Metals

Properties of metals

Physical properties

Typical physical properties of metals:

 high melting points

 good conductors of electricity
 good conductors of heat
 high density
 Malleable -- Malleable substances can be bent or hammered into shape without shattering,
while brittle substances shatter when bent or hit.
 Ductile - they can be drawn out into thin wires.

Metallic structure and bonding

In metals, the electrons leave the outer shells of metal atoms, forming positive
metal ions and a 'sea' of delocalized electrons. Metals are solids at room temperature,
so the structure of a solid metal consists of closely packed metal ions. These ions are
arranged in a regular way to form a metallic lattice structure. The lattice has layers of
metal ions.

Metallic bonding is the strong electrostatic force of attraction between the metal ions
and the delocalized electrons.
Conduction of electricity
Substances conduct electricity because they contain charged particles that are able to move.

When a voltage is applied to a metal, the delocalized electrons travel through the lattice
structure. The movement of these charged particles forms an electric current.

Materials like silicon and germanium are some of the commonly used
semiconductors. They are insulators but at certain conditions such as when
combined with small amount of certain elements or when the temperature
is increased, they become conductors.
To gain better understanding about conductivity, we will use the model
called band theory, which states that delocalized electrons move freely
through “bands” formed by overlapping molecular orbitals. Let’s consider
magnesium in illustrating this concept.
The electron configuration of Mg is, 1s2 2s2 2p6 3s2. Each Mg atom has 2
valence electrons in the 3s orbital and the electrons in the 1s, 2s, and 2p
orbitals are localized.

Figure 1. Metallic bonding in magnesium: The positive nuclei are

surrounded by delocalized electron.

When the 3s and 3p orbitals overlap, delocalized molecular orbitals are

formed. The electrical conductivity of metals is caused by the movement
of electrons in these orbitals. (Figure 1).

Small piece of magnesium consists of large number of magnesium atoms,

so the number of molecular orbitals they form is also very large. The term “band” refers to the
molecular orbitals that are so closely spaced on the energy scale. The band of energy where all
of the valence electrons reside is called valence band. Above the valence band is called
conduction band, which is described as empty, has high energy level, delocalized molecular
orbitals formed by the overlap of the 3p, and receives electrons from the valence band (Figure
2).
 Figure 2. Illustration of valence and conduction bands in magnesium

The electrical conductivity properties of a metal depend upon its band gap.

For metals, the valence band and the conduction band are adjacent to each other (Figure 3. a),
so the amount of energy needed to travel the electrons from valence band to conduction band
is very small (negligible). This setting accounts for good electrical conductivity of metals.

For insulators, however, the gap between the valence band and the conduction band is large
(Figure 3. c). Hence, much more energy is needed to promote an electron into the conduction
band. Without this amount of energy, electrons cannot move freely. Therefore, insulators,
cannot conduct electricity

For semiconductors, (Figure 3. b) the energy gap between the valence and conduction band of
these solids is much smaller than that for insulators. If these materials are provided with right
amount of energy needed to excite electrons from the valence band into the conduction band it
will conduct electricity.

Figure 3. Energy gaps in conductor, semiconductor and insulator

Semiconductors are classified as intrinsic and extrinsic.

Intrinsic semiconductor, it is made of one type of element. When the

temperature increases, few electrons become free to move through the lattice, hence creating
“holes”. These holes can be imagined as positive charges which take the moving electrons. The
free electrons and the holes account for the electrical conductivity in the semiconductor.

Figure 4. (a)
Silicon atoms at absolute zero temperature (b) at higher
Temperature = Hole = electron

The energy band diagram of intrinsic semiconductor.

Figure 5. (a)intrinsic semiconductors at 0K (b) at temperature > 0 K

At 0 Kelvin, intrinsic semiconductors behave like insulators. When the temperature is increased,
some of the valence electrons moved to conduction band leaving holes in the valence band.
The electrons reached at the conduction band and the holes created at the valance band are
free to move. This phenomenon accounts for electrical conductivity of intrinsic semiconductors.

Extrinsic semiconductors - conduct electricity by adding small amounts of certain impurities to

the element. The process is called doping.
Extrinsic semiconductors are further classified as n-type semiconductor and p-type
semiconductor.

For n-type semiconductor (where n stands for negative), the impurities provide conduction
electrons, known as donor impurities. To illustrate this type of semiconductor, let us consider
phosphorus and see what happens when a trace amount of this element is added to solid
silicon. Silicon has four valence electrons while phosphorus has five. In solid silicon, each Si
atom is covalently bonded to four other Si atoms (Figure 6). When phosphorus atom forms
covalent bonds with silicon, there will be extra electron from phosphorus.

Figure 6. Silicon crystal doped with

phosphorus. N-type

When voltage is applied in solid, this extra electron can be removed from the phosphorus atom. The free
electron moves through the structure and serves as a conduction electron. Because small amount of
phosphorus has large number of atoms; it provides millions of free electrons for conduction.

Figure 7. Energy band diagram for n-type semiconductor

When pentavalent impurity is added in a semiconductor, a large number of free electrons are available in
the conduction band. These electrons did not form covalent bonds in the crystal, hence free to move.
For p-type semiconductor (where p stands for positive), it contains impurities that are electron
deficient, called acceptor impurities.

Let’s use boron to illustrate how this type of semiconductors work. Boron atom has three
valence electrons (1s22s22p1). When a boron atom is added in the silicon crystal, a single
vacancy in a bonding orbital is formed (Figure 8). This causes a valence electron from a nearby
silicon to jump into this vacant orbital. The vacancy created at that silicon atom will become a
“hole” which can then be filled by an electron from a nearby silicon atom, and so on. The
electrons and “holes” move in opposite directions and this account for the electrical
conductivity of this type of semiconductor.

Figure 8: Silicon crystal doped

with boron. P-type

When small amount of trivalent impurities is added in a semiconductor, millions of holes

formed in the valence band. Because “hole” referred to as positive, this is called p-type.

Figure 9. Energy band diagram for p-type semiconductor

In extrinsic semiconductors, the number of holes will not equal the number of electrons
jumped.
 The state of conductivity in p-type semiconductor is less than that of n-type. This is because the
number of electrons in conduction band in p-type is less than that of n-type.

BASIS OF
p TYPE SEMICONDUCTOR n TYPE SEMICONDUCTOR
DIFFERENCE
Group of Doping In p type semiconductor III group element is In n type semiconductor V group
Element added as doping element. element is added as doping
element.
Nature of Doping Impurity added creates vacancy of Impurity added provides extra
Element electrons (holes) called as Acceptor Atom. electrons and is known as Donor
Atom.
Type of impurity Trivalent impurity like Al, Ga, In etc. are Pentavalent impurity like P, As, Sb,
added added. Bi etc. are added.
Majority Carriers Holes are majority carriers Electrons are majority carriers
Minority Carriers Electrons are minority carriers Holes are minority carriers
Density of Electrons The hole density is much greater than the The electron density is much greater
and Holes electron density. than the hole density.
nh >> ne ne >> nh

Energy level The acceptor energy level is close to the The donor energy level is close to
valence band and away from the the conduction band and away from
conduction band. the valence band.
Movement of Majority carriers move from higher to lower Majority carriers move from lower
Majority carriers potential. to higher potential.

Problems:
State whether silicon would form n-type or p-type semiconductors
with the following elements:
a. Ga
b. Sb
c. In