FPEM1013 Introduction to Engineering Materials

Chapter 5 Electrical Properties of Materials and Semiconductors

5.1 Electronic Materials
Silicon-based microelectronics are a ubiquitous part of modern life. With microchips
in items from laundry machines and microwaves to cell phones, in MP3 players and
from personal computers to the world’s fastest super computers, silicon was the
defining material of the later 20th century and will dominate computer-based and
information-related technologies for the foreseeable future.

While silicon is the substrate or base material of choice for most devices,
microelectronics include materials of nearly every class, including metals such as
copper and gold, other semiconductors such as gallium arsenide, and insulators such
as silicon dioxide.

5.2 Ohm’s Law and Electrical Conductivity

Most of us are familiar with the common form of Ohm’s law,

V = IR (1)

where V is the voltage (volts, V), I is the current (amperes or amps, A), and R is the
resistance (ohms, Ω) to the current flow. This law is applicable to most but not all
materials. The resistance (R) of a resistor is a characteristic of the size, shape, and
properties of the material according to

l l
R=ρ = (2)
A σA

where l is the length (cm) of the resistor, A is the cross-sectional area (cm2) of the
resistor, ρ is the electrical resistivity (ohm.cm or Ω.cm), and σ, which is the reciprocal
of ρ, is the electrical conductivity (ohm-1.cm-1). The magnitude of the resistance
depends upon the dimensions of the resistor. The resistivity or conductivity does not
depend on the dimensions of the material. Thus, resistivity or conductivity allows us
to compare different materials. For example, silver is a better conductor than copper.
Resistivity is a microstructure-sensitive property, similar to yield strength. The
resistivity of pure copper is much less than that of commercially pure copper, because
impurities in commercially pure copper scatter electrons and contribute to increased
resistivity. Similarly, the resistivity of annealed, pure copper is slightly lower than
that of cold-worked, pure copper because of the scattering effect associated with
dislocations. In components designed to conduct electrical energy, minimizing power
losses is important, not only to conserve energy, but also to minimize heating.

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The electrical power P (in watts, W) lost when a current flows through a resistance is
given by

P = VI = I2 R

A high resistance R results in larger power losses. These electrical losses are known
as Joule heating losses. A second form of Ohm’s law is obtained if we combine
Equations (1) and (2) to give

I V
=σ
A l

If we define I/A as the current density J (A/cm2) and V/l as the electric field E (V/cm),
then

J = σE

The current density J is also given by

J = nqv�

where n is the number of charge carriers (carriers cm3), q is the charge on each
carrier (1.6 x 10-19 C), and v is the average drift velocity (cm/s) at which the charge
carriers move [Figure 1-1(a)]. Thus,

v�
σE = nqv� or σ = nq
E

Diffusion occurs as a result of temperature and concentration gradients, and drift

occurs as a result of an applied electric or magnetic field. Conduction may occur as a
result of diffusion, drift, or both, but drift is the dominant mechanism in electrical
conduction.

The term ṽ/E is called the mobility μ(cm2/V.s) of the carriers (which in the case of
metals is the mobility of electrons):

v�
μ=
E

Finally,

σ = nqμ (3)

The charge q is a constant; from inspection of Equation 3, we find that we can control
the electrical conductivity of materials by (1) controlling the number of charge
carriers in the material or (2) controlling the mobility-or ease of movement-of the

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charge carriers. The mobility is particularly important in metals, whereas the number
of carriers is more important in semiconductors and insulators.

Figure 1-1 (a) Charge carriers, such as electrons, are deflected by atoms or defects
and take an irregular path through a conductor. The average rate at which the carriers
move is the drift velocity. (b) Valence electrons in metals move easily. (c) Covalent
bonds must be broken in semiconductors and insulators that do not contain
impurities for an electron to be able to move. (d) Entire ions may diffuse via a vacancy
mechanism to carry charge in many ionically bonded materials.

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Electrons are the charge carriers in metals [Figure 1-1(b)]. Electrons are, of course,
negatively charged. In semiconductors, electrons conduct charge as do positively
charged carriers known as holes [Figure 1-1(c)]. In semiconductors, electrons and
holes flow in opposite directions in response to an applied electric field, but in so
doing, they both contribute to the net current. Thus, Equation 3 can be modified as
follows for expressing the conductivity of semiconductors:

σ = nqμn + pqμp

In this equation, μn and μp are the mobilities of electrons and hole, respectively. The
terms n and p represent the concentrations of free electrons and holes in the
semiconductor.

In ceramics, when conduction does occur, it can be the result of electrons that ‘hop’
from one defect to another or the movement of ions [Figure 1-1(d)]. The mobility
depends on atomic bonding, imperfections, microstructure, and, in ionic compounds,
diffusion rates.

Because of these effects, the electrical conductivity of materials varies tremendously,

as illustrated in Table 1-1.

Table 1-1 Electrical conductivity of selected materials at T = 300 K*

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These values are approximate and are for high-purity materials at 300 K (unless
noted otherwise). Note that the values of conductivity for metals and semiconductors
depend very strongly on temperature. Electronic materials can be classified as (a)
superconductors, (b) conductors, (c) semiconductors, and (d) dielectrics or
insulators, depending upon the magnitude of their electrical conductivity. Materials
with conductivity less than 10-12Ω-1.cm-1, or resistivity greater than 1012Ω.cm, are
considered insulating or dielectric. Materials with conductivity less than 103Ω-1.cm-1
but greater than 10-12Ω-1.cm-1 are considered semiconductors. Materials with
conductivity greater than 103Ω-1.cm-1, or resistivity less than 10-3Ω-1.cm-1, are
considered conductors. (These are approximate ranges of values.)

We use the term ‘dielectric’ for materials that are used in applications where the
dielectric constant is important. The dielectric constant (k) of a material is a
microstructure sensitive property related to the material’s ability to store an
electrical charge. We use the term ‘insulator’ to describe the ability of a material to
stop the flow of DC or AC current, as opposed to its ability to store a charge. A measure
of the effectiveness of an insulator is the maximum electric field it can support
without an electrical breakdown.

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5.3 Band Structure of Solids
The electrons of atoms in isolation occupy fixed and discrete energy levels. The Pauli
exclusion principle is satisfied for each atom because only two electrons, at most,
occupy each energy level, or orbital. When N atoms come together to form a solid, the
Pauli exclusion principle still requires that no more than two electrons in the solid
have the same energy. As two atoms approach each other in order to form a bond, the
Pauli exclusion principle would be violated if the energy levels of the electrons did
not change. Thus, the energy levels of the electrons ‘split’ in order to form new energy
levels.

Figure 1-2 schematically illustrates this concept. Consider two atoms approaching
each other to form a bond.

Figure 1-2 The energy level boarden into bands as the number of electrons
grouped together increases.

The orbitals that contain the valence electrons are located (on average) farther from
the nucleus than the orbitals that contain the ‘core’ or innermost electrons. The
orbitals that contain the valence electrons of one atom thus interact with the orbitals
that contain the valence electrons of the other atom first. Since the orbitals of these
electrons have the same energy when the atoms are in isolation, the orbitals shift in
energy or ‘split’ so that the Pauli exclusion principle is satisfied. As shown in Figure
1-2, when considering two atoms, each with one orbital of interest, one of the orbitals
shifts to a higher energy level while the other orbital shifts to a lower energy level.
The electrons of the atoms will occupy these new orbitals by first filling the lowest
energy levels. As the number of atoms increases, so does the number of energy levels.
A new orbital with its own energy is formed for each orbital of each atom, and as the
number of atoms in the solid increases, the separation in energy between orbitals
becomes finer, ultimately forming what is called an energy band. For example, when

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N atoms come together to form a solid, the 2s energy band contains N discrete energy
levels, one for each atom in the solid since each atom contributes one orbital.

In order for charge carriers to conduct, the carriers must be able to accelerate and
increase in energy. The energy of the carriers can increase only if there are available
energy states to which the carriers can be promoted. Thus, the particular distribution
of energy states in the band structure of a solid has critical implications for its
electrical and optical properties.

Depending on the type of material involved (metal, semiconductor, insulator), there

may or may not be a sizable energy gap between the energy levels of the orbitals that
shifted to a lower energy state and the energy levels of the orbitals that shifted to a
higher energy state. This energy gap, if it exists, is known as the band gap.

Band Structure of Sodium Sodium is a metal and has the electronic

structure 1s22s22p63s1. Figure 1-3 shows a schematic diagram of the band structure
of sodium as a function of the interatomic separation. The energies within the bands
depend on the spacing between the atoms; the vertical line represents the
equilibrium interatomic spacing of the atoms in solid sodium.

Figure 1-3 The simplified band structure for sodium. The energy levels broaden
into bands. The 3s band, which is only half filled with electrons, is responsible for
conduction in sodium. Note that the energy levels of the orbitals in the 1s, 2s, and 2p
levels do not split at the equilibrium spacing for sodium.

Sodium and other alkali metals in column 1A of the periodic table have only one
electron in the outermost s level. The 3s valence band in sodium is half filled and, at
absolute zero, only the lowest energy levels are occupied. When electrons gain energy,

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they are excited into the empty higher energy levels. The promotion of carriers to
higher energy levels enables electrical conduction.

5.3.1 Band Structure of Semiconductors and Insulators

The elements in Group 4-carbon (diamond), silicon, germanium, and tin-contain two
electrons in their outer p shell and have a valence of four. Based on our discussion in
the previous section, we might expect these elements to have a high conductivity due
to the unfilled p band, but this behavior is not observed!

These elements are covalently bonded; consequently, the electrons in the outer s and
p bands are rigidly bound to the atoms. The covalent bonding produces a complex
change in the band structure. The 2s and 2p levels of the carbon atoms in diamond
can contain up to eight electrons, but there are only four valence electrons available.
When carbon atoms are brought together to form solid diamond, the 2s and 2p levels
interact and produce two bands (Figure 1-4).

Figure 1-4 The band structure of carbon in the diamond form. The 2s and 2p levels
combine to form two hybrid bands separated by an energy gap, Eg.

Each hybrid band can contain 4N electrons. Since there are only 4N electrons
available, the lower (or valence) band is completely full, whereas the upper (or
conduction) band is empty. A large energy gap or band gap (Eg) separates the valence
band from the conduction band in diamond (Eg ~ 5.5 eV). Few electrons possess
sufficient energy to jump the forbidden zone to the conduction band. Consequently,
diamond has an electrical conductivity of less than 10-18 ohm-1.cm-1. Other covalently
and ionically bonded materials have a similar band structure and, like diamond, are
poor conductors of electricity. Increasing the temperature supplies the energy
required for electrons to overcome the energy gap. For example, the electrical
conductivity of boron nitride increases from about 10-13 at room temperature to 10-4
ohm-1. cm-1 at 800°C.

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Figure 1-5 shows a schematic of the band structure of typical metals, semiconductors,
and insulators. Thus, an important distinction between metals and semiconductors is
that the conductivity of semiconductors increases with temperature, as more and
words, an increasing number of electrons from the covalent bonds in a semiconductor
is freed and becomes available for conduction. The conductivity of most metals, on
the other hand, decreases with increasing temperature. This is because the number
of electrons that are already available begin to scatter more (i.e., increasing
temperature reduces mobility).

Figure 1-5 Schematic of band structures for (a) metals, (b) semiconductors, and
(c) dielectrics or insulators. (Temperature is assumed to be 0 K.)

Although germanium (Ge), silicon (Si), and α-Sn have the same crystal
structure and band structure as diamond, their energy gaps are smaller. In fact, the
energy gap (Eg) in α-Sn is so small (Eg = 0.1 eV) that α-Sn behaves as a metal. The
energy gap is somewhat larger in silicon (Eg = 1.1 eV) and germanium (Eg = 0.67 eV),
these elements behave as semiconductors. Typically, we consider materials with a
band gap greater than 4.0 eV as insulators, dielectrics, or nonconductors; materials
with a band gap less than 4.0 eV are considered semiconductors.

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5.4 Semiconductors
Elemental semiconductors are found in Group 4B of the periodic table and include
germanium and silicon. Compound semiconductors are formed from elements in
Groups 2B and 6B of the periodic table (e.g., CdS, CdSe, CdTe, HgCdTe, etc.) and are
known as II-VI (two-six) semiconductors. They also can be formed by combining
elements from Groups 3B and 5B of the periodic table (e.g., GaN, GaAs, AlAs, AlP, InP,
etc.). These are known as III-V (three-five) semiconductors.

5.4.1 Intrinsic Semiconductor

An intrinsic semiconductor is one with properties that are not controlled by
impurities. An extrinsic semiconductor (n- or p-type) is preferred for devices, since
its properties are stable with temperature and can be controlled using ion
implantation or diffusion of impurities known as dopants. Semiconductor materials,
including silicon and germanium, provide the building blocks for many electronic
devices. These materials have an easily controlled electrical conductivity and, when
properly combined, can act as switches, amplifiers, or information storage devices.

The atoms of a semiconductor come together to form a solid, two energy bands are
formed [Figure 1-5(b)]. At 0 K, the energy levels of the valence band are completely
full, as these are the lowest energy states for the electrons. The valence band is
separated from the conduction band by a bandgap. At 0 K, the conduction band is
empty.

The energy gap Eg between the valence and conduction bands in semiconductors is
relatively small (Figure 1-5). As a result, as temperature increases, some electrons
possess enough thermal energy to be promoted from the valence band to the
conduction band. The excited electrons leave behind unoccupied energy levels, or
holes, in the valence band. When an electron moves to fill a hole, another hole is
created; consequently, the holes appear to act as positively charged electrons and
carry an electrical charge. When a voltage is applied to the material, the electrons in
the conduction band accelerate toward the positive terminal, while holes in the
valence band move toward the negative terminal (Figure 1-6). Current is, therefore,
conducted by the movement of both electrons and holes.

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Figure 1-6 When a voltage is applied to a semiconductor, the electrons move

through the conduction band, while the holes move through the valence band in the
opposite direction.

The conductivity is determined by the number of electrons and holes according to

σ = nqμn + pqμp

where n is the concentration of electrons in the conduction band, p is the

concentration of holes in the valence band, and μn and μp are the mobilities of
electrons and holes, respectively.

In intrinsic semiconductors, for every electron promoted to the conduction band,

there is a hole left in the valence band, such that

ni = p i

where ni and pi are the concentrations of electrons and holes, respectively, in an

intrinsic semiconductor. Therefore, the conductivity of an intrinsic semiconductor is

σ = qni (μn + μp )

In intrinsic semiconductors, we control the number of charge carriers and, hence, the
electrical conductivity by controlling the temperature. At absolute zero temperature,
all of the electrons are in the valence band, whereas all of the levels in the conduction
band are unoccupied [Figure 1-7(a)].

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Figure 1-7 The distribution of electrons and holes in the valence and conduction
bands (a) at absolute zero and (b) at an elevated temperature.

As the temperature increases, there is a greater probability that an energy level in the
conduction band is occupied (and an equal probability that a level in the valence band
is unoccupied, or that a hole is present) [Figure 1-7(b)].

As the temperature increases, the conductivity of a semiconductor also increases

because more charge carriers are available for conduction. Note that as for metals,
the mobilities of the carriers decrease at high temperatures, but this is a much weaker
dependence than the exponential increase in the number of charge carriers. The
increase in conductivity with temperature in semiconductors sharply contrasts with
the decrease in conductivity of metals with increasing temperature (Figure 1-8). Even
at high temperatures, however, the conductivity of a metal is orders of magnitudes
higher than the conductivity of a semiconductor.

Figure 1-8 The electrical conductivity versus temperature for intrinsic

semiconductors compared with metals.

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5.4.2 Extrinsic Semiconductors
The temperature dependence of conductivity in intrinsic semiconductors is nearly
exponential, but this is not useful for practical applications. We cannot accurately
control the behavior of an intrinsic semiconductor because slight variations in
temperature can significantly change the conductivity. By intentionally adding a small
number of impurity atoms to the material (called doping), we can produce an
extrinsic semiconductor. The conductivity of the extrinsic semiconductor depends
primarily on the number of impurity, or dopant, atoms and in a certain temperature
range is independent of temperature. This ability to have a tunable yet temperature
independent conductivity is the reason why we almost always use extrinsic
semiconductors to make devices.

n-Type Semiconductors Suppose we add an impurity atom such as

antimony (which has a valence of five) to silicon or germanium. Four of the electrons
from the antimony atom participate in the covalent-bonding process, while the extra
electron enters an energy level just below the conduction band (Figure 1-9).

Figure 1-9 When a dopant atom with a valence greater than four is added to silicon,
an extra electron is introduced and a donor energy state is created. Now electrons are
more easily excited into the conduction band.

Since the extra electron is not tightly bound to the atoms, only a small increase in
energy, Ed, is required for the electron to enter the conduction band. This energy level
just below the conduction band is called a donor state. An n-type dopant ‘donates’ a
free electron for each impurity added. The energy gap controlling conductivity is now
Ed rather than Eg (Table 1-2). No corresponding holes are created when the donor
electrons enter the conduction band. It is still the case that electron-hole pairs are
created when thermal energy causes electrons to be promoted to the conduction
band from the valence band; however, the number of electron-hole pairs is significant
only at high temperatures.

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Table 1-2 The donor and acceptor energy levels (in electron volts) when silicon
and germanium semiconductors are doped

p-Type Semiconductors When we add an impurity such as gallium

or boron, which has a valence of three, to Si or Ge, there are not enough electrons to
complete the covalent bonding process. A hole is created in the valence band that can
be filled by electrons from other locations in the band (Figure 1-10).

Figure 1-10 When a dopant atom with a valence of less than four is substituted into
the silicon structure, a hole is introduced in the structure and an acceptor energy level
is created just above the valence band.

The holes act as ‘acceptors’ of electrons. These hole sites have a somewhat higher
than normal energy and create an acceptor level of possible electron energies just
above the valence band (Table 1-2). An electron must gain an energy of only Ea in
order to create a hole in the valence band. The hole then carries charge. This is known
as a p-type semiconductor.

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