Semiconductors

The development of semiconductors is clearly among the most

significant technological achievements to evolve from the
study of solid-state chemistry and physics. Aside from their
well-known applications in computers and electronics,
semiconductors are also used in a wide variety of optical
devices such as lasers, light-emitting diodes, and solar panels.
The diversity of applications can be readily understood with
only a basic understanding of the theory behind these
materials.
Theory
The operation of semiconductors is best understood using band
theory. At its most fundamental level, band theory can be
extremely complex, requiring relatively advanced mathematics
and physics. When a large number of atoms combine to form a
solid, the electrons e − in the solid are distributed into energy
bands among all the atoms in the solid. Each band has a
different energy, and the electrons fill these bands from the
lowest energy to the highest, similar to the way electrons
occupy the orbitals in a single atom. The variation in properties
between electrical insulators, conductors ( metals ), and
semiconductors stems from differences in the band structures
of these materials (see Figure 1). For this discussion, three
terms must be defined. The highest energy band that contains
electrons is called the valence band, whereas the lowest energy
empty band is called the conduction band. The band gap is the
difference in energy between the valence and conduction
bands. The laws of quantum mechanics forbid electrons from
being in the band gap; thus, an electron must always be in one
of the bands.
In a metal (e.g., copper or silver), the valence band is only
partially filled with electrons (Figure 1a). This means that the
electrons can access empty areas within the valence band, and
move freely across all atoms that make up the solid. A current
can therefore be generated when a voltage is applied. In
general, for electrons to flow in a solid, they must be in a
partially filled band or have access to a nearby empty band. In
an electrical insulator, there is no possibility for electron flow
(Figure 1b), because the valence band is completely filled with
electrons, and the conduction band is too far away in energy to
be accessed by these electrons (the band gap is too large). A
semiconductor (Figure 1c) is a special case in which the band
gap is small enough that electrons in the valence band can
jump into the conduction band using thermal energy. That is,
heat in the material

A conventional tube amplifier, at left, and a solid-state memory

cell, at right. The size of such semiconductors allows for the
manufacturing of smaller devices.
Figure 1. Schematic of the electronic band structures of
different types of solids. Electrons are represented by shaded
areas.
(even at room temperature) gives some of the electrons enough
energy to travel across the band gap. Thus, an important
property of semiconductors is that their conductivity increases
as they are heated up and more electrons fill the conduction
band. The most well-known semiconductor is silicon (Si),
although germanium (Ge) and gallium arsenide (GaAs) are
also common.
To complete the development of semiconductor theory, the
concept of doping must be described (see Figure 2). In
principle, the idea is to introduce a different kind of atom into a
semiconductor in order to modify its electronic structure.
Consider, for example, adding a small amount of phosphorus,
P, into a silicon host. Phosphorus is one column to the right of
silicon in the Periodic Table, so it contains one additional
electron. This means that doping P into Si has the effect of
introducing additional electrons to the material, such that some
e − must go into the conduction band. Because extra negatively
charged electrons are added to the system, phosphorusdoped Si
is called an n- type semiconductor, and phosphorus is
described as a donor (of electrons). Similarly, a p- type
semiconductor can be fabricated by adding an element to the
left of Si in the Periodic Table. Boron, B, is a common dopant
for a p- type. In this case, the valence band will be missing
electrons. These empty locations in a p- type semiconductor
are also referred to as holes. Since holes represent the absence
of an electron, they carry a positive charge. In p- type
semiconductors, boron is referred to as an acceptor (of
electrons). From Figure 2, it can be seen that both n- and p-
type materials create partially filled bands, allowing for
electrical conduction. Dopant concentrations are fairly small,
around 10 16 atoms/cm 3 , constituting only about ten-billionths
of the total mass of the material.
If p- and n- type materials are layered together, a p-n junction
results (Figure 2c). Right at the interface, some of the excess
electrons from the n- type combine with holes from the p- type.
The resulting charge separation creates an energy barrier that
impedes any further movement of electrons. In most
technological applications, the important properties of
semiconductors are the result of the band structure of the p-n
junction. A single

Figure 2. Schematic diagrams of the band structures of (a) p

-type semiconductors, (b) n -type semiconductors, and (c) a p-
n junction.
junction based on the same host material (e.g., one interface of
p- and n- doped silicon) is called a homojunction. The
homojunction model is used here to describe the properties of
many devices that are based on semiconductors. However, it
should be noted that real systems are typically composed of
multiple p-p, n-n, and p-n junctions, called heterojunctions.
Such configurations greatly improve the performance of these
materials; in fact, the development of heterojunction devices
was critical to the widespread practical application of this

technology.
Semiconductors in Electronics
Semiconductors are used extensively in solid-state electronic devices and computers. The
majority of materials for these applications are based on doped silicon. An important
property of p-n junctions is that they allow electron flow only from the n side to the p
side. Such one-way devices are called diodes. Consider Figure 2c again. If a positive
voltage (also called a forward bias) is applied that lowers the energy barrier between n
and p, then the electrons in the conduction band on the n side can flow across the junction
(and holes can flow from p to n ). A reverse bias, however, raises the height of the barrier
and