EBB 215 Semiconductor

Materials
Dr. Khatijah Aisha Yaacob
mraisha@usm.my
Room no. : 2.09

School of Materials & Mineral Resources Engineering,

Engineering Campus, Nibong Tebal, Pulau Pinang

Content:
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Introduction
Semiconductor
Atomic model
Bonding forces in solid
Atom and Crystal in semiconductor
Atomic structure of Si and Ge
Crystal structure of Si and Ge
Intrinsic semiconductor
Extrinsic semiconductor

Bonding in solid
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Extend the Bohr model of the hydrogen atom

to the hydrogen ion, H+ & the hydrogen
molecule,H2.
By isolated, nuclei are sufficient far apart that
do not influence each other

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When the nuclei are allowed to approach each

other, an electron would be influenced by
both nuclei.
As the nuclei are brought together, the upper
energy levels merge and electrons in those
levels are shared between the atoms.

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The nuclei are sufficiently close together that all

energy levels are shared. Since the lowest level is
usually the only occupied level for hydrogen, if it
is occupied by two electrons H2 molecule is
stable.

Covalent bonding in crystalline solid

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The valence and conduction bands, in figure below, are common to

all the atom in the crystal.
Electron in these two lower energy shell are tightly bound to their
respective atom and play no role in the operation of devices.
The third shell of atomic silicon splits into two bands in crystalline Si.
The lower of these bands, valence band, contains four electron.
The four vacant state in the third shell of Si atom called conduction
band.

Electron affinity, Ionization and Band Gap

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The lowest energy in the conduction band is

designated as Ec, the conduction bans edge.
The highest energy in the valence band is denoted
Ev, the valance band edge.
The ionization energy,, is defined as the minimum
energy require to excite an electron from top of the
valance band in the crystal to the vacuum level.
The electron affinity, , is defined as the energy
difference between the vacuum level and the vacant
state of lower energy, in this case Ec.
Band Gap is the min energy required to excite an
electron from the VB to CB.

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Ionization energy = Evac Ev

The electron affinity = Evac Ec
Band gap Eg = Ec - Ev
= Eg +

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Bonding force in semiconductor

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Objective : Discuss differences in atomic bonding between

various solids.
A solid is formed by the chemical bonding of a large
number of atoms together.
Observation from the periodic structure of chemical
elements, is that elements having their shell complete are
chemically inert.
This means that a stable e configuration is one which has
its shells complete
The attractive forces differ in nature from one class of
materials to another, and this difference can be understood
on the basis of the shell structure of atoms.

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The general tendency is that atoms will give up e,

receive e from other atoms, or share e with other
atoms so that they may achieve individually or
collectively a stable e configuration.
According to the different ways in which atoms
achieve a stable configuration, the bonding
between atoms in a crystal is commonly classified
into 4 distinct types: the ionic bond, the covalent
bond, the metallic bond & the van der Waals bond.

Covalent bond
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The covalent bond is formed by the sharing of e between

the bonded atoms.
This sharing results from the overlap of the bonding orbital,
and the shared e can come either from one or from all the
atoms that take part in the bonding.
The covalent bonds is a bond between the atoms of the
same polarity; hence, it is also known as a homopolar bond.
Eg, the covalent bonds of crystal formed by the group IV
elements C, Ge & Si.
The covalent bond is very strong, and the materials formed
have high melting and boiling points.
The covalently bonded substances are relatively poor
conductors of electricity at normal temperature.

Silicon
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Let us consider Si (Z=14)

Electronic configuration 1s22s22p63s23p2
When Si atoms are brought together and share electrons with 4
other Si atoms.
The outer 3s3p shell (valance shell) is then full.

EXAMPLES: COVALENT BONDING

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H2
H
2.1
Li
1.0

Na
0.9

C(diamond)
SiC

Be
1.5

K
0.8

Mg
1.2
Ca
1.0

Rb
0.8

Sr
1.0

Cs
0.7

Ba
0.9

Fr
0.7

Ra
0.9

column IVA

H2O

Ti
1.5

Cr
1.6

Fe
1.8

F2
He
O
2.0

C
2.5

Ni
1.8

Zn
1.8

Ga
1.6

Si
1.8
Ge
1.8

As
2.0

Sn
1.8
Pb
1.8

GaAs

F
4.0

Ne
-

Cl
3.0

Ar
Kr
-

Br
2.8
I
2.5
At
2.2

Xe
Rn
-

Cl2

Ionic bond
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Formed between electronegative and electropositive elements.

Electropositive atom loses its valence e and become positively
charge ion.
The lost e are gained by the electronegative elements which
becomes negatively charge.
After this transfer of e, both ions have 8 e in their valence orbital
and are hold together by the electrostatic force of attraction
between negative and positive charges.
The ionic bond is fairly strong, and the ionic substances are usually
hard and have high melting and boiling points.
Since the valence e are rather tightly bound to their respective
ions, the movement of these e under an applied electric filed is
not possible and most ionic substances are insulators at room T.
At higher T, the ions themselves becomes mobile, giving rise to
ionic conduction.

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Fig. : Electron configuration in NaCl.

An e- transfer from Na to Cl results
in closed-shell configuration in both
Na+ and Cl- ions. The bonding in
NaCl is due to Coulomb attraction
between Na+ and Cl- ions.

Eg: Alkali metals such as sodium have a single valence e

outside closed shell, whereas halogens such as chlorine
are one e short of having a complete outer shell
An e transfer from alkali metal X to the halogen Y result in
both X+ and Y- ions.
eg Na+ - 1s22s22p6
Cl- - 1s22s22p63s23p6

One can use this tendency to satisfy the

noble gas configuration ns2np6(octet
rule)

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Semiconductor compound
Instead of every atom being of the same element, the crystal may consist
of regular arrangement of different element.
Eg: GaAs
Same general structure as Si, excepts that alternate atoms are gallium and
the one between them is arsenic.
Ga is from group III 3 e at the outer shell
As is from V has 5 e at outer shell.
These two atoms are neighbors, they can each fill their outer shell with 8 e
by sharing e The still spend most of their time in the region between the nuclei, but
now is slightly difference
Since As nucleus has grater +ve charge, the e- tends to be attracted towards
the As side of bond As slightly negatively and ionizing Ga atom is slightly
positively.
The III-Vs mostly covalent but partially ionic
The II-VI more ionic and less covalent (eg: CdTe)

EXAMPLES: IONIC BONDING

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Predominant bonding in Ceramics

NaCl
MgO
CaF2
CsCl

H
2.1

Li
1.0

Be
1.5

Na
0.9

Mg
1.2

K
0.8

Ca
1.0

Rb
0.8

He
-

O
F
3.5 4.0
Cl
3.0

Ne
-

Br
2.8

Kr
-

Sr
1.0

I
2.5

Cs
0.7

Ba
0.9

At
2.2

Xe
Rn
-

Fr
0.7

Ra
0.9

Ti
1.5

Cr
1.6

Give up electrons

Fe
1.8

Ni
1.8

Zn
1.8

As
2.0

Acquire electrons

Ar
-

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.

Partially Ionic Compounds

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From the last lecture, if two atoms forming a bond have

differing electronegativities, they will form a bond having
partial ionic character.

Q: But where is the dividing line between ionic bonding

and polar covalent bonding?
Ans: In the end, fully ionic bonding is probably never
achieved, and all ionic bonds can be considered polar
covalent, with varying degrees of ionic character.

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Covalent, (Si, Ge )

Ionic (NaCl, ZnS)

Increase ionic character

Polar covalent, (GaAs)

Metallic bond
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Is formed between electropositive elements.

The valence orbit of all metal atoms is either an s or p
subshell.
The size of the outer shells in these atoms is rather large,
and the valence e are not as tightly bound to the nucleus
as in nonmetal.
Such as the one e in 2s for Li and one e in 3s for Na

Eg: Sodium atoms are brought into close proximity, the

valence e interact in a way similar to that covalent bond
When a third sodium atom is brought into close
proximity with the first two, the valence e can also
interact & continue to form a bond.

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Solid sodium has BCC structure, so each atom has eight

nearest neighbours with each atom sharing many
valence e.
We can think of the positive metallic ions as being
surrounded by sea of negative e, the solid being held
together by the electrostatic forces.
These free e account for all the important properties of
the metals a good conductor.

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In class activity
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For the following semiconductor materials,

indicate to what degree you expect covalent
or ionic bonding, and why:
Ge
GaP
InGaAsP
HgCdTe