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354 Chapter Ten

Weidemann-Franz Law

T he free-electron model of metallic conduction was proposed by Paul Drude in 1900, only
three years after the discovery of the electron by J. J. Thomson, and was later elaborated
by Hendrik Lorentz. Fermi-Dirac statistics were unknown then, and Drude and Lorentz assumed
that the free electrons were in thermal equilibrium with a Maxwell-Boltzmann velocity distri-
bution. This meant that the  F in Eq. (10.16) was replaced by the rms electron velocity  rms. In
addition, Drude and Lorentz assumed that the free electrons collide with the metal ions, not
with the much farther apart lattice defects. The net result was resistivity values on the order of
10 times greater than the measured ones.
The theory was nevertheless considered to be on the right track, both because it gave the
correct form of Ohm’s law and also because it accounted for the Weidemann-Franz law. This
empirical law states that the ratio K (where   1) between thermal and electric conduc-
tivities is the same for all metals and is a function only of temperature. If there is a temperature
difference T between the sides of a slab of material  x thick whose cross-sectional area is A,
the rate Qt at which heat passes through the slab is given by
Q T
  KA 
t x
where K is the thermal conductivity. According to the kinetic theory of a classical gas applied to
the electron gas in the Drude-Lorentz model,
kn rms
K 
2
From Eq. (10.16) with  F replaced by  rms,
1 ne2
   
 m rms
Hence the ratio between the thermal and electric resistivities of a metal is
kn rms m rms km 2rms
K
  
 2  
ne2  
2e2
According to Eq. (9.15),  2rms  3kTm, which gives
K 3k2
    1.11 108 W /K2
T 2e2
This ratio does not contain the electron density n or the mean free path , so KT ought to
have the same constant value for all metals, which is the Weidemann-Franz law. To be sure, the
above value of KT is incorrect because it is based on a Maxwell-Boltzmann distribution of
electron velocities. When Fermi-Dirac statistics are used, the result is
K  2k2
    2.45 108 W /K2
T 3e2
which agrees quite well with experimental findings.

10.6 BAND THEORY OF SOLIDS

The energy band structure of a solid determines whether it is a conductor,
an insulator, or a semiconductor

No property of solids varies as widely as their ability to conduct electric current. Cop-
per, a good conductor, has a resistivity of   1.7 108  m at room temperature,
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The Solid State 355

Felix Bloch (1905–1983) was In 1928 in his doctoral thesis Bloch showed how allowed
born in Zurich, Switzerland, and and forbidden bands arise by solving Schrödinger’s equation
did his undergraduate work in for an electron moving in the periodic potential of a crystal.
engineering there. He went to This important step in the development of the theory of solids
Leipzig in Germany for his Ph.D. supplemented earlier work by Walter Heitler and Fritz
in physics, remaining there until London, who showed how energy levels broaden into bands
the rise of Hitler. In 1934 Bloch when atoms are brought together to form a solid. Later Bloch
joined the faculty of Stanford studied the magnetic behavior of atomic nuclei in solids
University where he stayed until and liquids, which led to the extremely sensitive nuclear
his retirement except for the war magnetic resonance method of analysis. Bloch received the
years, which he spent at Los Nobel Prize in physics in 1952 together with Edward Purcell
Alamos helping develop the atomic bomb, and for 1954 to of Harvard, who had also done important work in nuclear
1955, when he was the first director of CERN, the European magnetism.
center for nuclear and elementary-particle research in Geneva.

whereas for quartz, a good insulator,   7.5  1017   m, more than 25 powers of
ten greater. The existence of electron energy bands in solids makes it possible to un-
derstand this remarkable span.
There are two ways to consider how energy bands arise. The simplest is to look
at what happens to the energy levels of isolated atoms as they are brought closer and
closer together to form a solid. We will begin in this way and then examine the
significance of energy bands. Later we will consider the origin of energy bands in
terms of the restrictions the periodicity of a crystal lattice imposes on the motion of
electrons.
The atoms in every solid, not just in metals, are so near one another that their
valence electron wave functions overlap. In Sec. 8.3 we saw the result when two
H atoms are brought together. The original 1s wave functions can combine to form
symmetric or antisymmetric joint wave functions, as in Figs. 8.5 and 8.6, whose en-
ergies are different. The splitting of the 1s energy level in an isolated H atom into
two levels, marked E Atotal and E Stotal, is shown as a function of internuclear distance
in Fig. 8.7.
The greater the number of interacting atoms, the greater the number of levels pro-
duced by the mixing of their respective valence wave functions (Fig. 10.19). In a solid,
because the splitting is into as many levels as there are atoms present (nearly 1023 in
a cubic centimeter of copper, for instance), the levels are so close together that they
form an energy band that consists of a virtually continuous spread of permitted ener-
gies. The energy bands of a solid, the gaps between them, and the extent to which they
are filled by electrons not only govern the electrical behavior of the solid but also have
important bearing on others of its properties.

Conductors

Figure 10.20 shows the energy levels and bands in sodium. The 3s level is the first oc-
cupied level to broaden into a band. The lower 2p level does not begin to spread out
until a much smaller internuclear distance because the 2p wave functions are closer to
the nucleus than are the 3s wave functions. The average energy in the 3s band drops
at first, which signifies attractive forces between the atoms. The actual internuclear dis-
tance in solid sodium corresponds to the minimum average 3s electron energy.
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356 Chapter Ten

Energy
Internuclear distance

(a)
Energy

Internuclear distance

(b)
Energy

Internuclear distance

(c)

Figure 10.19 The 3s level is the highest occupied level in a ground-state sodium atom. (a) When two
sodium atoms come close together, their 3s levels, initially equal, become two separate levels because
of the overlap of the corresponding electron wave functions. (b) The number of new levels equals the
number of interacting atoms, here 5. (c) When the number of interacting atoms is very large, as in
solid sodium, the result is an energy band of very closely spaced levels.

An electron in a solid can only have energies that fall within its energy bands. The
various outer energy bands in a solid may overlap, as in Fig. 10.21a, in which case its
valence electrons have available a continuous distribution of permitted energies. In
other solids the bands may not overlap, as in Fig. 10.21b, and the intervals between
them represent energies their electrons cannot have. Such intervals are called forbidden
bands or band gaps.
Figure 9.11 shows the distribution of electron energies in a band at various tem-
peratures. At 0 K all levels in the band are filled by electrons up to the Fermi energy
F, and those above F are empty. At temperatures above 0 K, electrons with energies
below F can move into higher states, in which case F represents a level with a 50 per-
cent likelihood of being occupied.
A sodium atom has a single 3s valence electron. Each s (l  0) atomic level can
hold 2(2l  1)  2 electrons, so each s band formed by N atoms can hold 2N electrons.
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The Solid State 357

−10
Energy, ev

−20 Overlapping
energy bands

(a)

−30
Forbidden
band

0 0.367 0.5 1.0 1.5

Internuclear distance, nm (b)

Figure 10.20 The energy levels of sodium atoms become bands as their internuclear distance decreases. Figure 10.21 (a) The energy bands
The observed internuclear distance in solid sodium is 0.367 nm. in some solids may overlap to give
a continuous band. (b) A forbidden
band separate nonover-lapping en-
ergy bands in other solids.

Thus the 3s band in solid sodium is only half filled by electrons (Fig. 10.22) and the
Fermi energy F lies in the middle of the band. Solid sodium
When a potential difference is applied across a piece of solid sodium, 3s electrons
3s
can pick up additional energy while remaining in their original band. The additional
energy is in the form of KE, and the drift of the electrons constitutes an electric current.
2p
Sodium is therefore a good conductor, as are other solids with partly filled energy bands.
Magnesium atoms have filled 3s shells. If the 3s level simply spreads into a 3s band 2s
in solid magnesium, as in Fig. 10.21b, there would be a forbidden band above it and
the 3s electrons could not easily pick up enough energy to jump the forbidden band 1s
to the empty band above it. Nevertheless magnesium is a metal. What actually happens
Figure 10.22 The 3s energy band
is that the 3p and 3s bands overlap as magnesium atoms become close together to give in solid sodium is half filled with
the structure shown in Fig. 10.21a. A p (l  1) atomic level can hold 2(2l  1)  electrons. The Fermi energy F is
2(2  1)  6 electrons, so a p band formed by N atoms can hold 6N electrons. Together in the middle of the band.
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358 Chapter Ten

4N levels
8N levels
Conduction
band 6N levels
2p (carbon)
Energy
6 eV
3p (silicon)
1 eV
2s (carbon)
Valence band 3s (silicon)
2N levels
4N levels

Carbon Silicon
Internuclear distance

Figure 10.23 Origin of the energy bands of carbon and silicon. The 2s and 2p levels of carbon atoms
and the 3s and 3p levels of silicon atoms spread into bands that first overlap with decreasing atomic
separation and then split into two diverging bands. The lower band is occupied by valence electrons
and the upper conduction band is empty. The energy gap between the bands depends on the inter-
nuclear separation and is greater for carbon than for silicon.

with the 2N electrons the 3s band can hold, the 3s  3p band in magnesium can hold
8N electrons in all. With only 2N electrons in the band, it is only one-quarter filled
and so magnesium is a conductor.

Insulators

In a carbon atom the 2p shell contains only two electrons. Because a p shell can hold
six electrons, we might think that carbon is a conductor, just as sodium is. What ac-
tually happens is that, although the 2s and 2p bands that form when carbon atoms
come together overlap at first (as the 3s and 3p bands in sodium do), at smaller sep-
arations the combined band splits into two bands (Fig. 10.23), each able to contain
4N electrons. Because a carbon atom has two 2s and two 2p electrons, in diamond
there are 4N valence electrons that completely fill the lower (or valence) band, as in
Fig. 10.24. The empty conduction band above the valence band is separated from it
by a forbidden band 6 eV wide. Here the Fermi energy F is at the top of the valence
band. At least 6 eV of additional energy must be provided to an electron in diamond

Conduction band

6 eV Forbidden band

Valence band
eF

Figure 10.24 Energy bands in diamond. The Fermi energy is at the top of the filled lower band. Be-
cause an electron in the valence band needs at least 6 eV to reach the empty conduction band, dia-
mond is an insulator.
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The Solid State 359

Conduction band
eF
Valence band

Figure 10.25 The valence and conduction bands in a semiconductor are separated by a smaller gap
than in the case of an insulator. Here a small number of electrons near the top of the valence band
can acquire enough thermal energy to jump the gap and enter the conduction band. The Fermi en-
ergy is therefore in the middle of the gap.

if it is to climb to the conduction band where it can move about freely. With kT 
0.025 eV at room temperature, valence electrons in diamond do not have enough ther-
mal energy to jump the 6 eV gap.
Nor can an energy increment of 6 eV be given to a valence electron in diamond by an
electric field, because such an electron undergoes frequent collisions with crystal imper-
fections during which it loses most of the energy it gains from the field. An electric field
of over 108 Vm is needed for an electron to gain 6 eV in a typical mean free path of
5  108 m. This is billions of times stronger than the field needed for a current to flow
in a metal. Diamond is therefore a very poor conductor and is classed as an insulator.

Semiconductors

Silicon has a crystal structure like that of diamond and, as in diamond, a gap sepa-
rates the top of its filled valence band from an empty conduction band above it (see
Fig. 10.23). The forbidden band in silicon, however, is only about 1 eV wide. At low
temperatures silicon is little better than diamond as a conductor, but at room temper-
ature a small number of its valence electrons have enough thermal energy to jump the
forbidden band and enter the conduction band (Fig. 10.25). These electrons, though
few, are still enough to allow a small amount of current to flow when an electric field
is applied. Thus silicon has a resistivity intermediate between those of conductors and
those of insulators, and it and other solids with similar band structures are classed as
semiconductors.

Impurity Semiconductors
Small amounts of impurity can drastically change the conductivity of a semiconductor.
Suppose we incorporate a few arsenic atoms in a silicon crystal. Arsenic atoms have
five electrons in their outer shells, silicon atoms have four. (These shells have the con-
figurations 4s24p3 and 3s23p2 respectively.) When an arsenic atom replaces a silicon
atom in a silicon crystal, four of its electrons participate in covalent bonds with its
nearest neighbors. The fifth electron needs very little energy—only about 0.05 eV in
silicon, about 0.01 eV in germanium—to be detached and move about freely in the
crystal.
As shown in Fig. 10.26, arsenic as an impurity in silicon provides energy levels just
below the conduction band. Such levels are called donor levels, and the substance is
called an n-type semiconductor because electric current in it is carried by negative
charges (Fig. 10.27). The presence of donor levels below the conduction band raises
the Fermi energy above the middle of the forbidden band between the valence and
conduction bands.
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360 Chapter Ten

Conduction band
Donor
impurity eF Forbidden band
levels Valence band

Figure 10.26 A trace of arsenic in a silicon crystal provides donor levels in the normally forbidden
band, producing an n-type semiconductor.

Optical Properties of Solids

T he optical properties of solids are closely related to their energy-band structures. Photons
of visible light have energies from about 1 to 3 eV. A free electron in a metal can readily
absorb such an amount of energy without leaving its valence band, and metals are accordingly
opaque. The characteristic luster of a metal is due to the reradiation of light absorbed by its free
electrons. If the metal surface is smooth, the reradiated light appears as a reflection of the original
– incident light.
Extra For a valence electron in an insulator to absorb a photon, on the other hand, the photon
electron energy must be over 3 eV if the electron is to jump across the forbidden band to the conduc-
tion band. Insulators therefore cannot absorb photons of visible light and are transparent. Of
course, most samples of insulating materials do not appear transparent, but this is due to the
scattering of light by irregularities in their structures. Insulators are opaque to ultraviolet light,
whose higher frequencies mean high enough photon energies to allow electrons to cross the
+ Silicon
forbidden band.
atom
Because the forbidden bands in semiconductors are about the same in width as the photon
energies of visible light, they are usually opaque to visible light. However, they are transparent
to infrared light whose lower frequencies mean photon energies too low to be absorbed. For this
reason infrared lenses can be made from the semiconductor germanium, whose appearance in
– visible light is that of an opaque solid.

If we instead incorporate gallium atoms in a silicon crystal, a different effect occurs.

Gallium atoms have only three electrons in their outer shells, whose configuration is
4s24p, and their presence leaves vacancies called holes in the electron structure of the
+ Extra crystal. An electron needs relatively little energy to enter a hole, but as it does so, it
electron leaves a new hole in its former location. When an electric field is applied across a
silicon crystal containing a trace of gallium, electrons move toward the anode by
successively filling holes (Fig. 10.28). The flow of current here is conveniently described
with reference to the holes, whose behavior is like that of positive charges since they
– move toward the negative electrode. A substance of this kind is called a p-type
semiconductor.
In the energy-band diagram of Fig. 10.29 we see that gallium as an impurity in
silicon provides energy levels, called acceptor levels, just above the valence band. Any
electrons that occupy these levels leave behind them vacancies in the valence band that
permit electric current to flow. The Fermi energy in a p-type semiconductor lies below
+ Extra the middle of the forbidden band.
electron Adding an impurity to a semiconductor is called doping. Phosphorus, antimony, and
bismuth as well as arsenic have atoms with five valence electrons and so can be used
Figure 10.27 Current in an n-type as donor impurities in doping silicon and germanium to yield an n-type semiconductor.
semiconductor is carried by sur-
plus electrons that do not fit into Similarly, indium and thallium as well as gallium have atoms with three valence elec-
the electron structure of a pure trons and so can be used as acceptor impurities. A minute amount of impurity can pro-
crystal. duce a dramatic change in the conductivity of a semiconductor. As an example, 1 part
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The Solid State 361

Acceptor Conduction band

impurity eF Forbidden band
levels
Valence band –

Figure 10.29 A trace of gallium in a silicon crystal provides acceptor levels in the normally forbidden
band, producing a p-type semiconductor.
Missing
9
electron
of a donor impurity per 10 parts of germanium increases its conductivity by a factor
of nearly 103. Silicon and germanium are not the only semiconducting materials with +
practical applications: another important class of semiconductors consists of compounds
of trivalent and pentavalent elements, such as GaAs, GaP, InSb, and InP.

–
10.7 SEMICONDUCTOR DEVICES
The properties of the p-n junction are responsible for the microelectronics
Missing
industry
electron

The operation of most semiconductor devices is based upon the nature of junctions
between p- and n-type materials. Such junctions can be made in several ways. A method +
especially adapted to the production of integrated circuits involves diffusing impuri-
ties in vapor form into a semiconductor wafer in regions defined by masks. A series of
diffusion steps using donor and acceptor impurities is part of the procedure for
manufacturing circuits that can contain millions of resistors, capacitors, diodes, and
transistors on a chip a few millimeters across. The limiting factor in this method is the –
wavelength of the light that is shined through masks to expose and thereby harden the
Missing
electron

Figure 10.28 Current in a p-type

semiconductor is carried by the
motion of “holes,” which are sites
of missing electrons. Holes move
toward the negative electrode as a
succession of electrons move into
them.

The IBM PowerPC 601 microprocessor chip is 10.95 mm square

and contains 2.8 million transistors. The functions of the various
parts of the chip are indicated.

361