12.

6 Bonding in Metals and Semiconductors

Learning Objective

1. To describe the electrical properties of a solid using band theory.

To explain the observed properties of metals, a more sophisticated approach is needed than the

electron-sea model described in Section 12.5 "Correlation between Bonding and the Properties of

Solids". The molecular orbital theory we used in Chapter 9 "Molecular Geometry and Covalent

Bonding Models" to explain the delocalized π bonding in polyatomic ions and molecules such as

NO2−, ozone, and 1,3-butadiene can be adapted to accommodate the much higher number of atomic

orbitals that interact with one another simultaneously in metals.

Band Theory

In a 1 mol sample of a metal, there can be more than 1024 orbital interactions to consider. In our

molecular orbital description of metals, however, we begin by considering a simple one-dimensional

example: a linear arrangement of n metal atoms, each containing a single electron in an s orbital. We

use this example to describe an approach to metallic bonding called band theory, which assumes

that the valence orbitals of the atoms in a solid interact, generating a set of molecular orbitals that

extend throughout the solid.

One-Dimensional Systems

If the distance between the metal atoms is short enough for the orbitals to interact, they produce

bonding, antibonding, and nonbonding molecular orbitals. The left portion of Figure 12.21 "The

Molecular Orbital Energy-Level Diagram for a Linear Arrangement of ", which is the same as the

molecular orbital diagram in Figure 9.35 "Bonding in Ozone", shows the pattern of molecular

orbitals that results from the interaction of ns orbitals as n increases from 2 to 5.

Figure 12.21 The Molecular Orbital Energy-Level Diagram for a Linear Arrangement of n Atoms,

Each of Which Contains a Singly Occupied s Orbital

portion, corresponding to n = 30 and n = ∞. As n becomes very large, the energy separation between

adjacent levels becomes so small that a single continuous band of allowed energy levels results. The

lowest-energy molecular orbital corresponds to positive overlap between all the atomic orbitals to

give a totally bonding combination, whereas the highest-energy molecular orbital contains a node

between each pair of atoms and is thus totally antibonding.

As we saw in Chapter 9 "Molecular Geometry and Covalent Bonding Models", the lowest-energy

orbital is the completely bonding molecular orbital, whereas the highest-energy orbital is the

completely antibonding molecular orbital. Molecular orbitals of intermediate energy have fewer

nodes than the totally antibonding molecular orbital. The energy separation between adjacent
orbitals decreases as the number of interacting orbitals increases. For n = 30, there are still discrete,

well-resolved energy levels, but as n increases from 30 to a number close to Avogadro’s number, the

spacing between adjacent energy levels becomes almost infinitely small. The result is essentially a

continuum of energy levels, as shown on the right in Figure 12.21 "The Molecular Orbital Energy-

Level Diagram for a Linear Arrangement of ", each of which corresponds to a particular molecular

orbital extending throughout the linear array of metal atoms. The levels that are lowest in energy

correspond to mostly bonding combinations of atomic orbitals, those highest in energy correspond

to mostly antibonding combinations, and those in the middle correspond to essentially nonbonding

combinations.

The continuous set of allowed energy levels shown on the right in Figure 12.21 "The Molecular

Orbital Energy-Level Diagram for a Linear Arrangement of " is called an energy band. The difference

in energy between the highest and lowest energy levels is the bandwidth and is proportional to the

strength of the interaction between orbitals on adjacent atoms: the stronger the interaction, the

larger the bandwidth. Because the band contains as many energy levels as molecular orbitals, and

the number of molecular orbitals is the same as the number of interacting atomic orbitals, the band

in Figure 12.21 "The Molecular Orbital Energy-Level Diagram for a Linear Arrangement of "

contains n energy levels corresponding to the combining of s orbitals from n metal atoms. Each of

the original s orbitals could contain a maximum of two electrons, so the band can accommodate a

total of 2n electrons. Recall, however, that each of the metal atoms we started with contained only a

single electron in each s orbital, so there are only n electrons to place in the band. Just as with

atomic orbitals or molecular orbitals, the electrons occupy the lowest energy levels available.

Consequently, only the lower half of the band is filled. This corresponds to filling all of the bonding

molecular orbitals in the linear array of metal atoms and results in the strongest possible bonding.

Multidimensional Systems

The previous example was a one-dimensional array of atoms that had only s orbitals. To extrapolate

to two- or three-dimensional systems and atoms with electrons in p and d orbitals is straightforward

in principle, even though in practice the mathematics becomes more complex, and the resulting

molecular orbitals are more difficult to visualize. The resulting energy-level diagrams are essentially

the same as the diagram of the one-dimensional example in Figure 12.21 "The Molecular Orbital

Energy-Level Diagram for a Linear Arrangement of ", with the following exception: they contain as

many bands as there are different types of interacting orbitals. Because different atomic orbitals

interact differently, each band will have a different bandwidth and will be centered at a different

energy, corresponding to the energy of the parent atomic orbital of an isolated atom.
Band Gap

Because the 1s, 2s, and 2p orbitals of a period 3 atom are filled core levels, they do not interact

strongly with the corresponding orbitals on adjacent atoms. Hence they form rather narrow bands

that are well separated in energy (Figure 12.22 "The Band Structures of the Period 3 Metals Na, Mg,

and Al"). These bands are completely filled (both the bonding and antibonding levels are completely

populated), so they do not make a net contribution to bonding in the solid. The energy difference

between the highest level of one band and the lowest level of the next is the band gap. It represents a

set of forbidden energies that do not correspond to any allowed combinations of atomic orbitals.

Figure 12.22 The Band Structures of the Period 3 Metals Na, Mg, and Al
The 3s and 3p valence bands overlap in energy to form a continuous set of energy levels that can

hold a maximum of eight electrons per atom.

Because they extend farther from the nucleus, the valence orbitals of adjacent atoms (3s and 3p in

Figure 12.22 "The Band Structures of the Period 3 Metals Na, Mg, and Al") interact much more

strongly with one another than do the filled core levels; as a result, the valence bands have a larger

bandwidth. In fact, the bands derived from the 3s and 3p atomic orbitals are wider than the energy

gap between them, so the result is overlapping bands. These have molecular orbitals derived from

two or more valence orbitals with similar energies. As the valence band is filled with one, two, or

three electrons per atom for Na, Mg, and Al, respectively, the combined band that arises from the

overlap of the 3s and 3p bands is also filling up; it has a total capacity of eight electrons per atom

(two electrons for each 3s orbital and six electrons for each set of 3p orbitals). With Na, therefore,

which has one valence electron, the combined valence band is one-eighth filled; with Mg (two

valence electrons), it is one-fourth filled; and with Al, it is three-eighths filled, as indicated in Figure

12.22 "The Band Structures of the Period 3 Metals Na, Mg, and Al". The partially filled valence band

is absolutely crucial for explaining metallic behavior because it guarantees that there are unoccupied

energy levels at an infinitesimally small energy above the highest occupied level.

Band theory can explain virtually all the properties of metals. Metals conduct electricity, for

example, because only a very small amount of energy is required to excite an electron from a filled

level to an empty one, where it is free to migrate rapidly throughout the crystal in response to an

applied electric field. Similarly, metals have high heat capacities (as you no doubt remember from

the last time a doctor or a nurse placed a stethoscope on your skin) because the electrons in the

valence band can absorb thermal energy by being excited to the low-lying empty energy levels.

Finally, metals are lustrous because light of various wavelengths can be absorbed, causing the

valence electrons to be excited into any of the empty energy levels above the highest occupied level.

When the electrons decay back to low-lying empty levels, they emit light of different wavelengths.

Because electrons can be excited from many different filled levels in a metallic solid and can then

decay back to any of many empty levels, light of varying wavelengths is absorbed and reemitted,

which results in the characteristic shiny appearance that we associate with metals.

Requirements for Metallic Behavior

For a solid to exhibit metallic behavior, it must have a set of delocalized orbitals forming a band of

allowed energy levels, and the resulting band must be only partially filled (10%–90%) with

electrons. Without a set of delocalized orbitals, there is no pathway by which electrons can move

through the solid.

Metallic behavior requires a set of delocalized orbitals and a band of allowed energy levels that is

partially occupied.

Band theory explains the correlation between the valence electron configuration of a metal and the

strength of metallic bonding. The valence electrons of transition metals occupy either their valence

ns, (n − 1)d, and np orbitals (with a total capacity of 18 electrons per metal atom) or their ns and

(n − 1)d orbitals (a total capacity of 12 electrons per metal atom). These atomic orbitals are close

enough in energy that the derived bands overlap, so the valence electrons are not confined to a

specific orbital. Metals with 6 to 9 valence electrons (which correspond to groups 6–9) are those

most likely to fill the valence bands approximately halfway. Those electrons therefore occupy the

highest possible number of bonding levels, while the number of antibonding levels occupied is

minimal. Not coincidentally, the elements of these groups exhibit physical properties consistent with

the presence of the strongest metallic bonding, such as very high melting points.

Insulators

In contrast to metals, electrical insulators are materials that conduct electricity poorly because their

valence bands are full. The energy gap between the highest filled levels and the lowest empty levels

is so large that the empty levels are inaccessible: thermal energy cannot excite an electron from a

filled level to an empty one. The valence-band structure of diamond, for example, is shown in part

(a) in Figure 12.23 "Energy-Band Diagrams for Diamond, Silicon, and Germanium". Because

diamond has only 4 bonded neighbors rather than the 6 to 12 typical of metals, the carbon 2s and 2p

orbitals combine to form two bands in the solid, with the one at lower energy representing bonding

molecular orbitals and the one at higher energy representing antibonding molecular orbitals. Each

band can accommodate four electrons per atom, so only the lower band is occupied. Because the

energy gap between the filled band and the empty band is very large (530 kJ/mol), at normal

temperatures thermal energy cannot excite electrons from the filled level into the empty band. Thus

there is no pathway by which electrons can move through the solid, so diamond has one of the

lowest electrical conductivities known.

Figure 12.23 Energy-Band Diagrams for Diamond, Silicon, and Germanium

Semiconductors

What if the difference in energy between the highest occupied level and the lowest empty level is

intermediate between those of electrical conductors and insulators? This is the case for silicon and

germanium, which have the same structure as diamond. Because Si–Si and Ge–Ge bonds are
substantially weaker than C–C bonds, the energy gap between the filled and empty bands becomes

much smaller as we go down group 14 (part (b) and part (c) of Figure 12.23 "Energy-Band Diagrams

for Diamond, Silicon, and Germanium"). (For more information on bond strengths, see Chapter 8

"Ionic versus Covalent Bonding", Section 8.8 "Properties of Covalent Bonds".) Consequently,

thermal energy is able to excite a small number of electrons from the filled valence band of Si and Ge

into the empty band above it, which is called the conduction band.

Exciting electrons from the filled valence band to the empty conduction band causes an increase in

electrical conductivity for two reasons:

1. The electrons in the previously vacant conduction band are free to migrate through the

crystal in response to an applied electric field.

2. Excitation of an electron from the valence band produces a “hole” in the valence band that is

equivalent to a positive charge. The hole in the valence band can migrate through the crystal

in the direction opposite that of the electron in the conduction band by means of a “bucket

brigade” mechanism in which an adjacent electron fills the hole, thus generating a hole

where the second electron had been, and so forth.

Consequently, Si is a much better electrical conductor than diamond, and Ge is even better, although

both are still much poorer conductors than a typical metal (Figure 12.24 "A Logarithmic Scale

Illustrating the Enormous Range of Electrical Conductivities of Solids"). Substances such as Si and

Ge that have conductivities between those of metals and insulators are called semiconductors. Many

binary compounds of the main group elements exhibit semiconducting behavior similar to that of Si

and Ge. For example, gallium arsenide (GaAs) is isoelectronic with Ge and has the same crystalline

structure, with alternating Ga and As atoms; not surprisingly, it is also a semiconductor. The

electronic structure of semiconductors is compared with the structures of metals and insulators in

Figure 12.25 "A Comparison of the Key Features of the Band Structures of Metals, Semiconductors,

and Insulators".

Figure 12.24 A Logarithmic Scale Illustrating the Enormous Range of Electrical Conductivities of

Solids
Figure 12.25 A Comparison of the Key Features of the Band Structures of Metals, Semiconductors,

and Insulators

Metallic behavior can arise either from the presence of a single partially filled band or from two

overlapping bands (one full and one empty).

Temperature and Conductivity

Because thermal energy can excite electrons across the band gap in a semiconductor, increasing the

temperature increases the number of electrons that have sufficient kinetic energy to be promoted

into the conduction band. The electrical conductivity of a semiconductor therefore increases rapidly

with increasing temperature, in contrast to the behavior of a purely metallic crystal. In a metal, as an
electron travels through the crystal in response to an applied electrical potential, it cannot travel

very far before it encounters and collides with a metal nucleus. The more often such encounters

occur, the slower the net motion of the electron through the crystal, and the lower the conductivity.

As the temperature of the solid increases, the metal atoms in the lattice acquire more and more

kinetic energy. Because their positions are fixed in the lattice, however, the increased kinetic energy

increases only the extent to which they vibrate about their fixed positions. At higher temperatures,

therefore, the metal nuclei collide with the mobile electrons more frequently and with greater

energy, thus decreasing the conductivity. This effect is, however, substantially smaller than the

increase in conductivity with temperature exhibited by semiconductors. For example, the

conductivity of a tungsten wire decreases by a factor of only about two over the temperature range

750–1500 K, whereas the conductivity of silicon increases approximately 100-fold over the same

temperature range. These trends are illustrated in Figure 12.26 "The Temperature Dependence of

the Electrical Conductivity of a Metal versus a Semiconductor".

Figure 12.26 The Temperature Dependence of the Electrical Conductivity of a Metal versus a

Semiconductor
The conductivity of the metal (tungsten) decreases relatively slowly with increasing temperature,

whereas the conductivity of the semiconductor (silicon) increases much more rapidly.

Note the Pattern

The electrical conductivity of a semiconductor increases with increasing temperature, whereas the

electrical conductivity of a metal decreases with increasing temperature.

n- and p-Type Semiconductors

Doping is a process used to tune the electrical properties of commercial semiconductors by

deliberately introducing small amounts of impurities. If an impurity contains more valence electrons

than the atoms of the host lattice (e.g., when small amounts of a group 15 atom are introduced into a

crystal of a group 14 element), then the doped solid has more electrons available to conduct current

than the pure host has. As shown in part (a) in Figure 12.27 "Structures and Band Diagrams of ",

adding an impurity such as phosphorus to a silicon crystal creates occasional electron-rich sites in

the lattice. The electronic energy of these sites lies between those of the filled valence band and the

empty conduction band but closer to the conduction band. Because the atoms that were introduced

are surrounded by host atoms, and the electrons associated with the impurity are close in energy to

the conduction band, those extra electrons are relatively easily excited into the empty conduction

band of the host. Such a substance is called an n-type semiconductor, with the n indicating that the

added charge carriers are negative (they are electrons).

Figure 12.27 Structures and Band Diagrams of n-Type and p-Type Semiconductors
(a) Doping silicon with a group 15 element results in a new filled level between the valence and

conduction bands of the host. (b) Doping silicon with a group 13 element results in a new empty

level between the valence and conduction bands of the host. In both cases, the effective band gap is

substantially decreased, and the electrical conductivity at a given temperature increases

dramatically.

If the impurity atoms contain fewer valence electrons than the atoms of the host (e.g., when small

amounts of a group 13 atom are introduced into a crystal of a group 14 element), then the doped

solid has fewer electrons than the pure host. Perhaps unexpectedly, this also results in increased

conductivity because the impurity atoms generate holes in the valence band. As shown in part (b) in

Figure 12.27 "Structures and Band Diagrams of ", adding an impurity such as gallium to a silicon

crystal creates isolated electron-deficient sites in the host lattice. The electronic energy of these
empty sites also lies between those of the filled valence band and the empty conduction band of the

host but much closer to the filled valence band. It is therefore relatively easy to excite electrons from

the valence band of the host to the isolated impurity atoms, thus forming holes in the valence band.

This kind of substance is called a p-type semiconductor, with the p standing for positive charge

carrier (i.e., a hole). Holes in what was a filled band are just as effective as electrons in an empty

band at conducting electricity.

Note the Pattern

n-Type semiconductors are negative charge carriers; the impurity has more valence electrons than

the host. p-Type semiconductors are positive charge carriers; the impurity has fewer valence

electrons than the host.

The electrical conductivity of a semiconductor is roughly proportional to the number of charge

carriers, so doping is a precise way to adjust the conductivity of a semiconductor over a wide range.

The entire semiconductor industry is built on methods for preparing samples of Si, Ge, or GaAs

doped with precise amounts of desired impurities and assembling silicon chips and other complex

devices with junctions between n- and p-type semiconductors in varying numbers and

arrangements.

Because silicon does not stand up well to temperatures above approximately 100°C, scientists have

been interested in developing semiconductors made from diamonds, a more thermally stable

material. A new method has been developed based on vapor deposition, in which a gaseous mixture

is heated to a high temperature to produce carbon that then condenses on a diamond kernel. This is

the same method now used to create cultured diamonds, which are indistinguishable from natural

diamonds. The diamonds are heated to more than 2000°C under high pressure to harden them even

further. Doping the diamonds with boron has produced p-type semiconductors, whereas doping

them with boron and deuterium achieves n-type behavior. Because of their thermal stability,

diamond semiconductors have potential uses as microprocessors in high-voltage applications.

Example 8

A crystalline solid has the following band structure, with the purple areas representing regions

occupied by electrons. The lower band is completely occupied by electrons, and the upper level is

about one-third filled with electrons.

2. What would happen to the electrical properties if all of the electrons were removed from the

upper band? Would you use a chemical oxidant or reductant to effect this change?

3. What would happen to the electrical properties if enough electrons were added to completely

fill the upper band? Would you use a chemical oxidant or reductant to effect this change?

Given: band structure

Asked for: variations in electrical properties with conditions

Strategy:

A Based on the occupancy of the lower and upper bands, predict whether the substance will be an

electrical conductor. Then predict how its conductivity will change with temperature.

B After all the electrons are removed from the upper band, predict how the band gap would affect

the electrical properties of the material. Determine whether you would use a chemical oxidant or

reductant to remove electrons from the upper band.

C Predict the effect of a filled upper band on the electrical properties of the solid. Then decide

whether you would use an oxidant or a reductant to fill the upper band.
Solution:

1. A The material has a partially filled band, which is critical for metallic behavior. The solid

will therefore behave like a metal, with high electrical conductivity that decreases slightly

with increasing temperature.

2. B Removing all of the electrons from the partially filled upper band would create a solid with

a filled lower band and an empty upper band, separated by an energy gap. If the band gap is

large, the material will be an electrical insulator. If the gap is relatively small, the substance

will be a semiconductor whose electrical conductivity increases rapidly with increasing

temperature. Removing the electrons would require an oxidant because oxidants accept

electrons.

3. C Adding enough electrons to completely fill the upper band would produce an electrical

insulator. Without another empty band relatively close in energy above the filled band,

semiconductor behavior would be impossible. Adding electrons to the solid would require a

reductant because reductants are electron donors.

Exercise

A substance has the following band structure, in which the lower band is half-filled with electrons

(purple area) and the upper band is empty.

2. What would happen to the electrical properties if all of the electrons were removed from the

lower band? Would you use a chemical oxidant or reductant to effect this change?

3. What would happen to the electrical properties if enough electrons were added to completely

fill the lower band? Would you use a chemical oxidant or reductant to effect this change?

Answer:

1. The solid has a partially filled band, so it has the electrical properties of a conductor.

2. Removing all of the electrons from the lower band would produce an electrical insulator with

two empty bands. An oxidant is required.

3. Adding enough electrons to completely fill the lower level would result in an electrical

insulator if the energy gap between the upper and lower bands is relatively large, or a

semiconductor if the band gap is relatively small. A reductant is required.

Summary

Band theory assumes that the valence orbitals of the atoms in a solid interact to generate a set of

molecular orbitals that extend throughout the solid; the continuous set of allowed energy levels is an

energy band. The difference in energy between the highest and lowest allowed levels within a

given band is the bandwidth, and the difference in energy between the highest level of one band

and the lowest level of the band above it is the band gap. If the width of adjacent bands is larger

than the energy gap between them, overlapping bands result, in which molecular orbitals derived

from two or more kinds of valence orbitals have similar energies. Metallic properties depend on a

partially occupied band corresponding to a set of molecular orbitals that extend throughout the solid

to form a band of energy levels. If a solid has a filled valence band with a relatively low-lying empty

band above it (a conduction band), then electrons can be excited by thermal energy from the filled

band into the vacant band where they can then migrate through the crystal, resulting in electrical

conductivity. Electrical insulators are poor conductors because their valence bands are full.

Semiconductors have electrical conductivities intermediate between those of insulators and

metals. The electrical conductivity of semiconductors increases rapidly with increasing temperature,

whereas the electrical conductivity of metals decreases slowly with increasing temperature. The

properties of semiconductors can be modified by doping, or introducing impurities. Adding an

element with more valence electrons than the atoms of the host populates the conduction band,

resulting in an n-type semiconductor with increased electrical conductivity. Adding an element

with fewer valence electrons than the atoms of the host generates holes in the valence band,

resulting in a p-type semiconductor that also exhibits increased electrical conductivity.

 Bonding in metals and semiconductors can be described using band theory, in which a set of

molecular orbitals is generated that extends throughout the solid.

Conceptual Problems

1. Can band theory be applied to metals with two electrons in their valence s orbitals? with no

electrons in their valence s orbitals? Why or why not?

2. Given a sample of a metal with 1020 atoms, how does the width of the band arising from p

orbital interactions compare with the width of the band arising from s orbital interactions?

from d orbital interactions?

3. Diamond has one of the lowest electrical conductivities known. Based on this fact, do you

expect diamond to be colored? Why? How do you account for the fact that some diamonds

are colored (such as “pink” diamond or “green” diamond)?

4. Why do silver halides, used in the photographic industry, have band gaps typical of

semiconducting materials, whereas alkali metal halides have very large band gaps?

5. As the ionic character of a compound increases, does its band gap increase or decrease?

Why?

6. Why is silicon, rather than carbon or germanium, used in the semiconductor industry?

7. Carbon is an insulator, and silicon and germanium are semiconductors. Explain the

relationship between the valence electron configuration of each element and their band

structures. Which will have the higher electrical conductivity at room temperature—silicon

or germanium?

8. How does doping affect the electrical conductivity of a semiconductor? Draw the effect of

doping on the energy levels of the valence band and the conduction band for both an n-type

and a p-type semiconductor.

Answers

1.

2.

3. The low electrical conductivity of diamond implies a very large band gap, corresponding to

the energy of a photon of ultraviolet light rather than visible light. Consequently, diamond

should be colorless. Pink or green diamonds contain small amounts of highly colored

impurities that are responsible for their color.

4.
 5. As the ionic character of a compound increases, the band gap will also increase due to a

decrease in orbital overlap. Remember that overlap is greatest for orbitals of the same

energy, and that the difference in energy between orbitals on adjacent atoms increases as the

difference in electronegativity between the atoms increases. Thus, large differences in

electronegativity increase the ionic character, decrease the orbital overlap, and increase the

band gap.

6.

7.

8.

Numerical Problems

1. Of Ca, N, B, and Ge, which will convert pure silicon into a p-type semiconductor when

doping? Explain your reasoning.

2. Of Ga, Si, Br, and P, which will convert pure germanium into an n-type semiconductor when

doping? Explain your reasoning