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Basic Semiconductors
(Properties & Growth)
Solid State Device - a component whose operation
depends on the control of electrical or magnetic
phenomena in solids, such as a transistor, diode, or

We will concentrate on semiconductor devices.
What distinguishes semiconductors?
- resistance/resistivity
- crystalline structure

The resistance of a bar of material with dimensions L,
W, t and resistivity is:

metals: < 10
insulators: >10
semiconductors: 10
O-cm < < 10
Properties of Semiconductor
SC is a group of materials having electrical conductivity
intermediate between metals and insulators.

Conductivity can be varied by order of magnitude with
changes in temperature, optical excitations and impurity
Materials are found in column IV and neighboring
columns of periodic table
Energy band gap of SC materials is too different from
conductors and insulators

Different semi conducting materials have different
band gap. This property is specifically used in
constructing light emitting diodes and lasers of
different wavelengths over a broad range of
infrared and visible region of spectrum.

The band gap and consequently electronic and
optical properties of SC materials are strongly
affected by the impurities which may be added in
precisely controlled amounts.

As slight variation in the electronic structure due to
impurities can drastically change the properties of SC

Study of electronic and crystal
structure is very important
Group IV elements
e.g., Si, Ge etc.
Group III-V compounds
Group IIVI compounds
Semiconductors are found in columns II-VI
of the periodic table. Why is silicon so
popular if there are so many to choose
elemental semiconductors: Si, Ge
compound semiconductors: GaAs, InP
ternary semiconductors: AlGaAs, HgCdTe
quaternary semiconductors: InGaAsP, InGaAlP
Common semiconductor materials: (a) the portion of the
periodic table where semiconductors occur; (b) elemental and
compound semiconductors.
Elemental Semiconductors:

Si and Ge are the most commonly used used SC, initially for
diodes and transistors

Now Si is used for majority of rectifiers, transistors and ICs

Compound Semiconductors:

Mostly used in high speed devices requiring the emission or
absorption of light

Practical Examples
Light emitting Diode:

III-V Compounds like GaN, GaP, GaAs are common light
emitting diodes (LEDs)

TV Screen Fluorescent Materials:

ZnS, II-VI compunds

Light Detectors:
InSb, CdSe, PbTe, HgCdTe light detectors
Si and Ge infrared and Nuclear Radiation detectors
Gunn Diodes:

Microwave devices made of GaAs and InP

Semiconductor Lasers:

GaAs, AlGaAs and other ternary and quaternary compounds
Some characteristics of semiconductors

1) melting temperature
2) relative abundance/cost
3) band gap (light generation/absorption)
4) ease of doping
5) ease of growth
6) ease of processing
7) performance
Crystalline solids (Periodic structure):

A solid in which the atoms are arranged in periodic fashion mostly
single crystals

Amorphous Solids:

Solids in which there is no periodic structure like glass

Polycrystalline materials:

Solids composed of many small regions of single crystal materials
Figure 11
Three types of solids, classified according to atomic arrangement:
(a) crystalline and (b) amorphous materials are illustrated by
microscopic views of the atoms, whereas (c) polycrystalline structure is
illustrated by a more macroscopic view of adjacent single-crystalline
regions, such as (a).
Lattice: Periodic arrangement of atoms in a crystal is
called LATTICE Lattice is defined as a set of points in which
all the points are connected with some atoms or molecules.

Basis: Atoms, set of atoms or molecules placed at every
point of lattice are known as basis

Crystal Lattice + Basis

Basis Vectors: For three dimensional lattice the set of
three orthogonal vectors a, b, c which can form a representation
of any point of lattice are known as basis vectors

Figure 12
A two-dimensional lattice showing
translation of a unit cell by
r = 3a + 2b.
Primitive unit cell: A smallest possible cell in the periodic
structure is know as primitive cell.

Unit Cell: A unit cell is a volume that is repeated throughout
the crystal. A unit cell need not to be primitive all the time

-A two-dimensional lattice showing translation of a unit cell by
r = 3a + 2b.
a and b are known as basis vectors

- Points within the lattice are indistinguishable if the vector
between the points is given by
r = pa + qb + sc

Where p, q, s are integers
Figure 13
Unit cells for three types of cubic lattice
Figure 14
Packing of hard spheres in an fcc lattice.
Assuming the max packing (all nearest neighbors touching each other)
Consider one face, a is the length of side of cube (lattice constant)
a a
c a

| +

| = = =
The radius of the spheres =
each corner contributes 1/8
(8 corners) 1 sphere
each face contributes 1/2
(6 faces) 3 spheres
atoms/cell = 4
Volume of each sphere = t a
/ 24
Max. fraction of filled cells =
(No. of spheres vol. of each sphere)
total volume of each cell

= (4 t a
) / 24

= t 2
= 74 % filled
Planes and Directions
Specify the planes and directions within the lattice
Use a set of three integers to describe the position or direction of a
plane within the lattice

1. Find the intercepts of the plane with the crystal axes and express
these as integral multiple of basis vectors (the plane can e move in
or out from origin retaining its orientation until such an integral
intercept is discovered)
2. take the reciprocal of these intercepts and reduce it to smallest set
of integers h, k, and l, which have the same ratio to each other as
three reciprocals
3. Label the planes (hkl)

h, k, and l called miller indices
Figure 15
A (214) crystal plane.
Figure 16
Equivalence of the cube faces ({100} planes) by
rotation of the unit cell within the cubic lattice.
Miller indices in cubic lattice:
Looking at three faces miller inices (hkl) for different faces
Are hkl for blue upper face = (001)
hkl for dark grey face = (100)
hkl for light grey front face = (010)

Now due to symmetry of the cubic structure which is
rotationally invariant all these directions specify the same

All such face are described by hkl in braces {hkl}
{100} describes the set of six faces of cube
Specified with three integers with the same relationship
as the components of vector in that direction

vector describing the upper plane is 0i + 0j + k or [001]
describe the direction of plane (001)
[010] (010)
[100] (100)

For cubic structure all these directions are equivalent and
described by <100>

<100> is perpendicular to {100} for cubic lattice

Figure 17
Crystal directions in the cubic lattice.
Basic lattice structure for majority of semiconductors is diamond
Characteristic os Si and Ge
For compound semiconductors basic structure is diamond but different
atoms are placed at alternate sites.

The diamond lattice is thought of as an fcc structure with an
extra atom placed at a/4 + b/4 + c/4 from each of the fcc
Two interpenetrating fcc lattices with co-ordinates shifted
by (1/4,1/4 ,1/4)
Figure 18
Diamond lattice structure: (a) a unit cell of the diamond lattice constructed by
placing atoms from each atom in an fcc; (b) top view (along any <100>
direction) of an extended diamond lattice. The colored circles indicate one fcc
sublattice and the black circles indicate the interpenetrating fcc.
Diamond lattice:
If all the atoms are similar on both interpenetrating lattices
e.g, Si, Ge then the lattice is known as diamond lattice

Zincblend Lattice:
If one sublattice in fcc structure is of Ga and other sublattice
is formed by As then the structure is known as Zincblend lattice. Most of the
compound semiconductor have this kind of structure except few from group
II-VI compounds

Wurtzite lattice:

Few compounds from II-VI form wurtzite lattice

Example 1-3

Calculate the densities of Si and GaAs from the lattice
constants (appendix III), atomic weights, and avogadros
number. Compare the result with densities given in appendix
III. The atomic weight of Si, Ga, and As are 28.1, 69.7 and
74.9 respectively

For Si: a = 5.43 10
cm, 8 atoms/cm

For GaAs: a = 5.65 10
cm, 4 each As and Ga atoms/cm

For III-V compounds, mixture of elements on each of two
interpenetrating lattices of zincblend structure could be varied
in any composition

As refers to a ternary alloy in which one of the
sublattice will be occupied partly by Al and partly by Ga atoms,
whereas the other sublattice will be entirely filled by As atoms
Growth of crystals over entire composition range from x = 0
to x = 1.
Compounds f wide range of properties can be grown.

Figure 19
Diamond lattice unit cell, showing the four nearest neighbor structure. (From
Electrons and Holes in Semiconductors by W. Shockley, 1950 by Litton
Educational Publishing Co., Inc.; by permission of Van Nostrand Reinhold
Co., Inc.)
Bulk Crystal Growth
1948 Invention of transistor

1950 pure single crystal Si

Recently Si crystals grown for devices have impurity
level as less than 1 part in ten billion
Starting Materials
+ 2C Si + 2CO ~ 1800

Sand + coke MGS (metallurgical grade Si)
~ 100 1000 ppm impurities like Fe, Al etc.

MGS is refined to EGS (electronic grade Si)
Impurity level is 1ppb (1ppb = 5 10
Si + 3HCl SiHCl
+ H
is separated through fractional distillation

+ 2H
2Si + 6HCl

Figure 110
Pulling of a Si crystal from the melt (Czochralski method): (a) schematic
diagram of the crystal growth process; (b) an 8-in. diameter, <100> oriented Si
crystal being pulled from the melt. (Photograph courtesy of MEMC Electronics
Czochralski method (Growth of single crystal Ingots):
EGS is melted in quartz lined graphite crucible by resistive
Polycrystalline EGS to single crystal Si ingots
This technique is used to grow Si, Ge and other compound
e.g., GaAs, As is volatile, layer of molten B
is floated on
the molten to prevent vaporization

Technique is known as liquid encapsulated Czochralski
(LEC) growth
Figure 111
Silicon crystal grown by the Czochralski method. This large single-crystal ingot
provides 300 mm (12-in.) diameter wafers when sliced using a saw. The ingot
is about 1.5 m long (excluding the tapered regions), and weighs about 275 kg.
(Photograph courtesy of MEMC Electronics Intl.)
single crystal ingots are grounded mechanically
grounded cylinder
Most ingots are grown along <100> direction
From si Ingots, Si wafers are cut by using the diamond
tipped inner-hole blade saw to get ~ 775 micron thick
The si wafers are then rounded along the edges.
Finally wafers undergo chemical-mechanical polishing
using a slurry of fine SiO
particles in a basic NaOH
solution to give the front surface a mirror like finish
the wafers are ready for IC circuit fabrication.
Figure 112
Steps involved in manufacturing Si wafers: (a) A 300 mm Si cylindrical ingot, with a
notch on one side, being loaded into a wire saw to produce Si wafers; (b) a technician
holding a cassette of 300 mm wafers. (Photographs courtesy of MEMC Electronics Intl.)

To change the electronic properties of the Si, we add
intentional impurities or dopants to molten Si
Distribution co-efficient k
, which is the ratio of the
concentration of the impurity in the solid C
to the
concentration in the liquid C
at equilibrium

= C
/ C

This is the function of the material, the impurity, the
temperature of the solid-liquid interface and the growth

Epitaxial Growth
The technique of growing an oriented single crystal layer on a
substrate wafer is called epitaxial growth.
For the device applications we grow a thin layer on a wafer
(substrate) of compatible crystal.
The substrate could be same material or some other material
with same lattice structure
Substrate is acting like seed crystal
The growing layer will maintain the crystal structure of
Epitaxial growth can be performed at temperature below the
melting temperature of substrate
Growth Techniques
Chemical Vapor deposition (CVD)
Liquid phase epitaxy (LPE)
Vapour phase epitaxy (VPE)

Molecular beam epitaxy (MBE)
Lattice matching in epitaxial growth
For high quality single crystals, there should be lattice
matching of the substrate and the growth layer.
If it is desirable to obtain epitaxial layers that differ from the
substrate, then we call it heteroepitaxy
Some advanced techniques allow the growth of very thin
) layers of lattice mismatched crystal, resulting in
compression or tension along the surface plane. Such a layer is
a called pseudomorphoic.
For mismatched lattices if thickness of the layer t < t
critical thickness, then formation of dislocations will start
known as misfit dislocations
Figure 113
Relationship between band gap and lattice constant for alloys in the InGaAsP and AlGaAsSb systems. The
dashed vertical lines show the lattice constants for the commer-cially available binary substrates GaAs and
InP. For the marked example of In x Ga 1 x As, the ternary composition x 0.53 can be grown lattice-
matched on InP, since the lattice constants are the same. For quaternary alloys, the compositions on both the
III and V sub-lattices can be varied to grow lattice-matched epitaxial layers along the dashed vertical lines
between curves. For example, In x Ga 1 x As y P 1 y can be grown on InP substrates, with resulting
band gaps ranging from 0.75 eV to 1.35 eV. In using this figure, assume the lattice constant a of a ternary
alloy varies linearly with the composition x.
Figure 114
Heteroepitaxy and misfit dislocations. For example, in heteroepitaxy of a SiGe
layer on Si, the lattice mismatch between SiGe and Si leads to compressive
strain in the SiGe layer. The amount of strain depends on the mole fraction of
Ge. (a) For layer thicknesses less than the critical layer thickness, t
pseudomorphic growth occurs. (b) However, above t
, misfit dislocations form
at the interface which may reduce the usefulness of the layers in device
Liquid Phase Epitaxial Growth
Fig. Liquid-phase epitaxial growth of AlGaAs and GaAs layers on a substrate:
(a) cross section of the sample in contact with a Ga-rich melt containing Al
and As; (b) carbon slider used to move the GaAs substrate between various
melts. In this case, two pockets are provided, containing melts for AlGaAs
and GaAs growth. The GaAs substrate on the slider is moved first into the
AlGaAs growth chamber; after growth of this layer (shown in part a), the
excess melt is wiped off as the slider moves the substrate to the next growth
Figure 115
A barrel-type reactor for Si VPE. These are atmospheric pressure systems.
The Si wafers are held in slots cut on the sides of a SiC-coated graphite
susceptor that flares out near the base to promote gas flow patterns
conducive to uniform epitaxy.
Vapour Phase Epitaxy:

+ 2H
Si + 4HCl

Figure 116
Crystal growth by molecular beam epitaxy (MBE): (a) evaporation cells inside a
high vacuum chamber directing beams of Al, Ga, As, and dopants onto a GaAs
substrate; (b) scanning electron micrograph of the cross section of an MBE-grown
crystal having alternating layers of GaAs (dark lines) and AlGaAs (light lines).
Each layer is four monolayers (4 x a/2 = 11.3) thick. (Photograph courtesy of Bell
Molecular Beam epitaxy