Sunteți pe pagina 1din 18

Page 9.

1
SECTION 9: BAND THEORY OF SOLIDS

1. Energy bands: a qualitative introduction 2
2. A one-dimensional model of a solid 3
2.1 Periodic potentials 3
2.2 The displacement operator 4
2.3 Bloch functions 4
2.4 Crystal momentum k 5
2.5 Brillouin Zones 5
2.6 Periodic boundary conditions 6
2.7 The periodic potential 7
2.8 Formation of energy bands 9
3. Electrical Properties of Solids 10
4. Band Theory of Electrical Conductivity 11
4.1 Insulators 11
4.2 Conductors 12
4.3 Intrinsic semiconductors 13
4.4 Extrinsic or impurity semiconductors 15








References
The original version of these notes was based loosely on the textbook by Griffiths and Quantum Physics, by
S Gasiorowitz, published by Wiley (1974). See also Fundamentals of Physics, 6
th
edition, by C Halliday, R
Resnick and J Walker, published by Wiley. Specific references to these and other books are given as footnotes
to the text.

Original Version: October 2002; Last Major Revision: October 2007
Revision Date: 23 October 2009
Printed: 14 June 2010

Page 9.2
1. ENERGY BANDS: A QUALITATIVE INTRODUCTION
We consider only crystalline solids made up of a regular, repeating pattern of atoms or molecules forming a
rigid three-dimensional lattice structure; this specifically excludes materials such as rubber, wood, plastic and
glass.
In a crystalline solid, a few of the loosely bound valence electrons in each atom roam throughout the material
subject to the combined potential of the entire crystal lattice, and not just of the individual atoms. We
introduce a primitive model as an introduction to the band theory of solids, and explore its consequences for
electrical conductivity in solids.
Consider the energy states of a solid consisting of a regular lattice of N identical atoms
1
. The solid can be built
up by bringing together the atoms one by one, as illustrated schematically in Fig. 1.

Figure 1: Formation of energy bands in solids
As we have seen in the discussion of atomic structure, for a single electron, the energy levels will be
labelled 1s, 2s, 2p, 3s etc. in order of increasing energy, with degeneracies 2, 2, 6, 2 etc.
If we have two atoms sufficiently far apart that the electron wave functions do not overlap significantly,
the electron energy spectrum will be unchanged, except that the degeneracy of each level is doubled.
Imagine the two atoms are now brought closer and closer together. The electron wave functions begin to
overlap, starting with the outermost electrons which on average correspond to higher energy. As soon as
the two sets of electron wave functions overlap significantly, in order to satisfy the requirements of the
Pauli principle each energy level splits into two (as discussed in the section on exchange symmetry); the
closer the two atoms, the larger the splitting.
If we have three atoms close together, the energy levels will be split into three; with four atoms, each level
is split into four, and so on. With an extremely large number N of atoms, interacting to form a solid, each
multi-electron energy level is split into N extremely close-lying levels, forming an almost continuous band
of electron levels. The bands are normally separated by energy gaps where no electron states exist.
These bands have the following properties:

1
The original version of this section was based on section 42-3 of the textbook by Halliday, Resnick and Walker.
Page 9.3
The number of states in each band is equal to N times the number of states in the original electron energy
level from which the band was created. The bands can be labelled with the quantum numbers of the
original single-electron levels.
Electrons in lower energy levels spend most of their time close to the nucleus at the centre of the atom;
the wave functions of these electrons therefore do not overlap as much those in higher energy levels and
the splitting of the resulting bands is less. The bands of higher energy are therefore wider than those of
lower energy.
Typically bands are a few eV wide and they are separated by gaps a few eV wide. Higher-lying bands may
actually overlap each other; i.e. the energy gap disappears.
2. A ONE-DIMENSIONAL MODEL OF A SOLID
2

In a crystalline solid, the atoms are arranged in a regular pattern in a lattice. The potential experienced by
an electron due to the atomic nuclei is therefore periodic in space.
We assume than an electron moves freely in an effective potential containing
the periodic potential due to the positively-charged atomic nuclei;
some of the effects of other electrons by treating them as static distributions of negative charge with the
same periodicity as the lattice.
Since we neglect any other interaction between the electrons, we therefore have an independent-particle model
for the electrons, similar to the central-field approximation for an atom:
The wave function is the product of single-electron wave functions (but properly anti-symmetrised as we
have discussed in the case of atoms).
The energy is the sum of the energies of all the electrons.
2.1 Periodic potentials
We consider an idealized one-dimensional model of a crystal, in which the crystal lattice comprises a set of N
identical unit cells of length L; this is a simplified version of the model introduced by Kronig and Penney in
1931.
A unit cell is the basic building block of the crystal. Each cell may contain a single atom, or a group of
atoms in a fixed spatial configuration.
The length L is called the lattice constant. In most crystals (which are obviously three-dimensional objects)
this is typically 25 .
As discussed above, we must solve the Schrdinger equation for a single electron

2 2
2
( ) ( ) ( ) ( )
2
d
H x V x x E x
m dx

l
l = =
l
l

(1)

2
The original version of this section was based on section 5.3.2 of the textbook by Griffith. See also sections 7.4 and 7.5 of Quantum
Mechanics by Sara M McMurry, published by Addison-Wesley (1994).
Page 9.4
where the electron potential is obviously the same at equivalent points in each unit cell, i.e.
( ) ( ), 0,1, 2, V x nL V x n = = (2)
2.2 The displacement operator
Because of the symmetry built into the model, it is convenient to define a displacement operator T
L
that
produces a translation through distance L along the x axis in the positive x direction when it acts on any
function of position x. In particular, if (x) is the wave function of a single electron in the solid:

( )
( ) ( )
( ) ( )
L
n
L
T x x L
T x x nL


=
=
(3)
where n is any integer.
Clearly, T
L
commutes with the kinetic energy operator:
( )
L
d d d
T
dx d x L dx
= =


and, from eq.(2),
( ) ( ) ( ).
L
TV x V x L V x = =
Hence, T
L
commutes with the complete Hamiltonian and we can look for simultaneous eigenfunctions of the
Hamiltonian and the displacement operator.
2.3 Bloch functions
Blochs theorem (Bloch 1928) states that simultaneous eigenfunctions of H and T
L
must have the particular
form
3
:
( ) ( )
ikx
k k
x e u x = (4)
where the function u
k
(x) has the same periodicity as the potential, namely
( ) ( ),
k k
u x L u x = (5)
and k can take on any real value and is not a function of x. Wave functions satisfying eqs.(4) and (5) are called
Bloch functions.
Since the Hamiltonian has the same translational symmetry as the crystal lattice, we should expect the
electron probability distribution to satisfy
2 2
( ) ( )
k k
x nL x = ;
obviously, the Bloch functions satisfy this condition provided k is real.
Note that, from the definition of the displacement operator, eq.(3), and the properties of the Bloch functions,
eqs.(4) and (5), we have
( )
( ) ( ) ( )
( ).
ik x L
L k k k
ikx ikL
k
T x x L e u x L
e e u x


= =
=


3
For a proof of this theorem, see page 199 (1
st
edition) or page 225 (2
nd
edition) of the textbook by Griffith.
Page 9.5
In other words
( ) ( ) ( ).
ikL
L k k k
T x x L e x = = (6)
The Bloch function
k
(x) is an eigenfunction of the displacement operator with eigenvalue e
ikL
.
Since the eigenvalue is not real, the operator is not Hermitian and cannot represent an observable.
Because of Blochs theorem we need only solve the Schrdinger equation within a single unit cell, since the
solution everywhere else can be generated by repeated use of eq.(6).
2.4 Crystal momentum k
The wave function of a free electron in an infinite solid is given by
( )
ikx
k
x C e =
where C is a normalization constant, and the electron has momentum k and energy
2 2
2
k
m

.
However, in a crystal,
it is easily shown that
k
(x) is not an eigenfunction of the momentum operator
x
d
p i
dx
=
so that
k
(x) does not represent an electron state of well-defined linear momentum;
nonetheless, the quantity k is called the crystal momentum or the quasi-momentum of the electron;
the effect of the crystal structure on the free electrons is incorporated in the periodic function u
k
(x).
In the limit that the effects of the crystal structure become weak,
the function u
k
(x) approaches a constant C,
the Bloch function approaches the free-electron wave function Ce
ikx
, and
the quantity k becomes the true momentum of an electron.
2.5 Brillouin Zones
Consider two Bloch functions with different crystal momenta k and k where

2
, 0, 1, 2, k k n n
L

= = (7)
Now it follows from eqs.(6) and (7) that
2
( ) ( )
( )
( )
L
ik L
L k k
i nL ikL
k
ikL
k
T x e x
e e x
e x

=
=
=

since
2
1
L
i nL
e

= for n integer. In other words:
The wave function
k
(x) is an eigenvector of T
L
with the same eigenvalue as
k
(x).
In fact, the two wave functions
k
(x) and
k
(x) describe
4
the same physical state of crystal momentum k.
Thus we need consider only values of k within a single range of values of width 2/L.

4
See page 165 of the book by McMurry.
Page 9.6
The different ranges of k of width 2/L are called Brillouin Zones.

We usually need consider only the first zone, conventionally defined by
. k
L L


2.6 Periodic boundary conditions
In order to solve the Schrdinger equation for an electron, we must apply boundary conditions on the wave
function at either end of the one-dimensional solid:

1
2
1
2
x NL
x NL
=
=
(8)
where N is the number of unit cells in the solid (and is extremely large) and we have taken x = 0 as the centre
of the crystal.
The wave function of an electron deep inside a sample of macroscopic size will not depend critically on the
precise form of the boundary conditions. Therefore we choose the conditions to simplify the solution of the
problem, specifically:
1 1
.
2 2
k k
NL NL
1 1
=


( ) ( )

But from eq.(6)
( ) ( ),
ikNL
k k
x NL e x =
leading to
1 1
.
2 2
ikNL
k k
NL e NL
1 1
=


( ) ( )

Hence to satisfy the boundary conditions eq.(8) we require that e
ikNL
= 1,
which means that
2
integer. k
NL

=
Thus, the spectrum of k is discrete. Note that:
This condition implies that within each Brillouin zone of width 2/L there are exactly N possible values
of k.
Since N is extremely large, the separation between allowed values of k is extremely small. Thus k is
effectively continuous in the range /L k +/L.
Page 9.7
2.7 The periodic potential
The qualitative behaviour of a solid does not depend on the details of the periodic potential
5
. For simplicity
we use a one-dimensional Dirac comb a string of delta-function potential wells (or spikes if is negative):
/2
/2
( ) ( ).
N
p N
V x x pL

=
=


In this equation, is a constant giving the strength of the interaction, and the potential wells are at positions
x = pL, p = integer.
The potential is shown schematically in the figure below
6
.

Figure 2: The Dirac comb a periodic potential
We now solve the Schrdinger equation (1) for this potential. In the region 0 < x < L the potential is
V(r) = 0, and the Schrdinger equation becomes
2 2
2
( ) ( ).
2
d
x E x
m dx
=


The general solution is
( ) sin cos , 0 x A x B x x L = < < (9)
with
2 2
.
2
E
m

=


As discussed above, we can generate from this the solution for the range L < x < 0 by using eq.(6):
( ) ( ).
ikL
k k
x L e x =
This gives
( ) ( ) [ [ ( ) sin cos , 0.
ikL
x e A x L B x L L x

= < < (10)


We now apply the continuity conditions at the matching point x = 0.
The wave function (x) is continuous at x = 0. We get directly from eqs.(9) and (10)
[ [ sin cos .
ikL
B e A L B L

= (11)

5
In their original treatment, Kronig and Penney used finite-depth square well potentials (for further discussion, see pages 98-101 of
the book by Gasiorowicz). In the limit that the wells become infinitely deep and infinitely narrow, this is essentially equivalent to the
present treatment which is based on Griffiths.
6
Based on Figure 5.5 of the book by Griffiths.
Page 9.8
The derivative of (x) is not continuous at x = 0, since it is a general rule that the derivative is continuous
except at points at which the potential is infinite. Nonetheless, we can easily find
7
an expression for the
magnitude of the discontinuity at x = 0.
To achieve this, we integrate the Schrdinger equation from x = 0 to x = 0 and take the limit 0.


2 2
2
( )
( ) ( ) ( ) .
2
d x
dx V x x dx E x dx
m dx


The first integral gives
2
2
0 0
( )
lim lim .
x x
d x d d d
dx
dx dx dx dx


= =
' '
1 1 1
1 1

=
! !


( ) 1 1
1 1 + +





The third integral tends to zero as 0 since the wave function is continuous at x = 0:

0
lim ( ) 0. x dx


So we get


2
( ) ( ) ( ) ( )
2
d
V x x dx x x dx
m dx




1

= =


( )


or, rearranging and using the definition of the delta function to evaluate the integral:

2
2
(0).
d m
dx

1

=


( )

(12)
From eq.(9) we get

[ [

cos sin
in the limit 0
x
d
A B
dx
A

=
=

(13)
and from eq.(10)

( ) ( ) [ [
[ [

cos sin
cos sin in the limit 0
ikL
x
ikL
d
e A L B L
dx
e A L B L

=

(14)
From eq.(9) we also find
(0) . B = (15)
We substitute eqs.(13), (14) and (15) into eq.(12) and use eq.(11) to give, after much rearrangement,

2
cos cos sin .
m
kL L L

(16)
This is the fundamental result from which all else follows. For other choices of potential, the equation will
be more complicated, but the qualitative features remain unchanged.



7
This derivation is based on page 55 (1
st
edition) or page 72 (2
nd
edition) of the textbook by Griffith.
Page 9.9
2.8 Formation of energy bands
Consider the form of eq.(16):
The left-hand side of the equation is a function of the crystal momentum k, whereas the right-hand side
is a function of , or electron energy
2 2
/2 E m = .
The left-hand side is always in the range 1 to +1, whatever the crystal momentum. In fact, as k takes
on all its allowed values in the first Brillouin zone, coskL increases from 1 to +1 and back to 1.
The right hand side of the equation clearly has a magnitude greater than +1 or less than 1 for certain
ranges of values of . Thus the equation has no solution for some values of , that is for some values of the
electron energy
2 2
/2 E m = . We see that some electron energies are allowed, and some are forbidden.
This last point becomes clearer if we rewrite the right-hand side of the equation (16) as
sin
( ) cos
z
f z z
z
=
where z = L and
2
/ mL = . The figure below shows a graph of the function f (z) against z for a fixed value
of = .0.
It shows the formation of energy gaps, which represent ranges of forbidden electron energies (where
+1 < f (z) or f (z) < 1).
The gaps are separated by energy bands, ranges of allowed electron energies (where 1 < f (z) < 1).
The lower edge of a band occurs at z = L = , 2 where f(z) is exactly equal to 1 or +1.

Figure 3: Formation of energy bands and energy gaps
In general, as k takes on all of its N allowed values within a Brillouin zone,

2
integer
values of in a zone
k
NL
N k

=

the electron energy sweeps out a band, i.e. there are N electron energy states in a band.
Since N is extremely large, virtually any energy is allowed within a band, i.e. the energy levels are so close
together they effectively form a continuum.
Page 9.10
The resulting electron energy level diagram is shown schematically in the next figure
8
.
There are Nq free electrons in a solid, where N is the number of atoms and q is the number of free
electrons per atoms, q = 1, 2, 3,
At sufficiently low temperatures these will fill up the lowest Nq/2 electronic states (the factor of 1/2
arises because each energy state can accommodate two electrons with different spin orientations).
Since there are N electron states in each band, if q is even the electrons will completely fill the lowest
q/2 bands; if q is odd, the last occupied band will be half full.

Figure 4: Schematic diagram showing energy bands and gaps
In a real three-dimensional solid with more realistic potentials, the band structure is more complex and these
detailed conclusions may not be valid. However, the qualitative discussion will remain unaltered (see the
description of conductors, insulators and semiconductors below).
3. ELECTRICAL PROPERTIES OF SOLIDS
9

Solids are classified electrically according to three basic properties, as described in the following table.

Property Symbol Unit Description
Resistivity .m Resistivity is defined by E J =


E

is the field at some point in the material


J

is the current density at that point


Temperature coefficient of resistivity K
1

Defined by
1 d
dT

=
Number density of charge carriers n m
3
Measured using e.g. Hall effect

8
Based on Figure 5.7 of the book by Griffiths.
9
The original version of this section was taken from section 42-2 of the textbook by Halliday, Resnick and Walker.
Page 9.11
From measurements of resistivity at room temperature, it is found that some materials effectively do not
conduct electricity at all (or rather, there is no measurable current) these are called insulators. For example
24
(diamond) 10 (copper).
Materials that are not insulators can be divided into two major categories conductors (or metals) and
semiconductors.
Semiconductors have considerably higher resistivity than conductors.
The temperature coefficient of resistivity of conductors is positive (i.e. their resistivity increases with
temperature). Semiconductors have a temperature coefficient of resistivity that is both larger and
negative (i.e. their resistivity decreases with temperature).
Semiconductors have considerably fewer change carriers per unit volume.
These features are illustrated in the table below for copper, a metal, and silicon, a semiconductor.
Property Copper Silicon
(.m)

8
2 10


3
3 10
(K
1
)

3
4 10


3
70 10


n (m
3
)

28
9 10
16
1 10
All values are appropriate at room temperature (300 K).
4. BAND THEORY OF ELECTRICAL CONDUCTIVITY
We now apply the band theory of solids to explain their electrical properties
10
. As discussed for the simple
one-dimensional model described above:
There are Nq free electrons in a solid, where N is the number of atoms in the solid and q is the number
of free electrons per atoms.
At low temperatures these will fill up the lowest Nq/2 electronic states, with the factor of 1/2 arising
because each energy state can accommodate two electrons with different spin orientations.
4.1 Insulators
In some materials there are sufficient electrons to just fill the energy levels up to the top of one band; this band
is called the valence band, and an example of such a material is diamond.
In order for a current to flow when an electric field is applied to a solid, free electrons must be able to gain
kinetic energy by absorbing energy from the field. The flow of electrons, in a direction opposite to the field,
constitutes an electrical current.


10
See sections 42-4 to 42-7 of the book by Halliday, Resnick and Walker.
Page 9.12

Figure 5: Energy bands for an insulator
In a material such as diamond, none of the electrons in the valence band can absorb energy to move to a
higher energy level within the same band, since all states in the band are already filled. In addition, for
normal fields an electron at the top of the valence band cannot absorb sufficient energy to jump from the
valence band to the next band, called the conduction band, since the gap is too large. Materials such as
diamond are therefore electrical insulators.
If an extremely large field is applied, some electrons may gain sufficient energy to jump the gap and a
current will flow; i.e. the insulator breaks down. Such fields will in any case usually disrupt the electronic
structure of the crystal.
The magnitude of the energy gap between the valence and conduction bands also affects the optical properties
of a material. Photons in the visible spectrum have wave lengths in the range 400 to 700 nm, corresponding
to photon energies of 3.1 to 1.8 eV.
Photons in the visible spectrum have insufficient energy to raise electrons from the valence to conduction
band. Insulators such as diamond are therefore transparent to visible light, since the photons cannot be
absorbed within the material.
More generally, the absorption of radiation can be used to determine the magnitude of the gap energy of
a material.
4.2 Conductors
In some materials, for example metals, the band of highest energy is only partially filled, as in the diagram be-
low
11
. The energy of the highest-lying filled electron state is called the Fermi energy; this lies within the
conduction band for a conductor.

11
In materials of high valency such as aluminium, the filled valence band and partially-filled conduction band overlap, leading to a
partially filled combined band; all electrons in the combined band can contribute to an electric current.
Page 9.13

Figure 6: Energy bands for a conductor.
Electrons just below the Fermi energy can easily be excited to vacant levels just above the Fermi level,
since the spacing of energy levels within a band is extremely small.
Thus when an electric field is applied to the material these electron can absorb energy and form a current.
Their motion creates vacancies in the previously filled levels, and these are filled by electrons initially in
lower levels. In this way all the electrons in the conduction band can contribute to the current. The
material is therefore a conductor.
Photons in the visible spectrum can cause excitation of electrons within the conduction band. Such
photons are readily absorbed by electrons in the conduction band and the material is therefore opaque to
visible light.
4.3 Intrinsic semiconductors
Some materials have a band structure similar to insulators except that the gap between the valence and
conduction bands is significantly smaller. These materials are called semiconductors. For example:

Material Energy gap
0 K 300 K
silicon 1.17 eV 1.11 eV
germanium 0.74 eV 0.67 eV
gallium arsenide 1.52 eV 1.43 eV
At low temperatures, these materials are insulators for the reasons discussed above.
However, because of the smaller energy gap, at room temperature the thermal energy of the electrons is
sufficient to raise some of them from near the top of the valence band into the conduction band. This leaves
vacant electron energy levels, or holes, near the top of the valence band. A hole, corresponding to the absence
of an electron, acts just like a positively-charged electron.
Page 9.14

Figure 7: Energy bands for an intrinsic semiconductor at room temperature.
If an electric field is applied to the material:
The electrons in the conduction band because of thermal excitation absorb energy, being excited to vacant
higher energy states within the same band. The absorbed energy becomes kinetic energy, and the electrons
move in a direction opposite to that of the field (creating a current parallel to the field).
Electrons just below the levels left vacant in the valence band by thermal excitation absorb sufficient
energy from the field to fill these vacancies, thereby creating further vacancies. In other words, the holes
created in the valence band move in response to the applied field. The motion of the holes creates a current
in the same direction as the field.
The motions of the electrons in the conduction band and holes in the valence band contribute equally to
a measurable current, since the number of holes in the valence band equals the number of electrons in the
conduction band.
To see why electrons can be excited thermally from the valence band to the conduction band in silicon but not
in diamond, we consider the probability of an electron having sufficient energy at temperature T to jump the
energy gap E
gap
between the two bands; this can be estimated as follows.
The mean kinetic energy of the electrons at temperature T is approximately kT where k = 8.62 10

eV/K
is Boltzmanns constant. The probability of a single electron having energy E
gap
is given approximately by the
Boltzmann distribution law as exp
gap
E
kT
l

l
l
.
The table below compares this probability at room temperature for the insulator diamond with some common
semi-conducting materials. These values are very approximate because of the extreme sensitivity of the result
to the magnitude of the energy gap.
In a macroscopic sample of silicon or germanium, with of the order of Avogadros number of free electrons, a
reasonable number will be excited to the conduction band, but for diamond the number effectively zero.


Page 9.15
Material Energy gap Probability n (in cm
3
)
Diamond 5.5 eV 3 10
08

Silicon 1.1 eV 3 10
10
1.4 10
10

Germanium 0.7 eV 6 10
12
2.5 10
18

Gallium arsenide 1.4 eV 1 10
24
9 10
0

The approximate density of electrons in the conduction band at a temperature of 300 K is shown in the table
above
12
. This density rises steeply with temperature since the probability of thermal excitation from the
valence band increase sharply with temperature. (Note the implication that even an insulator can become
conducting at sufficiently high temperature, providing it does not melt!)
For comparison, in metals there are approximately 10
22
10
28
electrons per cm
8
in the conduction band.
4.4 Extrinsic or impurity semiconductors
All modern electronic devices involve extrinsic or impurity semiconductors, rather than the intrinsic semi-
conductors described above. These are formed by doping a semiconducting material with atoms with a
different value of the quantity q. For example:
Material Configuration No. of valence electrons
silicon
2 2
(3 ) (3 ) s p 4
antimony
2 3
(5 ) (5 ) s p 5
The effect of the antimony atoms can be understood by considering the bonds
13
that act between atoms in the
crystal lattice.

Figure 8: Covalent bonds in silicon

Figure 9: Bonds with antimony atom replacing silicon
In a sample of silicon, the bond between two adjacent silicon atoms is made from an electron donated by each
of the two atoms. As shown in the first diagram, a silicon atom contributes one electron to the formation of

12
These values are taken from Microelectronic Devices by K Leaver, 2
nd
edition, published by Imperial College Press (1997)
13
The figures, which are flattened two-dimensional representations of three-dimensional objects, are based on those in the book by
Leaver.
Page 9.16
the bond with each of its four neighbouring atoms; therefore for each atom four electrons take part in the
formation of bonds.
The electrons that form the bonds are the (3s) and (3p) electrons, the valence electrons listed in the table
above. These electrons constitute the valence band of the silicon sample. If an electron is freed from its bond
so that it is able to move through the lattice, we say that it has been raised from the valence band to the
conduction band. The minimum energy required to remove an electron from a bond is the gap energy E
gap
.
If an antimony atom replaces a silicon atom in a crystal, four of its five valence electrons take part in bonds
with neighbouring silicon atoms, and the remaining electron is very loosely bound to the antimony ion core,
as shown in the second diagram. This creates an additional electron state that is situated in the energy gap;
since the energy needed to free this loosely-bound electron is extremely small, the additional energy level is
only just below the conduction band.
Each antimony atom that replaces a silicon atom creates such an additional level. At very low temperatures
these levels will all be filled, but only minor thermal agitation is necessary to ionize the impurity atoms.
Therefore, even at relatively low temperatures, electrons will be excited from the additional levels to the
conduction band. The antimony atoms are called donor atoms, since they donate electrons to the conduction
band, and the additional levels are called a donor levels.

Figure 10: Energy bands for an n-type semiconductor (at very low temperature)
At room temperature, virtually all the electrons from the donor atoms are in the conduction band. When
an electric field is applied, these electrons are able to absorb energy and form a current. This is in addition
to the current that in any case would be present since silicon is an intrinsic semiconductor. The majority
carriers are now electrons and the holes in the valence band are the minority carriers.
Antimony is referred to as a donor-type impurity, and the doped material is an n-type semiconductor
(since the conduction is mainly due to negatively-charged electrons).
A different type of impurity semiconductor is created by doping silicon with atoms that have one fewer valence
electrons, such as indium.

Page 9.17
Material Configuration No. of valence electrons
silicon
2 2
(3 ) (3 ) s p 4
indium
2
(5 ) (5 ) s p 3
An indium atom introduced into a sample of silicon can form a covalent bond with only three of the four
neighbouring silicon atom, leaving an unsaturated bond with only one electron and a hole where the second
electron should be. However, it requires only a small amount of energy to remove an electron from a nearby
silicon-silicon bond to fill this hole. This of course creates a hole in the silicon-silicon bond, but this will be
filled by an electron from another bond, thereby creating a new hole. In this way the hole moves through the
lattice.

Figure 11: Bonds with indium atom replacing silicon
The indium atom is called an acceptor atom since it readily accepts an electron from another bond, i.e. from
the valence band of silicon. The electron occupies an energy level just above the top of the valence band, which
is called an acceptor level. At temperatures close to absolute zero such levels are empty, but only slight
thermal agitation is necessary to move an electron from the valence band into an acceptor level. At room
temperature, all acceptor levels will be occupied.
Under thermal agitation, a silicon electron is excited from the top of the valence band into the acceptor
level, leaving an unfilled level or hole in the valence band.
When an electric field is applied, the holes in the valence band drift in the direction of the field, creating
a positive current.
The number of holes in the valence band is very much larger than the number of electrons that exist in
the conduction band at room temperature in an intrinsic semiconductor. The majority carriers in this case
are therefore holes and the minority carriers are electrons. Indium is said to be an acceptor impurity and
the material is called a p-type semiconductor.
Page 9.18

Figure 12: Energy bands for a p-type semi-conductor at very low temperature
The table below summarizes the properties of semiconductors created by doping silicon with phosphorus and
aluminium.

Property Type of semiconductor
n type p type
Matrix material silicon silicon
Matrix energy gap 1.14 eV 1.14 eV

Dopant phosphorus aluminium
Type of dopant donor acceptor
Dopant valency 5 3
Dopant energy gap 0.045 eV 0.067 eV

Majority carriers electrons holes
Minority carriers holes electrons
Replacing 1 in 5 million Si atoms with P atoms increases the density of charge carriers by a factor of about
1 million, to approximately 10
16
cm
-3
. The conductivity is roughly proportional to the density of dopant
atoms.
Typically, 1 silicon atom in 10
5
10
10
would be replaced by dopant atoms in a commercially produced
semiconducting material.

S-ar putea să vă placă și