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More About Materials Science

Metals, Semiconductors, and
Defects
Insulators
Thermal Conductivity Thermal Expansion

Defects

It is useful to think about solids in terms of a regular repeating pattern of

planes of particles. But it is important to recognize that solids are seldom
perfectly ordered. There are four basic mechanisms for introducing a point
defect into the structure of a solid, as shown in the gure below. When a
particle is missing at one or more lattice sites we get a vacancy. When a
particle forces its way into a hole between lattice sites, we get an interstitial
impurity. Substitutional impurities result from replacing the particle that
should occupy a lattice site with a dierent particle, such as substituting a K +
ion for a Na+ ion in NaCl. (If an ion with a dierent charge is substituted, the
electrical neutrality of the crystal must be maintained. If a Ca 2+ ion is
substituted for a Na+ ion, for example, a second Na+ ion must leave the
crystal so that it doesn't pick up an electric charge.) Dislocations are one-
dimensional defects caused by holes that are not large enough to be a
vacancy.

When a signicant fraction of the original particles are replaced by

impurities, it is possible to get a solid solution. Alloys, such as bronze and
brass, are examples of solid solutions. Bronze is a solution of tin dissolved in
copper. Brass is a mixture of copper and zinc that can contain as little as
10%, or as much as 45%, zinc.

Distortions of the crystal lattice often occur when impurities are added to a
solid. As a result, point defects often determine the properties of a material.
They can change the ease with which a material conducts electricity, its
mechanical strength, its ability to be shaped by hammering (malleability), or
to be drawn into wires (ductility). Dissolving small amounts of carbon in iron,

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for example, give the alloy known as steel, which is signicantly stronger
than iron. But higher percentages of carbon make steel so brittle that it can
shatter when dropped.

Point defects distort the lattice and provide a way for atoms to move about
the solid. Atoms can move from a lattice site into a vacancy, for example,
creating a new vacancy, as shown in the gure below.

Theoretical calculations of the ease with which one plane of atoms should slip
over another suggest that metals should be much more resistant to stress
than they are. In other words, metals are softer than one would expect.
Metallurgists have explained this by assuming that metals contain defects
that allow planes of atoms to slip past each other more readily than expected.
This hypothesis has been conrmed by microscopic analysis, which shows
dislocations that run through the crystal. There are two types of dislocations:
edge or screw dislocations. An edge dislocation is an extra half plane of
atoms that goes part way through a solid structure, as shown in the gure
below.

Imagine, for example, a single playing card inserted halfway into a deck of
cards. The line formed by the inserted card would be a dislocation line. The
presence of a dislocation defect allows one plane of atoms to slip more easily
over its neighboring plane of atoms, as shown in the gure below. Not all the
atoms in the two planes move past each other simultaneously; they move one
row at a time.

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An often quoted analogy is that of moving a carpet. Dragging the carpet

across the oor is diicult because of the friction developed from the contact
of the surface of the carpet with the oor. Imagine what would happen,
however, if a wrinkle is put into the carpet, as shown in part (a) of the gure
below. The carpet can now be moved by pushing the wrinkle across the oor,
because only the friction between a small section of carpet and the oor has
to be overcome. A similar phenomenon occurs when one plane of atoms
moves past another by means of a dislocation defect.

Because they allow planes of atoms in a solid to move one row at a time,
dislocations can weaken a metal. Paradoxically, they can also strengthen a
metal when the dislocations intersect to product knots similar to the
intersecting wrinkles in the gure labeled "b" in the gure below. This
phenomenon is encountered with metals that have been work hardened.
Consider what happens, for example, when a piece of iron is heated,
hammered, cooled, reheated, and reworked to form wrought iron. In the
course of work hardening the metal, intersecting dislocations are generated
that hinder the movement of planes of atoms.

Screw dislocations are more diicult to visualize than edge dislocations.The

gure below shows how a screw dislocation is produced when one side of a
crystal is displaced relative to the other side. For either edge or screw
dislocations a distortion is produced around the dislocation with a
corresponding stress produced within the material.

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Metals, Semiconductors, and Insulators

A signicant fraction of the gross national product (GNP) of the United

States, and all of the contribution to the GNP from high-technology
industries, can be traced to eorts to harness dierences in the way metals,
semiconductors, and insulators conduct electricity. This dierence can be
expressed in terms of electrical conductivity, which measures the ease with
which materials conduct an electric current. It can also be expressed in terms
of electrical resistivity, the inverse of conductivity, which measures the
resistance of a material to carrying an electric charge.

Silver and copper metal are among the best conductors of electricity, with a
conductivity of only 106 ohm-cm. (This is why copper is the metal most often
used in electric wires.) The conductivity of semiconductors such as silicon
and germanium is 108 to 1010 times smaller. (When pure, these semimetals
have a conductivity of 10-2 to 10-4 ohm-cm.) Insulators include glass (10-10
ohm-cm), diamond (10-14 ohm-cm), and quartz (10-18 ohm-cm), which all have
an extremely small tendency to carry an electric current.

The 1024-fold range of conductivity is not the only dierence among metals,
semiconductors, and insulators. Metals become better conductors when they
are cooled to lower temperatures. Some metals are such good conductors at
very low temperatures that they no longer have a measurable resistance and
therefore become superconductors. Semiconductors show the opposite
behavior they become much better conductors as the temperature
increases. The dierence between the temperature dependence of metals and
semiconductors is so signicant it is often the best criterion for distinguishing
between these materials. The large range of conductivities of solids is shown
in the gure below.

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The range of conductivities of solids span roughly 24 orders of magnitude.

Semiconductors are very sensitive to impurities. The conductivity of silicon or

germanium can be increased by a factor of up to 106 by adding as little as
0.01% of an impurity. Metals, on the other hand, are fairly insensitive to
impurities. It takes a lot of impurity to change the conductivity of a metal by
as much as a factor of 10; and unlike semiconductors, metals become poorer
conductors when impure.

To explain the behavior of metals, semiconductors, and insulators, we need to

understand the bonding in solids in more detail. Because it is the lightest
element in the period table that is a solid at room temperature, let's start by
building a model of what happens when lithium atoms interact. As a rst
step, we can consider what happens when a pair of lithium atoms with a 1s2
2s1 conguration interact to form a hypothetical gas phase Li2 molecule. The
Li2 molecule is formed by placing two electrons in the bonding domain
between the two Li nuclei.

Now let's imagine what happens when enough lithium atoms come together
to form a piece of lithium metal. The valence electrons are no longer conned
to the region between pairs of lithium nuclei, as was the case for an isolated
Li2 molecule in the gas phase. In the metal, each lithium atom is perturbed by
its neighbors and the energy states of each atom are slightly altered. The 1s
orbitals on the various metal atoms interact to form a band of orbitals whose
energy falls within a range from slightly below the energy of the isolated 1s
orbital to slightly above this energy, as shown in the gure below. The same
thing happens to the 2s orbitals.

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Each of the orbitals in these bands can hold two electrons of opposite spin.
Because there were two electrons in each of the 1s orbitals that formed the
lower-energy band, the "1s" band is lled. But there was only one electron in
each of the 2s orbitals that formed the higher-energy band, which means that
the "2s" band is only half-lled. It takes little, if any energy, to excite one of
the electrons in the 2s band from one orbital to another in the band. (The
energy gap between orbitals in the 2s band in lithium is only about 10-45 kJ.)
By moving from orbital to orbital within the 2s band, electrons can move from
one end of the crystal to the other. This band of orbitals is therefore called a
conduction band because it enables lithium metal to conduct electricity.

Let's now turn to magnesium, which has a [Ne] 3 s2 conguration. The 3s

orbitals on the neighboring magnesium atoms would overlap to form a band
of 3s orbitals. Because there are two electrons in each 3s orbital, this band is
totally lled. The empty 3p orbitals on magnesium, however, also interact to
form a band of orbitals. This empty 3p overlaps the 3s band in magnesium, so
that the combined band is only partially lled, allowing magnesium to
conduct electricity.

The dierences in the way metals, semiconductors, and insulators conduct

electricity can be explained with the diagram in the gure below. Metals have
lled bands of core electrons, such as the 1s band in lithium or the 1s and 2s
bands in magnesium. But they also have partially lled bands of orbitals that
allow electrons to move from one end of the crystal to the other. They
therefore conduct an electric current. All of the bands in an insulator are
either lled or empty. Furthermore, the gap between the highest energy lled
band and the lowest energy empty band in an insulator is so large that it is
diicult to excite electrons from one of these bands to the other. As a result,
it is diicult to move electrons through an insulator.

Semiconductors also have a band structure that consists of lled and empty
bands. The gap between the highest energy lled band and the lowest energy
empty band is small enough, however, that electrons can be excited into the
empty band by the thermal energy the electrons carry at room temperature.
Semiconductors therefore fall between the extremes of metals and insulators
in their ability to conduct an electric current.

To understand why metals become better conductors at low temperature it is

important to remember that temperature is a macroscopic reection of the
kinetic energy of the individual particles. Much of the resistance of a metal to

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an electric current at room temperature is the result of scattering of the

electrons by the thermal motion of the metal atoms as they vibrate back and
forth around their lattice points. As the metal is cooled, and this thermal
motion slows down, there is less scattering, and the metal becomes a better
conductor.

Semiconductors become better conductors at high temperatures because the

number of electrons with enough thermal energy to be excited from the lled
band to the empty band increases.

To understand why semiconductors are sensitive to impurities, let's look at

what happens when we add a small amount of a Group VA element, such as
arsenic, to one of the Group IVA semiconductors. Arsenic atoms have one
more valence electron than germanium and silicon atoms. Arsenic atoms can
therefore lose an electron to form As+ ions that can occupy some of the
lattice points in the crystal where silicon or germanium atoms are normally
found.

If the amount of arsenic is kept very small, the distance between these atoms
is so large that they don't interact. As a result, the extra electrons from the
arsenic atoms occupy orbitals in a very narrow band of energies that lie
between the lled and empty bands of the semiconductor, as shown in the
gure below. This decreases the amount of energy required to excite an
electron into the lowest energy empty band in the semiconductor and
therefore increases the number of electrons that have enough energy to cross
this gap. As a result, this "doped" semiconductor becomes a very much better
conductor of electricity than the pure semiconductor. Because the electric
charge is carried by a ow of negative particles, these semiconductors are
called n-type.

It is also possible to dope a Group IVA semiconductor with one of the

elements in Group IIIA, such as indium. These atoms have one less valence
electron than silicon or germanium atoms, and they can capture electrons
from the highest energy lled band to form holes in this band. The presence
of holes in a lled band has the same eect as the presence of electrons in an
empty band it allows the solid to carry an electric current. The electric
charge is now carried by a ow of positive particles, or holes, so these
semiconductors are called p-type.

Bringing n-type and p-type semiconductors together produces a device that

has a natural one-directional ow of electrons, which can be turned o by

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applying a small voltage in the opposite direction. This junction between

n-type and p-type semiconductors was the basis of the revolution in industrial
technology that followed the discovery of the transistor by William Shockley,
John Bardeen, and Walter Brattain at Bell Laboratories in 1948.

Thermal Conductivity

You may have noticed that metal ice-cube trays feel signicantly colder then
plastic ice-cube trays when you remove them from the freezer. Your senses
are obviously misleading you because the trays are at the same temperature
the temperature of the freezer. The metal trays feel colder because metals
are much better conductors of heat than plastic.

The ease with which metals conduct heat is related to their ability to conduct
an electric current. Most of the energy absorbed by a metal when it is heated
is used to increase the rate at which the atoms vibrate around their lattice
sites. But some of this energy is absorbed by electrons in the metal, which
move from orbital to orbital through the conduction band. The net result is a
transport of kinetic energy from one portion of the metal surface to another.
Metals feel cold to the touch because the electrons in the conduction band
carry heat away from our bodies and distribute this energy through the metal
object.

Plastics, on the other hand, are thermal insulators. They are poor conductors
of heat because orbitals in which electrons are held tend to be localized on an
individual atom or between pairs of atoms. The only way for electrons to
carry energy through a plastic is to use this energy to excite an electron from
a lled orbital to an empty orbital. But the dierence between the energies of
the lled and empty orbitals is so large that this rarely happens.

The dierence between thermal conductors and thermal insulators can be

quantied by dening the thermal conductivity of a substance as the
quantity of heat transmitted per second through a plate of the material one
centimeter thick and one square centimeter in area when the temperature
dierential between the two sides of the plate is one degree Celsius or one
Kelvin. The copper used to for pots and pans has a thermal conductivity that
is more than 5000 times the value for the styrofoam used for coee cups, as
shown by the data in the table below. This table is consistent with experience,
which suggests that the air that gets trapped in the bers of a down-lled
jacket is a better insulator than cotton, which is a much better insulator than
nylon.

Thermal Conductivities of Various Substances

Thermal Thermal
Conductivity Conductivity
Material (J/scmK)a Material (J/scmK)a

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Air 0.00026 Pb 0.353

Glass wool 0.00042 Cs 0.359
MgO 0.360
Cotton 0.00057
(100F)
Styrofoam 0.00079 Rb 0.582
Carbon
0.0010 Fe 0.804
tetrachoride
White pine 0.0011 Li 0.848
Oak 0.0015 K 1.025
He 0.001520 C (graphite)b 1.1-2.2
Cardboard 0.0021 Zn 1.16
Nylon 0.0025 Brass 1.2
Water 0.0061 Na 1.42
Brick 0.0063 Mg 1.56
Glass 0.0072-0.0088 Be 2.01
Concrete 0.0086-0.013 BeO 2.20 (100F)
Hg 0.083 Al 2.37
SiC 0.090 (100F) Au 3.18
NaCl 0.092 (0C) Cu 4.01
ZnS (zinc blend) 0.264 (0C) Ag 4.29
Al2O3 0.303 (100C) C (diamond)c 9.9-23.2
aAll values are at room temperature unless otherwise noted.
bValue is dependent on the impurities in graphite and on the orientation
of graphite, being larger in the direction parallel to the layers of carbon
atoms.
cValue is highly dependent on impurities and defects.

Thermal Expansion

It is tempting to think about solids as if the particles were locked into

position, the way bricks are used to build a wall. This would be a mistake,
however, because the particles in a solid are in more or less constant motion
rocking back and forth and rotating about their xed positions in the
crystal. This motion depends on two factors, the temperature of the system
and the strength of the interactions that hold the particles together. The
higher the temperature, the faster the particles are moving. The stronger the
force of attraction between particles, the smaller the distances the particles
move apart. Because the van der Waals forces that hold molecules together
are much weaker than the bonds between atoms in a metal or between
positive and negative ions in an ionic compound, molecular crystal expand
more when heated than metals or ionic compounds.

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The dierence between the coeicients of thermal expansion of iron and

copper was the source of a major problem for the Statue of Liberty, which
consists of copper plates supported by an iron skeleton. The insulating
material used to keep these two metals from coming into contact was
inevitably rubbed away because of dierences in the rate at which these two
metals expand when heated and contract when cooled. (For each degree
change in the temperature of the Statue, the volume of the copper metal
changes by 40% more than the iron metal.) When this happened, the two
metals came into contact, forming an electric cell that greatly increased the
rate at which the iron skeleton corroded.

The same phenomenon, however, is used to form the thermostats that turn
electrical appliances on and o. When two metals with very dierent
coeicients of thermal expansion are joined to form a bimetallic strip, the
metal that expands the most when heated forces the adjoined metal strip to
bend toward the metal with the smallest thermal expansion. This bimetallic
strip can be used to make a device that will turn a heater on or o as contact
is made or broken with an electrical contact, as shown in the gure below.

Thermal expansion and thermal conductivity can work together to weaken a

material. If heat isn't transported quickly through an object that is heated,
one part expands more rapidly than another. If any cracks or aws are
present, the hotter part of the substance will pull on the colder part and
widen the crack, causing breakage.

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