( x ) = Ae ikx + Be ikx
k2 = 2m
2

( 4 .22 )
( 4 .23 )

(E V )

These solutions correspond to PLANE-WAVE propagation with wavenumber k and energy E When the barrier height EXCEEDS the energy the electron wavenumber is GN s de the ba e a d t s g ves se UNN NG IMAGINARY inside t e barrier and this gives rise to TUNNELING

 Taking our ORIGIN as indicated below we can use Blochs theorem to write the following WAVEFUNCTIONS

( x ) = Ae ix + Be ix , b < x < 0
( x ) = De ix + Fe ix , 0 < x < a
x

( 4.24)

( 4.25)

k ( x ) = e ik d [Ae i ( x d ) + Be i ( x d ) ] , a < x < d

( 4.26)

( x ) = e ik d [De i ( x d ) + Fe i ( x d ) ] , d < x < a + d

x

( 4.27)

Vo

2 =

2m
2

( E Vo )

( 4.28)

V=0 -b0 ad a+d

2 =

2m
2

( 4.29)

 Next we apply CONTINUITY CONDITIONS that require the wavefunction and its derivative to be SINGLE-VALUED functions at any one of the potential steps * Application of the boundary conditions at x = 0 yields the f ll i relations A li i f h b d di i i ld h following l i

A+ B = D + F
( A B) = ( D F )

( 4.30)
( 4.31)

* SIMILARLY application of the boundary conditions at x = a yields

e ik x d ( Ae ib + Be ib ) = De ia + Fe ia
e ik d ( Ae ib Be ib ) = ( De ia Fe ia )
x

( 4.32)
( 4.33)

 The only way in which solutions for the wavefunction variables A, B, C, and D can be obtained is if the DETERMINANT of their coefficients vanishes * This requirement leads in turn to the following conditions on the ALLOWED electron energies and wavenumbers When the electron energy is LESS than the height of the barriers (E < Vo) this condition may be written as shown in Equation 4.34

2 B2 cos(k x d ) = cos(a ) cosh(bB ) sin(a ) sinh(bB ) 2B

2m
2

( 4.34)

B=

(Vo E ) = i

( 4.35)

In terms of E, Equation 4.34 becomes

cos(k x d ) = cos( ( ( a 2mE ) cosh( ( b 2m(V0 E ) ) b 2m(V0 E ) V0 2 E a 2mE ( ) sinh( ( ) sin( 2 E (V0 E ) ( 4.34)

This is a DISPERSION RELATION for electrons since it provides a connection between their wavenumber (kx) on the LHS and their energy () on the RHS The importance of this equation is that it provides a CONDITION on the ALLOWED energies of the electron in the periodic potential

 In the figure below we plot the variation of the RHS of Equation 4.34 as a function of the parameter a (E) * The shaded regions correspond to ranges of a (E) for which solution of the LHS of Equation 4 34 possible E ti n 4.34 IS p ibl The UNSHADED regions allow NO solution of Equation 4.34 and so correspond to physically FORBIDDEN energies

R RHS OF EQUATIO 4.38 E ON

-1

In this figure the rhs of equation 4.34 is plotted as a function of the parameter a which is related to the energy of the electron 4 34 in order for the lhs of equation 4.34 to have a solution we require that 1 rhs 1 this condition is only satisfied for the ranges of a (energy) that are shown shaded all values of a outside of these ranges do not allow solution of the lhs of equation 4.34 and so correspond to forbidden energies
-1 0 -5

-2

a
0 a
o

10

RHS OF EQUA ATION 4.38 4

Allowed bands
cos( k x d ) = 1

- 1

cos( k x d ) = 1
E1 E2
o

- 2 - 1 0 - 5

0 a

E3 E4 E 5
5

E6

The allowed and forbidden bands are plotted in the E vs. k relation.