Metals, Alloys and

Semiconductors
Learning Objective
2.D.2 and 2.D.3

Bonding Models for Metals
Electron Sea Model: A regular array of metals
in a sea of electrons.
Band (Molecular Orbital) Model: Electrons
assumed to travel around metal crystal in MOs
formed from valence atomic orbitals of metal
atoms.
Conduction Bands: closely spaced empty
molecular orbitals allow conductivity of heat
and electricity.
Molecular-Orbital Model for Metals
Delocalized bonding requires the atomic orbitals on one
atom to interact with atomic orbitals on neighboring atoms.
Example: Graphite electrons are delocalized over a whole
plane, while benzene molecules have electrons delocalized
over a ring.
Recall that the number of molecular orbitals is equal to the
number of atomic orbitals.
In metals there are a very large number of orbitals.
As the number of orbitals increases, their energy spacing
decreases and they band together.
The available electrons do not completely fill the band of
orbitals.

Unit 4: Bonding
Molecular-Orbital Model for Metals
Therefore, electrons can be promoted to unoccupied energy bands.
Because the energy differences between orbitals are small the
promotion of electrons requires little energy.
As we move across the transition metal series, the antibonding
band starts becoming filled.
Therefore, the first half of the transition metal series has only
bonding-bonding interactions and the second half has bonding
antibonding interactions.
We expect the metals in the middle of the transition metal series
(group 6B) to have the highest melting points.
The energy gap between bands is called the band gap.
The electron-sea model is a qualitative interpretation of band
theory (molecular-orbital model for metals).

Unit 4: Bonding
Unit 4: Bonding
Molecular Orbital Theory
Recall that atomic
orbitals mix to give
rise to molecular
orbitals.
Fermi Level- Highest filled energy level
Unit 4: Bonding
The electronic band structure of nickel.
The left side of the figure shows the electron configuration of a single Ni atom, while the right-
hand side of the figure shows how these orbital energy levels broaden into energy bands in bulk
nickel. The horizontal dashed gray line denotes the position of the Fermi Level, which separates
the occupied molecular orbitals (shaded in blue) from the unoccupied molecular orbitals.
Unit 4: Bonding
Unit 4: Bonding
Molecular Orbital Theory
In such compounds,
the energy gap
between molecular
orbitals essentially
disappears, and
continuous bands of
energy states result.
Alloys

Alloys contain more than one element and have
the characteristic properties of metals.
Solid Solution alloys are homogeneous mixtures.
Pure metals and alloys have different physical
properties.
An alloy of gold and copper is used in jewelry (the
alloy is harder than the relatively soft pure 24
karat gold).
14 karat gold is an alloy containing 58% gold.

Unit 4: Bonding
Metal Alloys-Solid Solutions
Substance has mixture of element and
metallic properties.
1. Substitutional Alloy: some metal atoms
replaced by others of similar size. Electronegativities
usually are similar. The atoms must have similar
atomic radii.
The elements must have similar bonding
characteristics.
brass = Cu/Zn

Unit 4: Bonding
Metal Alloys
(continued)
2. Interstitial Alloy: Interstices (holes) in closest
packed metal structure are occupied by small atoms.
Solute atoms occupy interstices small holes
between solvent atoms. One element (usually a
nonmetal) must have a significantly smaller radius
than the other (in order to fit into the interstitial site).

steel = iron + carbon
3. Both types: Alloy steels contain a mix of
substitutional (Cr, Mo) and interstitial (Carbon) alloys.
Unit 4: Bonding
Alloys vs. Pure Metal
The alloy is much harder, stronger, and less ductile than the pure metal (increased
bonding between nonmetal and metal).
An example is steel (contains up to 3% carbon).
mild steels (<0.2% carbon)
useful for chains, nails, etc.
medium steels (0.2-0.6% carbon)
useful for girders, rails, etc.
high-carbon steels (0.6-1.5% carbon)
used in cutlery, tools, springs.
Other elements may also be added to make alloy steels.
Addition of V and Cr increases the strength of the steel and improves its resistance
to stress and corrosion.
The most important iron alloy is stainless steel. It contains C, Cr (from
ferrochrome, FeCr
2
), and Ni.
Heterogeneous alloys: The components are not dispersed uniformly (e.g., pearlite
steel has two phases: almost pure Fe and cementite, Fe
3
C).

Unit 4: Bonding
Substitutional
Alloy



Interstitial Alloy
Unit 4: Bonding
Ordered intermetallic structures.

(a) The face-centered cubic unit cell of a cubic close-packed metal. (b) The ordered
structure of Ni
3
Al with nickel atoms shown in gray and aluminum atoms in blue. (c) The
ordered structure of TiAl with titanium atoms shown in red and aluminum atoms in blue.
Unit 4: Bonding
Figure 23.17abcd
Unit 4: Bonding
Which two substances are most likely
to form an interstitial alloy?
Nickel and titanium
Silver and tin
Tin and lead
Copper and zinc
Tungsten and carbon
Unit 4: Bonding
Which two substances are most likely
to form an interstitial alloy?
Nickel and titanium
Silver and tin
Tin and lead
Copper and zinc
Tungsten and carbon
Unit 4: Bonding
Unit 4: Bonding
Types of Materials
Rather than having molecular orbitals
separated by an energy gap, these
substances have energy bands.
Energy bands in metals, semiconductors, and insulators.

Metals are characterized by the highest-energy electrons occupying a partially filled band.
Semiconductors and insulators have an energy gap that separates the completely filled band
(shaded in blue) and the empty band (unshaded), known as the band gap and represented by
the symbol E
g
. The filled band is called the valence band (VB), and the empty band is called
the conduction band (CB). Semiconductors have a smaller band gap than insulators.
Unit 4: Bonding
Unit 4: Bonding
Types of Materials
The gap between bands determines
whether a substance is a metal, a
semiconductor, or an insulator.
Unit 4: Bonding
Metals
Valence electrons are
in a partially-filled
band.
Unit 4: Bonding
Metals
There is virtually no
energy needed for an
electron to go from
the lower, occupied
part of the band to
the higher,
unoccupied part.
This is how a metal
conducts electricity.
Unit 4: Bonding
Unit 4: Bonding
Semiconductors
Semiconductors have
a gap between the
valence band and
conduction band of
~50-300 kJ/mol.
Unit 4: Bonding
Semiconductors
Among elements, only silicon,
germanium and graphite
(carbon), all of which have 4
valence electrons, are
semiconductors.
Inorganic semiconductors (like
GaAs) tend to have an average of
4 valence electrons (3 for Ga, 5
for As).
Figure 12.00CO2
Unit 4: Bonding
An intrinsic semiconductor is a semiconductor in its pure state. For every electron that jumps into
the conduction band, the missing electron will generate a hole that can move freely in the
valence band. The number of holes will equal the number of electrons that have jumped.
Unit 4: Bonding
Unit 4: Bonding
Insulators
The energy band gap
in insulating materials
is generally greater
than ~350 kJ/mol.
They are not
conductive.
The relationship between orbital
overlap and band gap (a).

(a) In diamond the CC
distance is relatively short (1.55
). This distance leads to
effective overlap of orbitals on
neighboring atoms, which in
turn leads to a large splitting
between the valence and
conduction bands (E
g
= 5.5 eV).
(b) In silicon the SiSi distance is much longer
(2.35 ), which diminishes the orbital overlap
leading to small splitting between the valence
and conduction bands (E
g
= 1.11 eV).
Unit 4: Bonding
The relationship between bond polarity and band gap.

In germanium the bonding is purely covalent. In gallium arsenide the difference in
electronegativity introduces polarity into the bonds. The gallium atoms are less
electronegative than germanium, which is reflected in an upward shift of the energies
of the gallium atomic orbitals. The arsenic atoms are more electronegative than
germanium, which is reflected in a downward shift of the energies of the arsenic atomic
orbitals. The introduction of bond polarity increases the band gap from 0.67 eV for Ge
to 1.43 eV for GaAs.
Unit 4: Bonding
The addition of controlled small amounts of impurities (doping) to a semiconductor changes the electronic
properties of the material.

Left: A pure, intrinsic semiconductor has a filled valence band and an empty conduction
band (ideally).
Middle: The addition of a dopant atom that has more valence electrons than the host
atom adds electrons to the conduction band (i.e., phosphorus doped into silicon). The
resulting material is an n-type semiconductor.
Right: The addition of a dopant atom that has fewer valence electrons than the host
atom leads to fewer electrons in the valence band or more holes in the valence band
(i.e., aluminum doped into silicon). The resulting material is a p-type semiconductor.
Unit 4: Bonding
Unit 4: Bonding
Doping
By introducing very small
amounts of impurities
that have more (n-Type)
or fewer (p-Type) valence
electrons, one can
increase the conductivity
of a semiconductor.
Unit 4: Bonding
Which of the following is a p-type semiconductor?
Sulfur-doped carbon

Boron-doped germanium
Phosphorus-doped silicon

Ultra-pure silicon
Carbon-doped copper
Unit 4: Bonding
Which of the following is a p-type semiconductor?
Sulfur-doped carbon

Boron-doped germanium
Phosphorus-doped silicon

Ultra-pure silicon
Carbon-doped copper
Unit 4: Bonding
Diode- Used to switch and convert between
electromagnetic radiation and electric current
Semiconductor created that has p-type on one half and n-type on
the other half
Known as p-n rectifying junction
The energy level adjust so the Fermi Levels are equal
This movement of levels creates valence level distortion and
Conduction Band Distortion
Valence Band n-type valence level is lower than p-type
Conduction Band of of N-type is greater than p-type
P- type has more positive holes in Valence level
Equilibrium Phenomena
Holes from p-type valence band flow to n-type Fermi Level and
electrons flow from n-type Valence Band into p-type Valence Band
Unit 4: Bonding
Light Emitting Diodes
p-type semiconductor The addition of a dopant atom that has
fewer valence electrons than the host atom leads to fewer
electrons in the valence band or more holes in the valence band
joined to a n-type semiconductor"the addition of a dopant atom
that has more valence electrons than the host atom adds
electrons to the conduction band
When Voltage applied positive to p-type and negative electrons
to n-type
When electron from conduction Band in n-type moves across
junction it can drop into a positive hole in the valence band of p-
type
This drop emits energy based on the Gap difference between
Conduction band of n-type and Valence Band of p-type. Band
Gap


Unit 4: Bonding
Light emitting diodes.
The heart of a light emitting diode is a p-n junction where an applied voltage drives
electrons and holes to meet. Bottom: The color of light emitted depends upon the band
gap of the semiconductor used to form the p-n junction. For display technology red,
green, and blue are the most important colors because all other colors can be made by
mixing these colors.
Unit 4: Bonding
Unit 4: Bonding
Color Voltage Drop Composition
Red

610 < < 760

1.63 < V < 2.03

Aluminium gallium arsenide (AlGaAs)
Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)

Orange 590 < < 610 2.03 < V < 2.10
Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)
Yellow 570 < < 590 2.10 < V < 2.18
Gallium arsenide phosphide (GaAsP)
Aluminium gallium indium phosphide (AlGaInP)
Gallium(III) phosphide (GaP)
Green 500 < < 570 1.9
[63]
< V < 4.0
Traditional green:
Gallium(III) phosphide (GaP)
Aluminium gallium indium phosphide (AlGaInP)
Aluminium gallium phosphide (AlGaP)
Pure green:
Indium gallium nitride (InGaN) / Gallium(III) nitride (GaN)
Blue 450 < < 500 2.48 < V < 3.7
Zinc selenide (ZnSe)
Indium gallium nitride (InGaN)
Silicon carbide (SiC) as substrate
Silicon (Si) as substrateunder development
Violet 400 < < 450 2.76 < V < 4.0 Indium gallium nitride (InGaN)
Figure 12.12
Unit 4: Bonding
Electricity from sunlight.
Unit 4: Bonding
Qualitative Comparison of Semiconductor Band Gaps
Will GaP have a larger or smaller band gap than ZnS? Will it have a larger or smaller
band gap than GaN?
Solution
Analyze: The size of the band gap depends upon the vertical and horizontal positions of
the elements in the periodic table. The band gap will increase when either of the following
conditions is met: (1) The elements are located higher up in the periodic table, where
enhanced orbital overlap leads to a larger splitting between bonding and antibonding
orbitals: or (2) The horizontal separation between the elements increases, which leads to
an increase in the electronegativity difference and the bond polarity.
Plan: We must look at the periodic table and compare the relative positions of the
elements in each case.
Solve: Gallium is in the fourth period and group 3A. Its electron configuration is
[Ar]3d
10
4s
2
4p
1
. Phosphorus is in the third period and group 5A. Its electron configuration
is [Ne]3s
2
3p
3
. Zinc and sulfur are in the same periods as gallium and phosphorus,
respectively. However, zinc, in group 2B, is one element to the left of gallium and sulfur in
group 5A, is one element to the right of phosphorus. Thus we would expect the
electronegativity difference to be larger for ZnS, which should result in ZnS having a larger
band gap than GaP.
For both GaP and GaN the more electropositive element is gallium. So we need only
compare the positions of the more electronegative elements, P and N. Nitrogen is located
above phosphorus in group 5A. Therefore, based on increased orbital overlap, we would
expect GaN to have a larger band gap than GaP. Additionally, nitrogen is more
electronegative than phosphorus, which also should result in a larger band gap for GaP.
Unit 4: Bonding
Qualitative Comparison of Semiconductor Band Gaps
Will ZnSe have a larger or smaller band gap than ZnS?
Answer: Because zinc is common to both compounds and selenium is below sulfur in
the periodic table, the band gap of ZnSe will be smaller than ZnS.
Practice Exercise
Unit 4: Bonding
Identifying Types of Semiconductors
Which of the following elements, if doped into silicon, would yield an n-type
semiconductor? Ga; As; C.
Suggest an element that could be used to dope silicon to yield a p-type material.
Answer: Because Si is in group 4A, we need to pick an element in group 3A. Boron
and aluminum are both good choicesboth are in group 3A. In the semiconductor
industry boron and aluminum are commonly used dopants for silicon.
Practice Exercise
Solution
Analyze: An n-type semiconductor means that the dopant atoms must have more
valence electrons than the host material. Silicon is the host material in this case.
Plan: We must look at the periodic table and determine the number of valence
electrons associated with Si, Ga, As, and C. The elements with more valence
electrons than silicon are the ones that will produce an n-type material upon
doping.
Solve: Si is in column 4A, and so has four valence electrons. Ga is in column 3A, and
so has three valence electrons. As is in column 5A, and so has five valence
electrons; C is in column 4A, and so has four valence electrons. Therefore, As, if
doped into silicon, would yield an n-type semiconductor.
Unit 4: Bonding