Course outline

Crystal Properties & Growth of

Semiconductors

Atoms & Electrons

Energy Bands & Charge Carrier in
Semiconductors

Junctions

Field-Effect Transistors

Bipolar Junction Transistors

Optoelectronic Devices

Integrated Circuits

Solid State Electronics (EE 6201)

Course Outline

By Dr. Yaseer A. Durrani

UET, Taxila
2

Books

Grading policy

Course Book

Solid State Electronic Devices, Ben G. Streetman, Sanjay K. Banerjee, 6th

Ed. Prentice Hall, Upper Saddle, NJ 07458, 2000ISBN # 013149726-X

Reference Books
Fundamental of Semiconductor Devices, Betty L. Anderson, Richard L. Anderson, McGraw Hill
Introduction to Solid State Physics, Charles Kittel, Wiley Pub. (6th Ed.)
Semiconductor Device Fundamentals, Robert Pierret, Addison-Wesley, 1996, ISBN
#0201543931
Solid State Electronic Devices, D.K. Bhattacharya, R. Sharma
Solid-State Physics for Electronics, Andre Moliton

Assignments
Quizzes
Mid
Final

08%
12%
30%
50%

Crystallography

Basic Knowledge of Elementary Crystallography is Essential for Solid
State Physicists!!!

Crystallography is the branch of science that deals with geometric
description of crystals & their internal arrangements. It is the science of
crystals & math used to describe them

Solid State Electronics (EE 6201

6201))

Crystals symmetry has a profound influence on many of its properties

Crystal structure should be specified completely, concisely &
unambiguously

Structures are classified into different types according to the symmetries
they possess

In this course, we only consider solids with simple structures

Crystal Properties & Growth of

Semiconductors
By Dr. Yaseer A. Durrani
UET, Taxila

States of Matter

Matter: has mass, occupies space

Mass: has weight, resistance to acceleration

Solids: has volume, shape

Liquids: has volume, no fixed shape, Flows
Gases: No volume, no shape. Takes volume & shape of its container
Plasma: No volume, no shape. Composed of electrically charged particles,
plasmas are electrically conductive, produce magnetic fields & electric
currents, & respond strongly to electromagnetic forces

Solids

Particles (ions, atoms, molecules) are packed closely together. Forces
between particles are strong enough so that particles cannot move
freely but can only vibrate. As a result, a solid has a stable, definite
shape, & definite volume. Solids can only change their shape by force,
as when broken or cut

Solids can be transformed into liquids by melting, & liquids can be
transformed into solids by freezing. Solids can also change directly into
gases through the process of sublimation

Solids can be classified under criteria based on: atomic arrangements,

electrical properties, thermal properties, chemical bonds etc.
Using electrical criterion: Conductors, Insulators, Semiconductors
Using atomic arrangements: Crystalline, Amorphous, Polycrystalline
Long term atomic arrangement determines the crystal type. Properties such as
electrical, mechanical & optical are intimately tied to crystal type

Types of Solids

Ionic Crystals or Solids

Lattice points occupied by cations and anions

Held together by electrostatic attraction
Hard, brittle, high melting point
Poor conductor of heat and electricity

CsCl

ZnS

CaF2

Molecular Crystals or Solids

Solids

Lattice points occupied by molecules

Held together by intermolecular forces
Soft, low melting point
Poor conductor of heat and electricity
Resistivity vs Temperature

Network or Covalent Crystals or Solids

(a) Linear rise in resistivity with increasing temperature at all but

very low temperatures
(b) Curve flattens & approaches a nonzero resistance as T 0
(c) Resistivity increases dramatically as T 0

Lattice points occupied by atoms

Held together by covalent bonds
Hard, high melting point
Poor conductor of heat and electricity

diamond

graphite

Metallic Crystals or Solids

Lattice points occupied by metal atoms

Held together by metallic bond
Soft to hard, low to high melting point
Good conductor of heat and electricity

Materials

10

Solid-State Electronic Materials

Solid electronic materials based on their conducting properties fall into
three categories:
Insulators
Resistivity () > 105 -cm
Semiconductors
10-3 < < 105 -cm
Conductors
< 10-3 -cm

Elemental semiconductors are formed from a single type of atom,
typically Silicon

Compound semiconductors are formed from combinations of column III
and V elements or columns II and VI

Germanium was used in many early devices

Silicon quickly replaced Germanium due to its higher bandgap energy,
lower cost, and is easily oxidized to form silicon-dioxide insulating
layers

11

12

Solid-State Electronic Devices

Semiconductor

Deals with circuits or devices built entirely from solid materials, in which
electrons, or other charge carriers, are confined entirely within solid material
Deals with circuit or devices involving theory of flow of electrons confined
within solid material. This includes devices like Diodes, Transistors etc.

Solid-state can include Crystalline, Polycrystalline, Amorphous solids refers to:

Electrical conductors, insulators, semiconductors (building material is most
often crystalline semiconductor)
Common solid-state devices include: Integrated circuit (IC), light-emitting diode
(LED), liquid-crystal display (LCD)

In solid-state component, current is confined to solid elements & compounds

engineered specifically to switch & amplify it
Current flow can be understood in two forms: as negatively charged
electrons, and as positively charged electron deficiencies called holes

13

Semiconductor Materials

Light detectors

Fluorescent materials
Television screens

Used in transistors, rectifiers, ICs

Infrared & nuclear radiation detectors

Used in LEDs

Al

Si

N
P

Zn

Ga

Ge

As

Se

Cd

In

Sb

Te

14

Significance of Semiconductors

Several semiconductors used in electronic & optoelectronic functions

Used earlier days of

developments in
transistors/diodes, & currently
Infrared & nuclear radiation
detectors

Semiconductor is a solid material that has electrical conductivity in between

conductor & insulator
Semiconductor is very similar to insulators. Two categories of solids differ
primarily in that insulators have larger energy band gaps that electrons must
acquire to be free to move from atom to atom
In Semiconductor production, doping is the process of intentionally introducing
impurities into extremely pure (referred as intrinsic) semiconductor in order to
change its electrical properties
Number of dopant atoms needed to create a difference in ability of a
semiconductor to conduct is very small
Small number of dopant atoms are added (order of 1 every 100,000,000
atoms) then doping is said to be low, or light
More dopant atoms are added (order of 1 in 10,000) then doping is said to
be heavy, or high. This is often shown as n+ for n-type dopant or p+ for ptype doping

Si

SiC

Ge

SiGe

AlP

ZnS

AlAs

ZnSe

AlSb

ZnTe

GaN

CdSe

GaP

CdTe

Computers, palm pilots, laptops: Silicon (Si) MOSFETs, ICs, CMOS

Cell phones, pagers: Si ICs, GaAs FETs, BJTs
CD players: AlGaAs, InGaP laser diodes, Si photodiodes
TV remotes, mobile terminals: Light emitting diodes
Satellite dishes: InGaAs MMICs
Fiber networks: InGaAsP laser diodes, pin photodiodes
Traffic signals, car: GaN LEDs (green, blue)
Taillights: InGaAsP LEDs (red, amber)

GaAs
GaSb
InP
InAs
InSb

15

16

How many Silicon atoms/cm-3?

Why Silicon dominates?

Abundant, cheap, wider band gap, wide operation temperature

SiO2 is very stable, strong dielectric & it is easy to grow on thermal process
Atomic number: 14, Atomic mass/weight: 28.0855
Silicon group: IV elements (C, Ge)
Crystal structure: diamond cubic
Silicon forms: fcc structure with lattice spacing: 5.430710 A (0.5430710 nm)
Band gap energy: 300 K 1.12eV
Each Si atom has 4 nearest neighbors
Density of solid: 2.33 gm/cm3
Magnetic ordering: diamagnetic
Electric resistivity : (20 C) 103]m
Thermal conductivity: (300 K) 149 Wm1K1
Thermal expansion: (25 C) 2.6 mm1K1
Speed of sound: (thin rod) (20 C) 8433 m/s
Youngs modulous: 185 Gpa Shear moduluos : 52 Gpa
Bulk modulous: 100 GPa
Melting point: 1414C, Boiling point: 2900C
Molar Volume: 12.06 cm3
17

Crystalline Solids

To understand the distinction b/w solid material types, we must first

understand the concept of order. Order can be described as the
repetition of identical structures or identical placement of atoms

# of Electrons
1
2
3
Z Name 1s 2s 2p 3s 3p 3d

Notation

1H

1s 1

2 He

1s 2
1s 2 2s 1

3 Li

4 Be

5B

1s 2 2s 2 2p1

6C

1s 2 2s 2 2p2

7N

1s 2 2s 2 2p3

8O

1s 2 2s 2 2p4

9F

10 Ne

11 Na

12 Mg

1s 2 2s 2

1s 2 2s 2 2p5
1s 2 2s 2 2p6
1s 2 2s 2 2p6 3s 1
1s 2 2s 2 2p6 3s 2

13 Al

1s 2 2s 2 2p6 3s 2 3p1

14 Si

1s 2 2s 2 2p6 3s 2 3p2

15 P

1s 2 2s 2 2p6 3s 2 3p3

16 S

1s 2 2s 2 2p6 3s 2 3p4

17 Cl

1s 2 2s 2 2p6 3s 2 3p5

18 Ar

1s 2 2s 2 2p6 3s 2 3p6

How many Silicon atoms/cm-3?

Number of atoms in a unit cell:
4 atoms completely inside cell
Each of 8 atoms on corners are shared among cells count as 1 atom inside cell
Each of 6 atoms on faces are shared among 2 cells  count as 3 atoms inside cell
Total number inside the cell=4+1+3=8
Cell volume:(0.543 nm)3 =1.6 x 10-22 cm3
Density of silicon atoms=(8 atoms)/(cell volume)=5x1022 atoms/cm3

Different crystal structures & same substance can have more than one structure
Iron has body-centred cubic structure at temperatures below 912 C, & facecentred cubic structure b/w 912-1394C
Ice has 15 known crystal structures at various temperatures & pressures

Perfect Crystal: is an idealization that does not exist in nature. In some ways,
even a crystal surface is an imperfection, because periodicity is interrupted there
Each atom undergoes thermal vibrations around their equilibrium positions
for temperatures T > 0K. These can also be viewed as imperfections
Real Crystals: always have foreign atoms (impurities), missing atoms
(vacancies), & atoms in b/w lattice sites (interstitials) where they should not be.
Each of these spoils the perfect crystal structure

For example, an atom has six nearby atoms, each 5 A away, arranged in a
pattern:

14 electrons occupying the 1st 3 energy levels: 1s,

2s, 2p orbitals filled by 10 electrons 3s, 3p orbitals
filled by 4 electrons
To minimize the overall energy, the 3s and 3p orbitals
hybridize to form 4 tetrahedral 3sp orbitals

Each has one electron and is capable of forming
a bond with a neighboring atom

18

Crystalline Solids

In crystalline solids, the particles (atoms, molecules, or ions) are

packed in a regularly ordered, repeating pattern

If one where to pick any other atom in material & find same arrangement, then
material would be described as having order. This order can be Short Range
Order (SRO) or Long Range Order (LRO)
SRO is typically on the order of 100 inter atom distances or less, while long
range is over distance greater than 1000 inter atom distances, with a
transitional region in between
19

20

Structure of Solids

Single Vs Polycrystals

Crystalline Solids:
Single/mono crystals have a periodic atomic structure across its whole
volume in 3-D long range
Any good quality semiconductor have periodic arrangements of atoms in 3-D
Atoms have both SRO & LRO
Amorphous Solids:
Continuous random network structure of atoms
Amorphous Si do not have any ordering at all
Atoms may have some local order, SRO, no LRO
E.g. Polymers, cotton candy, common window glass, ceramic
Polycrystalline Solids
An aggregate of a large number of small crystals or grains in which structure
is regular, but crystals or grains are arranged in a random fashion
Semiconductors deposited on non-lattice matched substrate have only short
range ordering of atoms

Single crystalline materials properties vary with direction, i.e. anisotropic

Polycrystalline materials may or may not vary with direction

If polycrystal grains are randomly oriented, properties will not vary with
direction i.e. isotropic
If polycrystal grains are textured, properties will vary with direction i.e.
anisotropic

Grains
21

22

Lattice Structure

Crystal Structure

Crystal structure is called Lattice or Lattice structure

Lattice is an infinite array of points in space in which each point has
identical surroundings to all others. The points are arranged exactly in a
periodic manner

Crystal structure consists of: lattice type, lattice parameters, motif

Lattice must be described in terms of 3-D coordinates related to

translation directions. Lattice points, Miller indices, Lattice planes (and
the d-spacings between them) are conventions that facilitate
description of lattice

Although it is an imaginary construct, lattice is used to describe the
structure of real materials

Lattice type: Location of lattice points within unit cell

Lattice parameters: Size & shape of unit cell
Motif/basis: List of atoms associated with each lattice point, along with their
fractional coordinates relative to lattice point. Since each lattice point is, by
definition, identical, if we add the motif to each lattice point, we will
generate the entire structure:
Simplest structural unit for a given solid is called the basis
Crystal Structure = Lattice + Basis
motif

Atoms do not necessarily lie at lattice points!!

23

24

Crystal Lattice

Lattice Vectors

In crystallography, only geometrical properties of crystal are of interest,

therefore one replaces each atom by a geometrical point located at the
equilibrium position of that atom

Crystalline structures are characterized by a repeating pattern in 3-D.
Periodic nature of structure can be represented using a lattice

Lattice vector is a vector joining any two lattice points

Any lattice vector can be written as a linear combination of unit cell
vectors a,b,c:
t = Ua+Vb+Wc or t = [UVW]
Negative values are not prefixed with a minus sign. Instead a bar is placed
above the number to denote that the value is negative:
t = Ua+VbW c

Infinite array of points in space

Each point has identical surroundings to all others
Arrays are arranged in a periodic manner

a
b

a
t

t
t

b
a
t=Ua+Vb

r=3a+2b

t=2a+1b

t=3a+2b

25

26

Unit Cell

Unit Cell Types

Simplest repeating unit in a crystal is called a unit cell

Simplest portion of structure which is repeated & shows its full symmetry

Primitive unit cells

Opposite faces of a unit cell are parallel

Edge of unit cell connects equivalent points
Not unique. There can be several unit cells of a crystal
Each unit cell is defined in terms of lattice points
Lattice point not necessarily at an atomic site
For each crystal structure, a conventional unit cell, is chosen to make the
lattice as symmetric as possible. However, conventional unit cell is not
always the primitive unit cell
By repeated duplication, a unit cell should reproduce the whole crystal

Contains single lattice point/cell, which is made up from lattice points at

each of the corners
Smallest area in 2-D, smallest volume in 3-D

Primitive unit cell whose symmetry matches the lattice symmetry is

called Wigner-Seitz cell

Non-primitive unit cells
Contain additional lattice points, either on a face of unit cell or within unit cell
Integral multiples of the area of primitive cell
2
1

At lattice points:
Atoms, Molecules, Ions

Wigner-Seitz cell
(a) 2-D space lattice
(b) BCC space lattice
(c) FCC space lattice

1,2,3=Primitive translation vector

4=Non Primitive translation vectors

lattice
point
Unit Cell

Unit cells in 3-D

27

28

Lattices Geometry

Crystal System

Unit cell: smallest repetitive volume which contains the complete

lattice pattern of a crystal

Length of unit cell along x,y,z direction are defined as a,b,c. Angles b/w
crystallographic axes are defined by:

Set of rotation & reflection symmetries

which leave a lattice point fixed

Lattice systems are grouping of
crystal structures according to axial
system used to describe their lattice

Each lattice system consists of a set
of 3-axes in particular geometrical
arrangement

= angle between b & c

= angle between a & c
= angle between a & b
a, b, c, , , are collectively know as lattice parameters

Cubic (Isometric), Hexagonal,

Tetragonal, Rhombohedral (Trigonal),
Orthorhombic, Monoclinic & Triclinic

a, b, and c are the lattice constant

29

Cubic Crystal Lattice

30

Cubic Crystal Lattice

Large number of semiconductors are cubic

Primitive(P) unit cell with one lattice point per unit cell
Face-centred(F) unit cell with additional lattice points at centre of each face &
four lattice points per unit cell
Body-centred(I) unit cell with a lattice point in middle of unit cell & two lattice
points per unit cell
Other cell types are C-face-centred & rhombohedral unit cell
All unit vectors identifying the traditional unit cell have same size
Crystal structure is completely defined by single number. This number is the
lattice constant, a

SC
a,b,c are basis
vectors along edges

8-corners

BCC
New atom is at:
a/2+b/2+c/2

FCC
New atoms are at:
(a/2+b/2),(b/2+c/2),(a/2+c/2),
(a+b/2+c/2),(a/2+b+c/2),(a/2+b/2+c)

Diamond Lattice
FCC & then add 4-additional internal atoms at locations
a/4+b/4+c/4 away from each of atoms

31

32

Crystalline Structure

Crystalline Structure

Basic FCC Cell

8 atoms at each corner, 6 atoms

on each face, 4 atoms entirely
inside the cell

Merged FCC Cells

Omit atoms
outside Cell

Bonding of Atoms
Wurtzite

Rocksalt

33

Cubic Crystal Structures

Number of
atoms/unit
cell

Nearest
Neighbour
Distance

Na, W
Al, Au

2
4

3 a/2
2 a/2

F.C.C.

Si, Ge

3 a/4

Hexagonal

Mg

Zinc Blende

F.C.C.

GaAs

4A+4B

a
3 a/4(A-B)
2 a/2(A-A,BB)

Wurtzite

Hexagonal

CdS

7A+7B

Rock Salt

F.C.C.

NaCl

4A+4B

Simple
Cubic
B.C.C.
F.C.C.
Diamond
Cubic
H.C.P.

Bravais or
Space
Lattice
Simple
Cubic
B.C.C.
F.C.C.

Crystal Lattices

Example

Crystal
Structure

34

2-D Crystals

(a) Square
(d) hexagonal
(b) Rectangular
(e) oblique
(c) centered rectangular

a/2(A-B)
2 a/2(A-A,BB)

3-D Crystals
35

36

Miller indices

Crystallographic Planes & Si Wafers

Miller indices describes the directions & planes in a crystal

To find miller indices of plane:

Silicon wafers are usually cut along a {100} plane with a flat or notch to
orient the wafer during IC fabrication:

1. Find the intercepts of plane in each of 3-axes in terms of lattice constants

2. Take reciprocals of these numbers
3. Converts them to the smallest 3-intergers having the same ratio, by
multiplying with appropriate integers

Notations: (hkl) -> plane; [hkl]-> denotes a crystal direction
Notation

Interpretation

(hkl)

crystal plane

{hkl}

equivalent planes

[hkl]

crystal direction

<hkl>

equivalent directions

h: inverse x-intercept of plane

k: inverse y-intercept of plane
l: inverse z-intercept of plane
(Intercept values are in multiples of the lattice constant;
h, k and l are reduced to 3 integers having the same ratio.)

[011]

[111]

[100]

(100)

Direction

Plane
37

Planes with Negative Indices

38

Example

Planes (100), (010), (001), (100), (010), (001) are

equivalent planes. Denoted by {1 0 0}
Atomic density and arrangement as well as electrical,
optical, physical properties are also equivalent

(001) plane
(010)
plane

(100)
plane
y
x

39

40

Example

Example

Plane has intercepts at 2a, 4b and 1c along three crystal axes

Take the reciprocal: (1/2, , 1)

Multiplying by 4: (2,1,4) plane
Exception: if the intercept is a fraction of lattice constant a, in this case we
do not reduce it to the lowest set of integers

(100),(110),(111) surfaces considered above are the so-called low index

surfaces of cubic crystal system ("low" refers to Miller indices being small
numbers - 0 or 1 in this case)

z
(214)
Surface(110)
Intercepts : a , a ,
Fractional intercepts :1,1,
Miller Indices : (110)

y
c

Surface (111)
Intercepts : a , a , a
Fractional intercepts :1,1,1
Miller Indices : (111)

Surface (210)
Intercepts : a , a ,
Fractional intercepts : ,1,
Miller Indices : (210)

41

42

Examples

Crystal Directions

x y z
[1] Draw a vector and take components

0 2a 2a

[2] Reduce to simplest integers

0 1 1

[3] Enclose the number in square brackets

[0 1 1]

y
x

x y z

[1] Draw a vector and take components

0 -a 2a

[2] Reduce to simplest integers

0 -1 2

[3] Enclose the number in square brackets

[0 1 2]

y
x

< 100 > [100 ], [ 010 ], [ 001 ], [ 1 00 ], [ 0 1 0 ], [ 00 1 ]

1: [100]
Equivalent directions due to crystal symmetry: 2: [010]
3: [001]

y
x

43

2
1

44

Example

1..
2.
3.

4.
5.
6.

Examples

The intercepts of a crystal plane with the axis defined by a set of unit vectors
are at 2a, -3b and 4c. Find the corresponding Miller indices of this and all other
crystal planes parallel to this plane?
The Miller indices are obtained in the following three steps:
Identify the intersections with the axis, namely 2, -3 and 4
Calculate the inverse of each of those intercepts, resulting in 1/2, -1/3 and 1/4
Find the smallest integers proportional to the inverse of the intercepts.
Multiplying each fraction with the product of each of the intercepts (24=2x3x 4)
does result in integers, but not always the smallest integers
These are obtained in this case by multiplying each fraction by 12
Resulting Miller indices is 6 4 3
Negative index indicated by a bar on top

[1] Determine intercept of plane with each axis

[2] Invert the intercept values

1/a 1/ 1/

[3] Convert to the smallest integers

[4] Enclose the number in round brackets

(1 0 0)

z=

y
x=a
y=

x
z

[1] Determine intercept of plane with each axis

2a

2a

2a

[2] Invert the intercept values

1/2a 1/2a 1/2a

[3] Convert to the smallest integers

[4] Enclose the number in round brackets

(1 1 1)

1
x
z

[1] Determine intercept of plane with each axis

-a

[2] Invert the intercept values

1/a -1/a 1/a

[3] Convert to the smallest integers

[4] Enclose the number in round brackets

45

Diamond Lattice

Zinc-blend Crystal Structure

Basic crystal structure of many important semiconductors is fcc lattice

with basis of 2-atoms, giving rise to diamond structure, characteristic of
Si, Ge, C in diamond form

Many compound semiconductors, atom are arranged in basic diamond
structure but are different on alternating sites. This is called zinc-blende
structure and typical of III-V compounds GaAs, InP, GaP, GaN, etc.
have crystal structure that is similar to diamond

Each atom still has four covalent bonds, but these are bonds to atoms
of other type

Important for optoelectronics & high-speed ICs

Diamond lattice of Si & Ge

Unit cell of diamond lattice

constructed by placing ,1/4,1/4
from each atom in fcc
47

-1

-1

(1 1 1 )

y
x

46

III-V compounds has the ability to vary mixture of elements on each of two
interpenetrating fcc sublattices of sinc-blende crystal
Ternary compound (AlGaAs):
It is possible to vary composition of ternary alloy by choosing fraction of Al or
Ga atoms on column III sublattice
AlxGa1-xAs contains a fraction of x of Al atoms and 1-x of Ga atoms
Al0.3Ga0.7 has 30% Al & 70% Ga on column III sites, with interpenetrating
column V sublattice occpied entirely by As atoms
It is extremely useful to grow ternary alloy crystal

48

Materials & Packing

Metallic Crystal Structures

Crystalline materials:

Atoms are packed into lattice in different arrangements

Distance b/w neighboring determined by balance b/w forces that attract
them together and other forces for particular solids

Tend to be densely packed

Atoms pack in periodic, 3-D arrays

Typical of: Metals, Many Ceramics, Some Polymers
Si

NonCrystalline materials:
Atoms have no periodic packing
Occurs for: Complex structures, Rapid Cooling

Oxygen

Crystalline SiO2

Typically, only one element is present, so all atomic radii are same
Metallic bonding is not directional
Nearest neighbor distances tend to be small in order to lower bond energy
Electron cloud shields cores from each other

How can we stack metal atoms to minimize empty space?

2-dimensions
Noncrystalline SiO2

vs.
Non dense, random packing

Dense, ordered packing

Dense, ordered packed structures tend to have lower energies

Now stack these 2-D layers to make 3-D structures

49

Cubic Cells

50

Atomic Packing Factor (APF)

51

Atomic packing factor (APF) or packing fraction is the fraction of volume in a

crystal structure that is occupied by atoms

It is dimensionless & always less than unity

For practical purposes, APF of crystal structure is determined by assuming
that atoms are rigid spheres

Radius of spheres is maximal value such that atoms do not overlap

52

Cubic Cells

Cubic Cells

Distance b/w neighboring determined by balance b/w forces

Assuming 1- atom/lattice point in primitive cubic lattice with cube side length a

Shared by 2 unit cells

Shared by 8 unit cells

1 atom/unit cell

2 atoms/unit cell

4 atoms/unit cell

(8 x 1/8 = 1)

(8 x 1/8 + 1 = 2)

(8 x 1/8 + 6 x 1/2 = 4)

53

54

Example

Atomic Packing Factor (APF):BCC

What fraction of SC Lattice can be filled by atoms?

Atoms touch each other along cube diagonals

All atoms are identical; center atom is shaded differently only for ease of
viewing
ex: Cr, W, Fe (), Tantalum, Molybdenum

Assume atoms are perfect hard sphere & touching their nearest neighbour,
called Hard Pack approximation
Each sides of SC have length a, thus the volume of cube is a3

a
R=0.5a

2 atoms/unit cell: 1 center + 8 corners x 1/8

close-packed directions

SC Lattice

Atom at origin

Coordination # = 8

contains 8 x 1/8 =
1 atom/unit cell

3a
a
= 0.68

R a
55

2a
56

Face Centered Cubic Structure: (FCC)

Hexagonal Close-Packed Crystal Structure

Atoms touch each other along face diagonals

All atoms are identical; the face-centered atom is shaded differently only for
ease of viewing
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

For Hexagonal Close-Packed (HCP) structure the derivation is similar. The unit
cell is a hexagonal prism containing six atoms. Let a be the side length of its
base and c be its height. Then:

2
a
a

57

Structure of Crystalline Solids

Density= =

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

58

Examples
nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number= 6.022 x 1023 atoms/mol
a = 4R/ 3 = 0.2887 nm
Ex: Cr (BCC)
g/mol
A = 52.00 g/mol atoms/unit cell
2 52.00
=
R = 0.125 nm
23
atom/mol
a3 6.022 x 10
n = 2 atoms/unit cell

volume/unit cell

theoretical = 7.18 g/cm3

actual
= 7.19 g/cm3

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60

Which one has most packing ?

Growth of
Semiconductors
For that reason, FCC is also referred to as cubic closed packed (CCP)

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Si Starting material

Growth of Single-Crystal Ingots

Silicon prepared by the reaction of high-purity silica with wood,

charcoal, & coal, in electric arc furnace using carbon electrodes
at more than 1900, carbon reduces silica to silicon
SiO2 + C Si + CO2
SiO2 + 2C Si + 2CO (~1800C)

Growth process of purifying silicon: It converts high purity but still

polysilicon EGS to single crystal Si ingots or boules

Heating to produce 95% ~ 98% pure polycrystalline Si

Form of metallurgical grade Si (MGS)

Si has impurities like Al, Fe & heavy metal at 100s to 1000s parts/million
MGS is further refined with electronic-grade Si (EGS): Levels of impurities are
reduced to parts pet billion or ppb 5x1013 cm-3

Czochralski (CZ) Growth: Main stream growth technology for large

diameter wafer

Float Zone (FZ) Growth: For small & medium diameter wafer less
contaminations than CZ method

Si +3HCl
SiHCl3 + H2
2SiHCl3+2H22Si+6HCl

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Seed Crystal

Czochralski Si Growth

A seed crystal is a small piece of single crystal/polycrystal material from

which a large crystal of same material typically is to be grown. The
large crystal can be grown by dipping the seed into a supersaturated
solution, into molten material that is then cooled, or by growth on the
seed face by passing vapor of the material to be grown over it

To grow single-crystal material, it is necessary to have a seed which can

provide a template for growth

To melt EGS in a quartz-lined graphite crucible by resistively heating it
to melting point of Si (1412C)

Seed crystal is lowered into molten material and then is raised slowly,
allowing the crystal to grows to provide a slight stirring of melt and to
average out any temperature variations that would cause inhomogenous
solidification of compound semiconductors

Critical Control:
Seed Crystal
First Pull
Pulling Speed
Rotation Speed

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Czochralski Si Growth

Growth Control:
Pulling Speed
Rotation Speed

Final Control:
Pulling Speed
Rotation Speed

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Float Zone Si Growth

A cylindrical ingot of high purity monocrystalline semiconductor, such

as Si or Ge, is formed by pulling a seed crystal from a 'melt

Donor impurity atoms, such as boron or phosphorus in case of Si, can
be added to molten intrinsic material in precise amounts in order to
dope the crystal, thus changing it into n-type or p-type extrinsic
semiconductor

Start with polysilicon rod inside chamber either in vacuum or an inert gas
RF heating coil melts 2 cm zone in rod
RF coil moves through the rod, moving the molten silicon region with it
This melting purifies the silicon rod
Oxygen can be diffused into silicon called Diffusion Oxygenated Float Zone
(DOFZ) (done at the wafer level)

Poly silicon

RF Heating coil
Single crystal silicon

Float Zone Growth

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Liquid-Encapsulated Czochralski GaAs Growth

Crystalline Wafer

To prevent volatile elements (e.g. As) from vaporizing, it requires to

add a dense & viscous molten layer (B2O3) over the melt. Such
process is called liquid-encapsulated Czochralski growth technique

To prevent the decomposition of GaAs under molten condition, a high
pressure is used over the GaAs melt

Wafers are formed of highly pure (99.9999999% purity) nearly defectfree single crystalline material

Ingot is sliced with a wafer saw (wire saw) & polished to form wafers

Size of wafers for photovoltaics is 100200mm square & thickness is
200300 m

Electronics use wafer sizes from 100300mm diameter

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Doping

From Ignot to Wafer

Shaping
Grinding
Sawing or Slicing
Edge Rounding
Lapping
Etching
Polishing
Cleaning
Inspection
Packaging
Shipping

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Doping during growth of substrate

Intentional addition of impurities or dopants to the crystal to change its

electronic properties (varying conductivity of semiconductors)

Doping of 1014 to 1017 atom/cm3

Typically hydrides of atoms are used as the source of dopants e.g.
PH3, AsH3 or B2H6 for controlled doping

Purpose: To change the electronic properties of the molten Electronic-grade Si

(EGS), we add international impurities or dopants to Si melt
Method: Dopant atoms usually have one (or in some cases more) electrons
deficient or excess compared to atoms of semiconductor. Excess electrons can
contribute to conduction and dope the material n-type. In case of electron
deficiency, holes are formed and they can also take part in conduction,
through not as efficiently as electrons (holes are more sluggish)

Distribution Coefficient (kd): Ratio of concentration of impurity in solid

Cs to the concentration in liquid CL at equilibrium
Kd=Cs/CL
Dependence of kd:
Material properties
Impurities
Temperature of solid-liquid interface
Growth rate

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Example

Epitaxial Growth

Growth of a thin crystal layer on a wafer of a compatible crystal

Purpose: To achieve desired electrical, mechanical, or thermal
properties of thin film material grown. Epitaxial crystal layer usually
maintains the crystal structure & orientation of substrate

Methods:
Chemical Vapor Deposition (CVD)
Molecular Beam Epitaxy (MBE)
Liquid-Phase Expitaxy (LPE)

Advantage over bulk (wafer) growth techniques: Epitaxial technique can

make possible controlled growth of very thin films, with well controllable
doping & composition that are essential for modern day electronic
devices. Some devices such as quantum mechanical ones, would not
the possible without epitaxial growth

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Epitaxial Growth with Lattice match

Epitaxial Growth with Lattice match

Homo-epitaxy: Expitaxial layer grown is same as substrate (Same

substrate & film)

Lattice structure and lattice constant must match for two materials e.g.
GaAs and AlAs both have zincblende structure

Main advantage is to control thickness & doping of epitaxial layer

E.g. Si on Si, GaAs GaAs

Hetero-epitaxy: Expitaxial layer grown is different (and has different

lattice constant, which depends on composition) from substrate
Different substrate & film)
Advantage is tunability of bandgap difference of adjacent layers (apart
from thickness and doping) which is a bid deal in device designs
e.g. Si on Sapphire

1.43 eV

Some examples of lattice matched hetero-epitaxy:

AlxGa1-xAs on GaAs
In0.53Ga0.47As on InP
In0.5Ga0.5P on GaAs
InxGa1-xAsyP1-y on InP or GaAs

In0.53Ga0.47As
0.36 eV

5.65
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6.06
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Types of Epitaxy

Types of Epitaxy

Liquid phase epitaxy

Vapor phase epitaxy

It is performed by chemical vapor deposition (CVD)
Provides excellent control of thickness, doping and crystallinity
High temperature (800 C 1100C)
Crystallization from vapor phase
Better purity and crystal perfection
Offers great flexibility in the actual fabrication of devices
Epitaxial layers are generally grown on Si substrates by controlled
deposition of Si atoms onto the surface from a chemical vapor
containing Si e.g. SiCl4 + 2H2 Si + 4HCl (for deposition as well as
for etching)
Four Si sources used for growing epitaxial Si: Silicon tetrachloride
(SiCl4), Dichlorosilane (SiH2Cl2), Trichlorosilane (SiHCl3), Silane
(SiH4)

III-V epitaxial layer GaAs

Grow crystals from liquid solution below their melting point
Low temperature eliminates many problems of impurity
Refreeze of laser melted silicon

Molecular beam epitaxy

Crystalline layer grows in vacuum

Substrate is held in high vacuum in the range 10-10 torr
Components along with dopants, are heated in separate
cylindrical cells.
Collimated beams of these escape into the vacuum and are
directed into the surface of a substrate
Sample held at relatively low temperature (600oC for GaAs)
Conventional temperature range is 400o C to 800oC
Growth rates are in the range of 0.01 to 0.3 m/min

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Chemical Vapor Deposition (CVD)

Metalorganic Chemical Vapour Decomposition (MOCVD)

Basics: Expitaxial Growth that is achieved by crystallization from vapor

phase of the reactants

Example: Growth of Si thin film on Si substrate, growth of SiC layers on
SiC substrate

SiCl4 + 2H2  Si + 4HCl

Generic CVD machine

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Basics:The expitaxial layer is formed by the reaction between hydride species

such as NH3, AsH3, and metalorganic species such as Tri-methyl Ga(TMG), Trimethyl Indium (TMI), Tri-methyl Aluminum (TMA) etc. Note all the reactants are
in the vapor phase, hence this technique is a subset of the CVD technique.
Example: Expitaxial growth of compound semiconductors such as GaAs, GaP,
GaN

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Molecular Beam Epitaxy (MBE)

Substrate is held in a high vacuum while molecular or atomic beams of constituents

impinge upon its surface
In growth of AlGaAs layers on GaAs substrates, Al, Ga, & As components along with
dopants are heated in separate cylindrical cells
Collimated beams in vacuum are directed onto the surface of substrate & strike the
surface closely controlled and growth of very high quality crystals results

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