NCHE 674

APPLIED MATERIALS CHEMISTRY

 2
Study
Unit
BASED ON BAND STRUCTURE

After completion of this Study Unit you should be able to:

• identify different classification of solids based on band

structures;

• discuss chemical and physical properties of solids on the

basis of band structures; and

• discuss the application of solids based on band structures.

 Classification of solids- band structure

There are three categories of solids, based on their band structure

(conducting properties):
• conductors
• semiconductors Conduction band
• insulators
BAND GAP

Valence band

• Insulators have a large energy gap

– electrons can’t jump from valence to conduction bands
– no current flows
• Conductors (metals) have a very small (or nonexistent) energy gap
– electrons easily jump to conduction bands due to thermal excitation
– current flows easily
• Semiconductors have a moderate energy gap
– only a few electrons can jump to the conduction band leaving
“holes”
– only a little current can flow
 Conducting properties of solids

• The band structures of insulators and Conduction Band

semiconductors resemble each other

qualitatively. Normally there exists in
both insulators and semiconductors a
filled energy band (referred to as the Valence Band
valence band) separated from the
next higher band (referred to as the
conduction band) by an energy gap. Conductor Semiconductor Insulator

• If this gap is at least several electron  This separation of the valence and
volts, the material is an insulator. It is conduction bands determines the electrical
too difficult for an applied field to properties of the material
overcome that large an energy gap,
 For energy gaps smaller than about 1
and thermal excitations lack the energy electron volt, it is possible for enough
to promote sufficient numbers of electrons to be excited thermally into the
electrons to the conduction band. conduction band, so that an applied electric
field can produce a modest current.

 Smaller energy gaps create semiconductors

 What are semiconductors
• Semiconductors are materials which have a conductivity
between conductors (generally metals) and nonconductors
or insulators (such as most ceramics). Semiconductors can be pure
elements, such as silicon or germanium, or compounds such as gallium
arsenide or cadmium selenide.

– generally crystalline in structure for devices

• In recent years, however, non-crystalline semiconductors have
become commercially very important

Polycrystalline amorphous crystalline

 Electrical Resistivity and Conductivity of semiconductors

The electrical conductivity at room

temperature is quite different for
each of these three kinds of solids

Metals and alloys have the highest

conductivities followed by
semiconductors
and then by insulators

 Low resistivity => “conductor”

 High resistivity => “insulator”
 Intermediate resistivity =>
“semiconductor”

-conductivity lies between that of

conductors and insulators
 Resistivity vs. Temperature

(a) Resistivity versus temperature for a typical conductor. Notice the linear rise
in resistivity with increasing temperature at all but very low temperatures.
(b) Resistivity versus temperature for a typical conductor at very low
temperatures. Notice that the curve flattens and approaches a nonzero
resistance as T → 0.
(c) Resistivity versus temperature for a typical semiconductor. The resistivity
increases dramatically as T → 0.
 Temperature and Resistivity

• When the temperature is increased from T = 0, more and more

atoms are found in excited states.

• The increased number of electrons in excited states explains the

temperature dependence of the resistivity of semiconductors.

Only those electrons that have jumped from the valence band to
the conduction band are available to participate in the
conduction process in a semiconductor. More and more
electrons are found in the conduction band as the temperature is
increased, and the resistivity of the semiconductor therefore
decreases.
 Band Theory of Solids

• In order to account for decreasing resistivity with

increasing temperature as well as other properties of
semiconductors, a new theory known as the band
theory is introduced.

• The essential feature of the band theory is that the

allowed energy states for electrons are nearly
continuous over certain ranges, called energy bands,
with forbidden energy gaps between the bands.
 Electronic Properties of semiconductors

 There are 2 types of mobile charge-carriers in a

semiconductor:
– Conduction electrons are negatively charged;
– Holes are positively charged.

 The concentration of conduction electrons and holes in a

semiconductor can be modulated in several ways:
1. by adding special impurity atoms (dopants)
2. by applying an electric field
3. by changing the temperature
4. by irradiation
 SILICON

• Silicon is a semiconductor material.

• Pure Si has a relatively high electrical resistivity at room temperature
• Atomic density: 5 x 1022 atoms/cm3
• Si has four valence electrons. Therefore, it can form covalent bonds with
four of its nearest neighbors.
• When temperature goes up, electrons can become free to move about the
Si lattice.
 Electron-Hole Pair Generation
When a conduction electron is thermally generated, a “hole” is also generated.
A hole is associated with a positive charge, and is free to move about the Si lattice
as well.
 Impurity Semiconductor
• It is possible to fine-tune a semiconductor’s properties by adding a small
amount of another material, called a dopant, to the semiconductor
creating what is a called an impurity semiconductor.

• As an example, silicon has four electrons in its outermost shell (this

corresponds to the valence band) and arsenic has five.
Thus, while four of arsenic’s outer-shell electrons participate in covalent
bonding with its nearest neighbors (just as another silicon atom would),
the fifth electron is very weakly bound.
It takes only about 0.05 eV to move this extra electron into the
conduction band.

• The effect is that adding only a small amount of arsenic to silicon greatly
increases the electrical conductivity.
 Doping

Semiconductors are classified in to P-type and N-type semiconductor

P-type: A P-type material is one in which holes are majority carriers

i.e. they are positively charged materials (++++)

N-type: A N-type material is one in which electrons are majority charge

carriers i.e. they are negatively charged materials (-----)

For the p-type semiconductor, its Fermi level is near to the VB, while
the Fermi level of n-type is located near to the CB.
 Doping (N type)
• Semiconductors can be “doped” with other elements to
change its electrical properties.

• For example, if Si is doped with phosphorus (P), each P atom

can contribute a conduction electron, so that the Si lattice has
more electrons than holes, i.e. it becomes “N type”:

Notation:
n = conduction electron
concentration

• The new phosphorus energy levels just below the conduction band are
called donor levels because an electron there is easily donated to the
conduction band.
 Doping (P type)

• If Si is doped with Boron (B), each B atom can contribute a hole, so

that the Si lattice has more holes than electrons, i.e. it becomes “P
type”:

Notation:
p = hole concentration
 Acceptor levels p-Type semiconductors

• Consider what happens when indium is added to silicon.

– Indium has one less electron in its outer shell than silicon. The result is one
extra hole per indium atom. The existence of these holes creates extra
energy levels just above the valence band, because it takes relatively little
energy to move another electron into a hole

– Those new indium levels are called acceptor levels because they can
easily accept an electron from the valence band. Again, the result is an
increased flow of current (or, equivalently, lower electrical resistance) as
the electrons move to fill holes under an applied electric field
• It is always easier to think in terms of the flow of positive charges
(holes) in the direction of the applied field, so we call this a p-type
semiconductor (p for positive).
– acceptor levels p-Type semiconductors
• In addition to intrinsic and impurity semiconductors, there are many
compound semiconductors, which consist of equal numbers of two
kinds of atoms.
Summary of Charge Carriers (Si)
 DIODES

Electronic devices created by bringing together a p-type and n-type region

within the same semiconductor lattice. Used for rectifiers, LED etc

It is represented by the following symbol, where the

arrow indicates the direction of positive current flow.
 Forward Bias and Reverse Bias

Forward Bias : Connect positive of the Diode to positive of supply…negative

of Diode to negative of supply

Reverse Bias: Connect positive of the Diode to negative of supply…

negative of diode to positive of supply.

Characteristics of Diode
 Diode always conducts in one direction.
 Diodes always conduct current when “Forward Biased” ( Zero resistance)
 Diodes do not conduct when Reverse Biased (Infinite resistance)
 Light Emitting Diodes

• An important kind of diode is the light-emitting diode (LED).

Whenever an electron makes a transition from the conduction band to
the valence band (effectively recombining the electron and hole) there
is a release of energy in the form of a photon. In some materials the
energy levels are spaced so that the photon is in the visible part of the
spectrum. In that case, the continuous flow of current through the LED
results in a continuous stream of nearly monochromatic light.

Schematic of an LED. A photon is released as an electron falls from the conduction band
to the valence band. The band gap may be large enough that the photon will be in the
visible portion of the spectrum. 21
 Photovoltaic Cells
• An exciting application closely related to the LED is the solar cell, also known as the
photovoltaic cell. Simply put, a solar cell takes incoming light energy and turns it into electrical
energy.

• A good way to think of the solar cell is to consider the LED in reverse. A pn-junction diode can
absorb a photon of solar radiation by having an electron make a transition from the valence band
to the conduction band. In doing so, both a conducting electron and a hole have been created. If
a circuit is connected to the pn junction, the holes and electrons will move so as to create an
electric current, with positive current flowing from the p side to the n side. Although the efficiency
of most solar cells is low, their widespread use could potentially generate significant amounts of
electricity. Remember that the “solar constant” (the energy per unit area of solar radiation
reaching the Earth) is over 1400 W/m2, and more than half of this makes it through the
atmosphere to the Earth’s surface. There has been tremendous progress in recent years toward
making solar cells more efficient.

22
 Transistors

• Another use of semiconductor technology is in the fabrication of

transistors, devices that amplify voltages or currents in many kinds of
circuits. The first transistor was developed in 1948 by John Bardeen,
William Shockley, and Walter Brattain (Nobel Prize, 1956). As an example
we consider an npn-junction transistor, which consists of a thin layer of p-
type semiconductor sandwiched between two n-type semiconductors. The
three terminals (one on each semiconducting material) are known as the
collector, emitter, and base. A good way of thinking of the operation of the
npn-junction transistor is to think of two pn-junction diodes back to back.

(a) In the npn transistor, the base is a p-type material, and the emitter and collector are n-type. (b) The
two-diode model of the npn transistor. (c) The npn transistor symbol used in circuit diagrams. (d) The
pnp transistor symbol used in circuit diagrams.
23
 Types of heterojunctions

A heterojunction is generally defined as the interface between two regions of different

semiconductors with unequal band structure, and create interfacial band alignments.

Based on the different energy levels of the CB and VB of the two semiconductors, the
formed heterojunction can be classified into several types:

Type I (those with a straddling alignment)

Type II (those with a staggered alignment)
 Type I, II and III heterojunctions

a straddling band alignment.

(b) Type II heterojunction

(a) Type I heterojunction:
• The VB and CB of semiconductor 1 • Type II heterojunctions have
are respectively lower and higher unique staggered band structures
than those of semiconductor 2. between the two semiconductors

• Therefore, when the holes and electrons gain

energy under light irradiation, photogenerated
holes can migrate from the VB of semiconductor 1 (c) Type III heterojunction
to the VB of semiconductor 2, while photoinduced
electrons can transfer from the CB of
semiconductor 1 to the CB of semiconductor 2.
 p-n heterojunctions
Although the Type II heterojunction can ideally separate charge pairs in space, the
achieved improvement in the electron-hole separation across the Type II heterojunction
is not sufficient to overcome the ultrafast electron-hole recombination on the
semiconductor.

In regard of this, the concept of constructing a p-n heterojunction photocatalyst is put

forward, which is able to provide an additional electric field to accelerate the electron-
hole pairs transfer.