CHAPTER

ELECTRONS IN SOLIDS

2.1

INTRODUCTION

All semiconductor devices depend on the behavior of electrons in a solid. The behavior
of electrons in free space as well as in solids is represented by the Schrodinger wave
equation The Schrodinger wave equation is not convenient for discussion of semicon
ductor devices, but it may be used to obtain the familiar quantities which adequately
describe semiconductors, such as the energy gap and the intrinsic carrier concentration.

If Si was the only commercially important semiconductor, then a table and brief descrip
tion of the important properties would be an adequate introduction before a detailed con
sideration of semiconductor-device behavior. Specialized applications of many other

semiconductor materials make a vast array of unique products possible. For example,

the compact disk (CD) player uses a III-V (three-five) compound semiconductor laser
to read the disk. Other semiconductor materials include the group-four (IV) compound
semiconductor SiC, and II-VI (two-six) compound semiconductors such as zinc selenide (ZnSe). To be able to deal with this growing list of semiconductor materials,
a more complete description of properties such as the energy gap is essential. These

properties can be illustrated by considering both Si and the III-V compound gallium
arsenide (GaAs).

The wave-particle duality for the electron is introduced m Sec. 2.2 by a discussion

of the hydrogen atom. The orbit radius and ionization energy for the single electron
12

2.2

THE HYDROGEN ATOM

13

bound to the^hydrogen nucleus are useful in describing the ionization energy of impu
Schrodinger

rities in semiconductors. The Schrodinger wave equation is considered in Sec. 2.3 to

wave equation

permit the description of the motion of the electrons in a single-crystal solid. From the
Schrodinger wave equation, the relation between the electron energy E and the wave
vector k, which is also called the phase or propagation constant, will be established. The

effective mass

relation between E and k is shown in Sec. 2.4 to be represented by an effective mass for
a free carrier in a semiconductor. In fact, many properties of real solids are summarized
by this E versus k relationship. To represent the number of free electrons in a semicon

density of

intrinsic

ductor, it is necessary to derive the concept of the density of states, which is given in
Sec. 2.5. At a given temperature, the electrons are distributed among the allowed energy
levels as described by the Fermi-Dirac distribution function. Section 2.6 introduces the
Fermi-Dirac distribution function and illustrates the useful concept of the effective den
sity of states. The electron concentration of a pure semiconductor, the intrinsic carrier
concentration, is derived in Sec. 2.7. In Sec. 2.8, the control of the concentration of free
carriers in the semiconductor by the introduction of small amounts of impurities into
the semiconductor is presented. The significant concepts introduced in this chapter are

carrier

summarized in Sec. 2.9, together with the physical constants, Si and GaAs parameters,

states

Fermi function
effective
density of
states

concentration

and the expressions useful for representing free carriers in semiconductors.

The first part of Appendix A at the end of this chapter gives the expressions for
the fraction of the donors or acceptors which are ionized as a function of the impurity
ionization energy, the position of the Fermi level, and the temperature. In the second
part of Appendix A, the concentration dependence of the ionization energy is presented.
For devices considered in this text, the ionized impurity concentration will be given
rather than the total impurity concentration which may exceed the ionized impurity
concentration.

2.2

THE HYDROGEN ATOM

Gauss's law in
integralform:
eoj%-da =

j pdv = qand
% = q/47re0r2.
Then, 9 =

Before the structure of the atom was well known, scattering experiments led Rutherford1
to propose that the nucleus was the center of the atom. This nucleus was composed
of positive protons and neutral neutrons, with electrons moving in orbits around the
nucleus. For a neutral atom, the number of electrons equals the number of protons.
This model for the hydrogen atom is shown in Fig. 2.1. For the electron in Fig. 2.1, the
balance of the centrifugal force and the Coulomb force gives the following equation:

4776o

(2.1)

where q is the charge, ra0 is the free electron mass, r is the orbit radius, and o is the
dielectric constant of free space. From classical electromagnetic theory, charged particle
acceleration (v2/r) would result in light emission. With the loss of energy because of
radiation, the electron radius would decrease and the electron would spiral into the
nucleus. This behavior would predict a continuous range of frequency of the emitted

14

CHAPTER 2

ELECTRONS IN SOLIDS

FIGURE 2.1

Illustration of an electron moving in a

circular orbit around a proton.

light for an excited hydrogen gas. However, experimentally, the hydrogen emission
stectrum was known to consist of discrete emission lines.

To resolve this inconsistency, Bohr3 proposed that the laws of classical electro

dynamics must be modified by utilizing Planck's empirical formulation of quantized

radiation4 He postulated that an electron can exist only in certain orbits at a defi
nite energy and an electron can change from a higher energy orbit (E2) to a lower

energy orbit (E,) by emitting a photon of energy hv, where h is Planck s constant
(4.1354 X 10"15 eV-s) and v is the frequency:

E2 - Ei = hv.

<2-2)

Another concept necessary for understanding the hydrogen atom was the proposal

by de Broglie5 that particles should be assigned a wavelength,

A = A/|p|

(2.3)

where A is the wavelength of the electron as a wave, and |p| is the magnitude of the
dectron momentum. Electrons were shown to undergo diffraction as expected for a
wave in an experiment by Davisson and Germer.

The orbits postulated by Bohr suggest that the orbit length should be an integer

multiple of the wavelength:

2-77T = n\ = nh/\p\ = n/i/(mo|v|),

where n is an integer number and Eq. (2.3) has been used to relate A to |p|. With
nh

2irmor

(2.5)

from Eq. (2.4), and substituting into Eq. (2.1),

r = (n2h2e)l(>nmW) ~ 0-529 X l(T8n2 cm|,

(2.6)

where r is the stable radius of the nth orbit. The radius of the ground state for n - 1 is

%%T*?2%LJ Scribed
^
*%%T?2%L*J
S by Bq. (2.4), an integral
il number
b off
whole wavelengths must be fitted around the circumference. Although an oversimphfi-

2.2

THE HYDROGEN ATOM

15

FIGURE 2.2 An electron orbit with a circumference

of six wavelengths. The dashed line is the classical
orbit and the solid line represents the quantum

mechanical wave function with the wavelength A.7

cation, an example of an orbit with an integral number of wavelengths is illustrated in

Fig. 2.2.

The total energy of the electron is equal to the sum of its potential and kinetic

energy,

(2.7)

E =

with Eq. (2.1) for m0v2. With r from Eq. (2.6), the energy En of the nth orbit in Eq. (2.7)
becomes

En

-q4m0
%e2h2n2 '

(2.8)

Then, the change in energy corresponding to a transition from an initial orbit nin to a
final orbit nf is
(2.9)

The binding energy of the electron to the nucleus would be for nin = 1 and nf = ,
which gives

A = -13.6eV.

(2.10)

The Bohr radius given by Eq. (2.6) and the binding energy given by Eq. (2.10) will be
useful concepts when considering impurity elements in semiconductors.

EXAMPLE 2.1 To illustrate the conversion of eV to ergs, find the velocity of a free
electron with a mass m0 = 9.1 x 10"28 g and a kinetic energy of 1 eV. Note that the

conversion of eV to joules (j) or ergs is given by 1 eV = 1.6X 10 19 j = 1.6X 10

erg.