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ELECTRONIC MATERIALS, DEVICES,

AND FABRICATION
ELECTRONIC MATERIALS,
DEVICES, AND FABRICATION
Section I: Electronic materials

Parasuraman Swaminathan
IIT Madras

A JOHN WILEY & SONS, INC., PUBLICATION


To my family
FOREWORD

The book covers topics covered in the course MM5017 introduced as a graduate elective
for students at IITM. The topics covered in the book follow the lecture series posted in
NPTEL. In Section I the chapters on electronic materials are included.

Chennai Parasuraman Swaminathan

vii
PREFACE

The book is developed based on the course notes on Electronic materials, devices, and
fabrication. The book is designed to develop an understanding of the materials, devices,
and processing techniques used in the current semiconductor industry. The course is geared
towards advanced undergraduate and graduate students with a background in Metallurgy,
Mechanical, Chemical and Electrical engineering.

The course provides the students with the basic physics behind semiconductor materi-
als, types of semiconductors, and the reason for the dominance of silicon in the electronics
industry. The course also covers the basics of devices with emphasis on their electronic
characteristics. Optical devices like LEDs, lasers, solar cells, will also be explained. The
current manufacturing processes in the silicon based semiconductor industry, starting from
silicon wafer production to final IC (integrated circuit) development, will be explained.
The focus will be on industry challenges during miniaturization and the role of materials
in overcoming the challenges. Along with the chapters there are problem sets to help un-
derstand the concepts clearly.

This section deals with the Electronic Materials part of the course. The basics of band
theory are developed along with concepts of Fermi energy, density of states, intrinsic and
extrinsic semiconductors. This will lay the foundation for understanding the principle be-
hind electronic devices.

PARASURAMAN S WAMINATHAN

ix
ACKNOWLEDGMENTS

The course notes were designed using the following reference books
1. Principles of Electronic Materials and Devices, S.O. Kasap, 3rd edition, McGraw-
Hill Education (India) Pvt. Ltd., 2007
2. Semiconductor devices: Physics and Technology, S.M. Sze, 2nd edition, Wiley, 2008.

3. VLSI technology, S.M. Sze, 2nd edition, McGraw-Hill Education (India) Pvt. Ltd.,
2003.
4. Solid State Electronic Devices, B.G. Streetman and S. Banerjee, 6th edition, PHI
Learning, 2009.

5. Introduction to solid state physics, C. Kittel, 8th edition, Wiley, 2012.


6. Microchip Fabrication, Peter van Zant, 5th edition, McGraw-Hill, 2004.
7. Fundamentals of semiconductor manufacturing and process control, G.S. May and
C.J. Spanos, Wiley-IEEE press, 2006.

Figures adapted from the books and other sources are acknowledged in the captions.
They were redrawn, with modifications, by Ms. Anushree Santhosh and her team at
NPTEL (National Program on Technology Enhanced Learning) office, IIT Madras. A
big thanks to her for help with the figures.

Parasuraman Swaminathan

xi
CONTENTS

Foreword vii
Preface ix
Acknowledgments xi

1 Electronic materials 1
1.1 Introduction 1
1.2 Molecular orbital formation 2
1.3 Molecular orbitals in extended systems 3
1.4 Energy bands in metals 5

2 Semiconductors: Introduction 11
2.1 Introduction 11
2.2 Band formation in semiconductors 11
2.3 Classification of semiconductors 15
2.4 Electron effective mass 20

3 Electron statistics in a solid 23


3.1 Density of states 23
3.1.1 DOS in a 3D uniform solid 24
3.1.2 DOS for a 2D solid 26
3.1.3 DOS for a 1D solid 27
xiii
xiv CONTENTS

3.2 Electron occupation probability 27


3.2.1 Fermi-Dirac statistics 29
3.3 Density of states in silver 30
3.4 Fermi function vs. Boltzmann function 30
Problems 31

4 Intrinsic semiconductors 33
4.1 Introduction 33
4.2 Intrinsic Si 33
4.3 Conductivity equation 35
4.3.1 Electron mobility in Si 37
4.4 Carrier concentration in semiconductors 38
4.5 Intrinsic carrier concentration 40

5 Intrinsic semiconductors-conductivity 41
5.1 Carrier concentration in intrinsic Si 41
5.2 Carrier concentration in intrinsic semiconductors 42
5.3 Fermi level in intrinsic semiconductors 43
5.4 Temperature effect on ni 44
Problems 46

6 Extrinsic semiconductors 49
6.1 Introduction 49
6.2 n-type doping 50
6.3 p-type doping 53
6.4 Conductivity in extrinsic Si 54
6.5 Compensation doping 55

7 Extrinsic semiconductors - Fermi level 57


7.1 Dopant materials 57
7.2 EF in extrinsic semiconductors 61
7.3 Temperature dependence of carrier concentration 61
7.3.1 Low temperature regime (T < Ts ) 63
7.3.2 Medium temperature regime (Ts < T < Ti ) 63

8 Extrinsic semiconductors - mobility 65


8.1 Carrier mobility 65
8.1.1 Lattice scattering 66
8.1.2 Impurity scattering 67
8.1.3 Conductivity in extrinsic semiconductors 67
8.2 Degenerate semiconductors 71
8.3 Amorphous semiconductors 71
CONTENTS xv

Problems 73
Index 75
xvi
CHAPTER 1

ELECTRONIC MATERIALS

1.1 Introduction

When we think of electronic materials the physical property that is important is resistance.
Based on resistance materials can be classified into 3 major types

Conductors

Semiconductors

Insulators

The unit of resistance is Ohm () and is related to the applied voltage and current by
Ohms law
V = IR (1.1)
where V is the applied voltage (units Volts), I is the current (units Amperes) and R is the
resistance. Resistance depends on the sample dimensions. Reducing the thickness of a film
or decreasing the diameter of a wire would lead to an increase in resistance. We can define
a material independent property called resistivity () which removes this dependence on
sample dimensions. Resistance is related to resistivity by

l
R= (1.2)
A
Second Edition. 1
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
2 1

Table 1.1: Resistivity values of some typical metals


Metal (109 m)
Copper 15.7
Gold 22.8
Platinum 98
Silver 14.6

Table 1.2: Resistivity values of some typical semiconductors


Semiconductor (m)
Germanium 103 - 10
Silicon 0.1 - 103
Zinc oxide 102 - 104
Gallium Arsenide 106 - 102

Table 1.3: Resistivity values of typical insulators


Insulator (m)
Wood (damp) 103 - 104
Deionized water 105
Glass 1010 - 1014
Fused quartz 1017

where l is the length of the sample and A is the cross sectional area. The unit of resistivity
is m. Conductivity is defined as the inverse of resistivity. The symbol for conductivity
is and unit is 1 m1 . We can compare typical values for resistivity for conductors,
semiconductors, and insulators. When we deal with conductors they will mostly be metals.
Some typical values of metal conductivity are shown in table 1.1.
Metals are characterized by low resistivity. The values quoted in table 1.1 are in the
range of nano m. Compared to metals, semiconductors have higher resistivity values,
as seen in table 1.2. Semiconductor resistivities usually have a range since they depend
on the impurity level and also on the crystalline state (single or poly crystalline). Overall,
semiconductor resistivities are 5-6 orders of magnitude higher than metals. Insulators have
the highest resistivities, these are tabulated in 1.3.
Thus, we have a range of values for resistivity for different materials and this is related
to their electronic properties. To understand this range we need to understand how band
gap evolves in materials. We will look at a basic picture of how band gap forms, with a
focus mainly on metals and then semiconductors. We will also introduce some concepts
on density of states, Fermi energy, and Fermi-Dirac statistics to understand the difference
in conductivity.

1.2 Molecular orbital formation

Energy levels in an atom are sharp and well defined. To understand what happens when
these atoms come together to form solids, we can start with the simplest atom, hydrogen
MOLECULAR ORBITALS IN EXTENDED SYSTEMS 3

(H). Hydrogen has 1 electron located in the K shell with electronic configuration 1s1 . When
2 H atoms come together there are 2 1s atomic orbitals (AOs) and these form 2 molecular
orbitals (MOs). For simplicity, let us denote the atomic orbital of H atom by 1s . In
quantum mechanics refers to the wave function of the electron in the 1s orbital. The
wave function can be solved using Schrodingers equation in spherical coordinates and the
wavefunction solution for the 1s orbital is
1 1 r
(r) = ( )3/2 exp( ) (1.3)
a0 a0
Here, a0 refers to the Bohr radius and has a value of 0.53 A. This is an exponential function
with the maximum when r = 0, corresponding to the nucleus and exponentially decreasing
away from the nucleus.
Consider two H atoms A and B, with AOs 1s A and B . There are two ways in which
1s
the 2 AOs can come together to form two MOs. The two AOs can be added, this the
bonding orbital, or they can be subtracted, giving the anti-bonding orbital, . This can
be represented by
A B
= 1s + 1s
(1.4)
= 1s
A B
1s
The bonding orbital represents the symmetric MO while the anti-bonding orbital represents
the anti-symmetric MO. They are shown pictorially in figure 1.1. The bonding orbital
shows a local minimum in the wavefunction in the region between the 2 H atoms but the
function does not go to zero. Thus there is a finite probability of finding the electron
between the 2 atoms. The anti-bonding orbital wavefuntion goes to zero between the 2
atoms and hence the probability of finding the electron between the 2 atoms is zero. This
is called a node. Thus, the bonding orbital has zero nodes and the anti-bonding orbital has
1 node. The electron probability distribution is shown in figure 1.2.
In terms of energy the bonding orbital has a lower energy than the individual orbitals
which have a lower energy than anti-bonding orbital. This is because in the electron
can be influenced by both the nuclei which leads to a lower energy. If two H atoms come
together then both electron will go to the bonding orbital (with opposite spin) since this
will lower the overall energy of the system. This can be represented by a energy vs. bond
length plot. This is shown in figure 1.3. At large interatomic distances the H atoms have
individual atomic energy levels. When they start to come together (R starts to reduce) the
2 atoms start to see the influence of each other. The atomic orbitals start to mix and form
the MOs and . There is an equilibrium distance of separation when the energy of
the system is at a minimum. Both electron occupy this minimum in the bonding orbital.
Figure 1.3 also shown the schematic representation of the formation of the MOs and the
energy minimization using horizontal lines to represent the orbitals. From this diagram it
is clear why He2 will not form. Each He atom has 2 electrons so that there are a total of
4 electrons. Out of these 2 electrons will go to and two to since each MO can only
take a maximum of 2 electrons (opposite spin). The overall energy of the He2 molecule
will then be higher than the energy of 2 individual He atoms and hence He2 will not form.

1.3 Molecular orbitals in extended systems

Consider the case when we have 3 H atoms. Each atom has a 1s atomic orbital and these
3 AOs will come together to form 3 MOs. Let the 3 H atoms be A, B, and C with atomic
4 1

Figure 1.1: Formation of (a) bonding and (b) anti-bonding orbitals when 2 H atoms come
together. Adapted from Principles of Electronic Materials - S.O. Kasap.
ENERGY BANDS IN METALS 5

Figure 1.2: Electron probability distribution in (a) bonding ( ) and (b) anti-bonding ( )
orbitals. Lines of constant probability are shown. For the anti-bonding orbital there is
zero probability of finding the electron betwen the two atoms i.e. node. Adapted from
Principles of Electronic Materials - S.O. Kasap.

A , B , and C . The 3 AOs can be put together to form 3 MOs while maintaining
orbitals 1s 1s 1s
symmetry of the resultant wave function in the following way.
A B C
a = 1s + 1s + 1s
A C
b = 1s 1s (1.5)
A B C
c = 1s 1s + 1s
a , b , and c are the 3 MOs that are formed. This formation is shown in figure 1.4. a is
the symmetric solution with no nodes. b is the antisymmetric solution with a node in the
location of the middle atom (this is the reason for no contribution from B in equation 1.5).
c is again a symmetric solution but with 2 nodes, between the 2 sets of atoms. In terms of
energy a is the lowest followed by b and then c . The energy vs. bond length diagram
for 3 H atoms is shown in figure 1.5. Out of the 3 electrons that are available 2 go to the
lowest energy MO i.e. a with 0 nodes and the remaining one goes to b with 1 node.
More the number of nodes greater is the energy of the MO. Instead of 3 H atoms, if we
have 4 atoms then there are 4 AOs which form 4 MOs with 0, 1, 2, and 3 nodes (arranged
in order of increasing energy). Each of these MOs can take 2 electrons (opposite spin) so
that there are a total of 8 energy states (including spin). The argument can be generalized
saying that if there are N atoms, there are N atomic orbitals, and hence N molecular or-
bitals, and 2N energy states. As long as the energy of the configuration is lower than the
individual atoms the solid will be stable.

1.4 Energy bands in metals

We can try to extend this model beyond H. Consider the case of Li, which has 3 electrons.
The electronic configuration is 1s2 2s1 . The 1s electrons form the inner shell and are usually
6 1

Figure 1.3: (a) Energy vs. bond length plot for 2 H atoms. (b) The schematic representation
of the formation of the H2 molecule. Both electrons go to the bonding orbital while the
anti-bonding orbital is empty. Adapted from Principles of Electronic Materials - S.O.
Kasap.
ENERGY BANDS IN METALS 7

Figure 1.4: MOs formed when 3 H atoms come together. The number of nodes increases
while the stability decreases. The configuration with the lowest number of nodes is most
stable. Adapted from Principles of Electronic Materials - S.O. Kasap.

not involved in bonding. Hence, for bonding we have the 2s shell with 1 electron and this
can be considered similar to the H atom. So, if we have N Li atoms, there will be N MOs,
and 2N energy states (including spin). This is shown schematically in figure 1.6.
The spacing between the individual MOs depends on the equilibrium interatomic spacing
and the value of N. Larger the value of N, closer the individual levels. For really large N
(e.g. if we have 7 g of Li then N will be 6.023 1023 or Avogadros number) the individual
MOs are so close that we can consider them to be continuous. Thus an energy band will
be obtained. This band is called the valence band since it is obtained from the outermost
shell. The band formation for Li is shown in figure 1.7. In the case of Li the band formed
from the outer 2s levels is half full since there are a total of 2N energy states and only N
electrons.
The separation between the filled states and the empty states is called the Fermi energy
and is denoted by EF . Another way of defining the Fermi energy is that this is the highest
filled state in a metal at 0 K. The energy required to remove an electron from the Fermi
level to vacuum level (where the electron is free of the influence of the metal) is called
the work function. The Fermi level and work function for Li are shown in figure 1.8.
Energy levels can be referenced either with respect to the vacuum level (takes as zero) or
with respect to the bottom of the valence band. Thus, metals like Li have a partially filled
valence band.
We can extend this model to Be, which has 2 electrons in the outer 2s shell. According to
the model we developed for Li where we have a band with 2N energy states and N electrons
we have now have 2N states and 2N electrons so that the band should be completely full.
So how is Be a metal? The reason is because Be has empty 2p shells which are close
in energy to the 2s shell and they overlap. Because of this overlap there are empty states
available for conduction. There are overlap states in Li as well, but we do not need these to
8 1

Figure 1.5: Energy vs. bond length diagram for 3H atoms forming 3 MOs. The 3 electrons
occupy the configuration with 0 noes (2 electrons) and 1 node (1 electron). Adapted from
Principles of Electronic Materials - S.O. Kasap.

Figure 1.6: Energy vs. bond length diagram for N Li atoms. There are a total of 2N energy
states (including spin) out of which N are occupied, half full. This makes Li a metal.
Adapted from Principles of Electronic Materials - S.O. Kasap.
ENERGY BANDS IN METALS 9

Figure 1.7: Energy vs. bond length diagram for large values of N showing a continuous
band formation. The overlap between the 2s, 2p, and 3s levels are also shown. Adapted
from Principles of Electronic Materials - S.O. Kasap.

Figure 1.8: Fermi energy and work function in Li. By convention the vacuum level is taken
as zero and energy levels within the metal are shown as negative. If the lowest energy level
in the valence band is used as reference all these energy levels become positive. Adapted
from Principles of Electronic Materials - S.O. Kasap.
10 1

Figure 1.9: Energy band in a metal formed through overlap of individual bands. This
diagram is similar to figure 1.7, at the equilibrium distance. Adapted from Principles of
Electronic Materials - S.O. Kasap.

explain conduction since the starting band is half full anyway. We can call the band formed
by the empty 2p shell as the conduction band. In metals, the valence and conduction band
overlap to give a continuous band of filled and empty states. This is shown schematically
in figure 1.9. In the presence of an electric field electrons can move by occupying these
empty energy states and this makes metals good conductors of electricity.
CHAPTER 2

SEMICONDUCTORS: INTRODUCTION

2.1 Introduction

Metals have electrical conductivity. This is related to the fact that the energy band of the
metal consists of continuous filled and empty states. This is related to either a half full orb-
tial (alkali metals) or due to overlap between filled and empty orbitals (alkali earth metals).
At 0 K the highest filled state is called the Fermi energy (EF ). Because the energy differ-
ence between the states in the outer band is non-existent, at room temperature, electrons
can easily move in the metal during application of an external field. The electrons in the
outer band of a metal are said to be delocalized, i.e. they belong to the entire solid rather
than being tied down to a specific atom. These delocalized electrons are responsible for
the high conductivity. A schematic for electrical conduction in metals is shown in figure
2.1.
The formation of energy bands in semiconductors and by extension insulators can be ex-
plained in an analogous manner to metals. The difference being that in semiconductors
(insulators) there is an energy gap between the filled valence band and the empty conduc-
tion band.

2.2 Band formation in semiconductors

Consider the example of energy band formation in Si (the most dominant in today micro-
electronics industry). Si has an atomic number of 14 and the electronic configuration is
Second Edition. 11
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
12 2

Figure 2.1: Electrical conduction in metals due to presence of empty electron states in close
proximity to filled states. Upon application of an external field electrons move opposite to
the field. Adapted from Principles of Electronic Materials - S.O. Kasap.

Figure 2.2: Electronic configuration of Si atom. The 3s and 3p together forms the outer
shell while the others form the inner shells. Adapted from Principles of Electronic Mate-
rials - S.O. Kasap.

1s2 2s2 2p6 3s2 3p2 shown schematically in figure 2.2. The 3s2 3p2 forms the outer shell and
we can ignore the inner shells as far as electrical conductivity is considered. The 3s and 3p
orbitals in Si are close in energy and can hybridize to form sp3 orbitals. Given that there
are 4 electrons a total of 4 sp3 hybrid orbtials are formed. These form 4 bonds that are
directed along the corners of a tetrahedron, as shown in figure 2.3.
Hybridization is a common property of elements of Group IV of the periodic table to
BAND FORMATION IN SEMICONDUCTORS 13

Figure 2.3: (a) Isolated Si atoms showing the outer shell orbitals. (b) In a solid, these
orbitals hybridize to form 4 sp3 orbitals, just before bonding. Adapted from Principles of
Electronic Materials - S.O. Kasap.
14 2

Figure 2.4: Formation of energy bands in Si. (a) Si atom with 4 electrons in outer shell form
(b) 4 sp3 hybrid orbitals. (c) The hybrid orbitals form and orbitals. (d) These orbitals
overlap in a solid to form the valence and conduction band. Adapted from Principles of
Electronic Materials - S.O. Kasap.

which Si belongs to. C which is in top of the group can form a variety of hybrid orbitals
(sp3 , sp2 , sp). Both Si and the element below it, Ge, can form sp3 hybrid orbitals. Sn and
Pb (below Ge) are metals with low melting points. In the case of Si, the hybrid orbitals
interact the same way that atomic orbitals interact in metals. Consider a bond formed be-
tween 2 sp3 hybrid orbitals (1 from each Si atom). The two orbitals can interact to form a
bonding ( ) and anti-bonding ( ) orbital. Since each Si atom will contribute one electron
to the bond there will be a total of 2 electrons which will both go to the bonding orbital.
Thus, each Si atom can form a bond with 4 other Si atoms and in all cases the bonding or-
bital ( ) will be full. A solid will be formed from a large number of these orbitals. When
the bonding orbitals interact they will form an energy band, called valence band. This
valence band will be completely full since the bonding orbital is full. Similarly, the anti-
bonding orbitals can interact to form an energy band, called conduction band. This will
be completely empty. Unlike metals, the valence and conduction band in a semiconductor
is separated by a forbidden energy gap, this is called band gap. The formation of bands in
Si crystal is show in figure 2.4.
In the case of Si, the band gap (Eg ) has a value of 1.11 eV at room temperature (300 K).
The same argument for formation of a band gap (filled valence band and empty conduction
band with a forbidden energy gap) can be extended to other semiconductors and insulators.
The difference between them is related to the magnitude of Eg . Insulators have a band gap
greater than 3 eV while semiconductors have band gap less than 3 eV . This boundary is re-
lated to the energy boundary between the visible and UV regions of the spectrum (roughly
400 nm). Some typical values of band gap for different materials are listed in table 2.1.
CLASSIFICATION OF SEMICONDUCTORS 15

Table 2.1: Room temperature band gap of typical semiconductors and insulators. Materials
with band gap less than 3 eV are semiconductors while greater than 3 eV are insulators.
ZnO is usually considered a wider band gap semiconductor rather than an insulator.
Material Band gap (eV )
Si 1.11
Ge 0.67
GaAs 1.43
CdS 2.42
ZnO 3.37
Al2 O3 7.0
SiO2 9.0

2.3 Classification of semiconductors

There are different ways of classifying semiconductors depending on the property being
measured. One classification that is fairly straightforward is
1. Elemental semiconductors
2. Compound semiconductors
Out of the elemental semiconductors Si and Ge are the most common. There are different
type of compound semiconductors - II-VI and III-V are the most common and these can
be understood by looking at the portion of the periodic table, shown in figure 2.5.
Elemental semiconductors (Si and Ge) belong to group IVA of the periodic table. C which
is on top of the group is an insulator (diamond) with Eg of 5.5 eV while Sn and Pb are met-
als. Compound semiconductors can be formed by combining elements of groups IIIA and
VA - the III-Vs. Examples include GaAs, GaP, GaN, InSb. AlN is also a III-V but its band
gap is around 6.2 eV making it an insulator. Similarly II-VI compound semiconductors
can be formed, examples include ZnO, ZnS, CdSe, CdTe.

Another way of classifying semiconductors based on their band structure is


1. Direct band gap semiconductor
2. Indirect band gap semiconductor
This can be understood from the band picture of the semiconductor, as shown in figure 2.6.
Semiconductors have a filled valence band and an empty conduction band. Electrons from
the valence band can be excited to the conduction band by either thermal excitation or by
optical absorption. When the electron returns to the valence band the energy is released
either as heat or as photons. In direct band gap semiconductors the dominant mechanism
by which the energy is released (in the absence of defects) is by photons(electromagnetic
radiation) while in indirect band gap semiconductors the energy is released by phonons
(heat). Direct band gap semiconductors are useful for opto electronic devices like LEDs,
and lasers.
The difference between direct and indirect band gap semiconductors is related to their band
structure. Electrons in solids have a wave like character. An electron wave is characterized



by a wave vector k . Thus, for crystalline materials it possible to plot E vs. k diagrams.
16 2

Figure 2.5: Portion of the periodic table showing the group IV elements and their common
dopants. Source http://chemistry.about.com/od/periodictable/ss/How-To-Use-A-Periodic-
Table.htm
CLASSIFICATION OF SEMICONDUCTORS 17

Figure 2.6: Band picture of a semiconductor showing the full valence band and empty
conduction band. The gap between these is called the band gap. At room temperature
thermal excitation can cause some electrons to move from valence to conduction band.
Adapted from Principles of Electronic Materials - S.O. Kasap.

These are related to the simple band diagrams that show the valence and conduction band.
The complete electronic band structure for Si is shown in figure 2.7.
Without going into the details of the notations in the plot, the 0 eV refers to the top of the
valence band and at absolute zero all the energy levels below it are full. This is denoted by
the point 250 . The line above this, L1 , has a minimum at point X1 , which represents the
bottom of the conduction band (empty at 0 K). In the case of Si, the valence band maximum
and the conduction band minimum are not on top of each other. This makes Si an indirect
band gap semiconductor. Another example for an indirect band gap semiconductor is Ge,
whose band structure is shown in figure 2.8.
In a direct band gap semiconductor, on the other hand, the top of the valence band and
bottom of the conduction band lie on top of each other. An example is GaAs, which is
compared to Si in figure 2.9. Here the maximum at L4,5 is at 8 (valence band) and the
minimum at L6 is at 6 (conduction band). thus, an electron can get excited from the
valence band to the conduction band without change of the wave vector. This can be
accomplished easily by absorption of a photon of the appropriate energy. Similarly, an
electron from the conduction band can transition to the valence band easily by emission
of a photon. In Si and Ge, where the valence band top and conduction band bottom do
not line up, this transition requires a change in the electron wave vector. This has to be
supplied by the Si lattice, in the form of phonons, so that these are said to be indirect band
gap semiconductors.
18 2

Figure 2.7: E vs. k diagram for Si. The dotted line at 0 eV is the top of the valence band
and the grey region above it is the band gap. The point marked X1 is the bottom of the
conduction band. Source http://commons.wikimedia.org/wiki/Category:Silicon diagrams
CLASSIFICATION OF SEMICONDUCTORS 19

Figure 2.8: E vs. k diagram for Ge. Ge is also an indirect band gap semiconductor. The
portion to the right shows the filled and empty density of states in the valence and con-
duction band respectively. Source http://www.materialsdesign.com/appnote/energy-band-
structure-germanium
20 2

Figure 2.9: E vs. k diagram compared for GaAs and Si. GaAs is a direct band gap semi-
conductor while Si an indirect band gap semiconductor. The grey shaded region represents
the band gap. Source http://users-phys.au.dk/philip/pictures/physicsfigures/node8.html

2.4 Electron effective mass

Electrons in the valence band of Si are bound to the covalent bond between the Si atoms.
These electrons are not free to move in the solid. When the electron gets excited to the
conduction band they are said to be delocalized and can move through the solid. This can
be contrasted with metals where the electrons in the valence band are delocalized and are
shared with all the atoms in the solid (metallic bond). When an electron in Si gets excited
from the valence band to the conduction band it leaves behind a hole in the valence band.
The hole is the absence of an electron and it is denoted by h or h+ . Hole formation is shown
schematically in figure 2.6. The hole can move in the valence band by electron hopping
from one bond to another and thus can be said to be delocalized.
When we apply an electric field these electron and holes can move. Consider the motion
of free electron and electrons in a solid, in the presence of a field, as shown in figure 2.10.
The electric field goes from positive to negative, so that the electrons travel in the direction
opposite to the field. In vacuum the acceleration of the electrons (ae ) is given by
eEx
ae = (2.1)
me
where Ex is the electric field and me is the rest mass of the electron (ignoring relativistic
effects).
In the case of an electron in a solid, under an external field, the interaction with the solid
atoms should also be taken into account. Let Fint represent the sum of the interaction of
the electron with the atoms in the solid. Then the acceleration of the electron, given by
using equation 2.1, is
eEx + Fint
ae = (2.2)
me


The value of the internal forces depends on the location of the electron in the E vs. k
landscape and hence equation 2.2 can be simplified by saying that the electron has an
ELECTRON EFFECTIVE MASS 21

Figure 2.10: Electron motion in (a) vacuum and (b) solid. In a solid the motion is affected
by the interaction with the atoms. This is manifest as an effective mass of the electron.
Adapted from Principles of Electronic Materials - S.O. Kasap.
22 2

Table 2.2: Effective masses of electrons and holes in some selected materials. For metals,
only electrons are listed since there are no explicit holes in them. For semiconductors.
electron effective mass is for the conduction band and hole effective mass is for the valence
band.
me Cu Ag Au
me 1.01 0.99 1.10
me Si Ge GaAs ZnO
me 1.09 0.55 0.067 0.29
mh
1.15 0.37 0.45 1.21
mh

effective mass, me , so that we can rewrite equation 2.2 simply as

eEx
ae = (2.3)
me

The effective mass represents the effect of all the internal forces on the motion of the elec-
tron in the conduction band. Similarly, we can define an effective mass, mh , for the hole
movement in the valence band. It should be emphasized that there is no change in the
actual mass of the electron but only the representation of the internal forces of the atoms
in the solid on the motion of the electron or hole.
For metals like Cu, Ag, or Au the valence electrons are nearly free because they are delo-
calized and can move easily in the solid. In such cases the effective masses are nearly equal
to the rest mass of the electron. In the case of semiconductors, where there is substantial
interaction between the electrons in the bonds and the lattice there is a finite deviation.
Some typical values of effective masses are tabulated in table 2.2.
CHAPTER 3

ELECTRON STATISTICS IN A SOLID

3.1 Density of states

In the band theory of the solid, developed earlier, N atoms with N atomic orbitals formed
N molecular orbitals. Each MO can take 2 electrons (opposite spin) so that there are a total
of 2N energy states. These are discrete states but for large values of N the spacing between
them are so small that they can be considered to be continuous, forming an energy band.
Density of states (DOS) is defined as the number of available energy states per unit
energy per unit volume. The units are J 1 m3 or eV 1 cm3 and it provides informa-
tion on how the energy states are distributed in a given solid. It is typically denoted as
g(E). The experimental density of states of a material can be measured by photo electron
spectroscopy or Scanning Tunneling Microscopy (STM) or Electron Energy Loss spec-
troscopy (EELS). These techniques probe the density of empty or filled states around the
Fermi energy, called Local DOS (LDOS). Density functional calculations can also be used
to calculate the density of states. These model the electron density distribution in a solid
and also model the atomic potential within the solid. Figure 3.1 shows the calculated DOS
for Cu around the Fermi energy.
The density of states can be used to calculate the total number of electron in a band. If
g(E) is the DOS, then the total number of electrons in a band, S(E) is given by

Z
S(E) = g(E)dE (3.1)
E

Second Edition. 23
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
24 3

Figure 3.1: Calculated DOS of Cu around the Fermi level. The filled states lie below EF
while the empty states lie above EF . The broad peak below EF corresponds to the filled 3d
states. Adapted from http://www.personal.psu.edu/ams751/VASP-Cu/

where the integration is performed over the entire energy band. This equation assumes that
the probability of occupation of the state is 1. This is not always true when we look at
the conduction band of a semiconductor, where the occupation probability is defined by
a Fermi function. An energy expression for the density of states, g(E), will be useful for
evaluation of the integral in equation 3.1.

3.1.1 DOS in a 3D uniform solid


To simplify the calculation for g(E) consider a 3D solid with uniform potential. This is
a simplification of a real solid but is a good approximation of the valence band of metals
where the electrons are loosely bound to the atom and are delocalized. We will also use this
approximation for electrons and holes near the edge of the band. For simplicity the uniform
potential can be taken to be zero. For this solid the electron is defined by 3 quantum
numbers (n1 ,n2 , n3 ) and its energy is given by

h2
E = (n2 + n22 + n23 ) (3.2)
8me L2 1
Equation 3.2 is for a cubic solid of length L with the 3 quantum numbers for the 3 axes.
me is the free electron mass. We can replace the 3 quantum numbers by a single value n so
that equation 3.2 is modified into
h2 n2
E = (3.3)
8me L2
For small values of n these energy levels are quantized, but for large values of n the spacing
between them are close so that the energy levels can be considered to be continuous. So
DENSITY OF STATES 25

Figure 3.2: Energy states in a solid with uniform potential. The portion of the sphere
corresponds to the constant energy surface. Only the first quadrant is to be considered
since the quantum numbers are non-zero positive integers. Adapted from Principles of
Electronic Materials - S.O. Kasap.

n represents the radius of a sphere, where the total number of states within the sphere is
given by its volume. This is shown schematically in figure 3.2. Since the quantum numbers
can only be positive (the quantum numbers represent the electron wavefunction and it can
be shown that to avoid exponential increasing functions the quantum numbers have to be
non-zero positive integers) we can only take the first quadrant of the sphere.
Hence the total number of orbitals (energy states), Sorb (n), is given by the volume of the
sphere in the first quadrant
1 4 3 1
Sorb (n) = ( n ) = n3 (3.4)
8 3 6
Since each orbital can take two electrons of opposite spin, the total number of energy states
(including spin), S(n), is given by
1 3
S(n) = 2Sorb (n) = n (3.5)
3
We can relate n (quantum number of the electron in the solid) to the energy E using equa-
tion 3.2 to write the total number of states in terms of energy, S(E). This is given by

1 3 L
3
S(E) = (8me E) 2 3 (3.6)
3 h
Dividing by the volume of the cube will give total number of states per unit volume, Sv (E).
The density of states is the differential of the total number of states, so that g(E) is given
by
me 3
g(E) = 8 2 ( 2 ) 2 E (3.7)
h
26 3

x 10
46 3D DOS
10

8
g(E) (J1m3)

0 1 2 3 4 5
Energy (eV)

Figure 3.3: Plot of DOS vs. E for a 3D solid using free electron mass. This is a plot of
equation 3.7 using MATLAB.

Equation 3.7 gives the DOS in a solid with a uniform potential. At the bottom of the band,
which is normally chosen as the reference so energy is set to 0, DOS is zero. As the energy
increases g(E) also increases. The functional form is shown schematically in figure 3.3.
g(E) represents the density of available states. It does not provide information whether
those states are occupied or not. The occupation is given by the Fermi function and is
usually a function of temperature.

3.1.2 DOS for a 2D solid


The density of states function will change upon changing the dimensionality of the solid.
Consider the case of a 2D solid with a uniform potential. There are 2 quantum numbers,
n1 and n2 , which are related to the energy, similar to equation 3.2.

h2 2 2 h2 n2
E = (n1 + n 2 ) = (3.8)
8me L2 8me L2
For a 2D case, n, represents the radius of a circle, shown in figure 3.4, and only the first
quadrant can be considered since the quantum numbers should be positive. It is possible to
calculate the density of states per unit area, Sarea (n), including spin

n2
Sarea (n) = (3.9)
2
Using equation 3.8 it is possible to calculate the DOS in terms of energy, Sarea (E)
4me
Sarea (E) = E (3.10)
h2
Differentiating equation 3.10 gives the density of states in two dimensions
4me
g(E) = (3.11)
h2
The density of states function is independent of energy, unlike 3D where g(E) increases
with energy. It is represented as a step function at different energy values.
ELECTRON OCCUPATION PROBABILITY 27

Figure 3.4: Energy states in a 2D solid with uniform potential. Instead of a sphere states
of constant energy form a circle and only the first quadrant is relevant. Adapted from
Principles of Electronic Materials - S.O. Kasap.

3.1.3 DOS for a 1D solid


The calculation for a 1D solid is similar to the earlier calculations except that there is only
one quantum number and spatially it is represented on a line (instead of circle in 2D and
sphere in 3D). The total number of states, per unit length, S(n), is just 2n and this is related
to energy by equation 3.12. r
8me
n= E (3.12)
h2
The density of states is given by
r
8me 1
g(E) = (3.13)
h2 E
In a 1D solid the density of states decreases with energy. For a zero dimensional solid,
energy states are only discrete. Solids with two, one, and zero dimensionality can be
obtained by reducing the length in one or more dimensions. A thin film is an example of a
two dimensional solid (or a single or bi layer of graphene ), while a quantum wire is a one
dimensional solid. A quantum dot is a zero dimensional solid. The density of states and
hence the electronic properties of these materials are different from a bulk solid. The DOS
for solids of different dimensionalities are shown in figure 3.5.

3.2 Electron occupation probability

Density of states gives the number of available states for electrons to occupy. At absolute
zero, electrons occupy the lowest energy state. Above 0 K, there is always some thermal
energy for the electrons to occupy the unoccupied energy states. There are different statis-
tics to describe the occupation of energy levels. The simplest statistics is the Boltzmann
28 3

Figure 3.5: DOS for bulk, 2D, 1D, and 0D solids. The y-axis is a qualitative representation
for the different dimensions. Adapted from http://britneyspears.ac/physics/dos/dos.htm

1
Boltzmann function
0.8

0.6
p(E)

0.4

0.2

0 0.2 0.4 0.6 0.8 1


Energy (eV)

Figure 3.6: Boltzmann probability distribution vs. energy at 1000 K. The probability drops
steeply as energy increases due to the exponential nature of the function. The plot was
generated in MATLAB.

statistics which gives the probability of occupation, p(E), of a given energy state, E,

E
p(E) = A exp( ) (3.14)
kB T

A is a constant. At 0 K all the particles have energy 0 and at any given T, p(E) gives the
probability of occupation. For a given temperature, p(E) reduces as E increases, as shown
in figure 3.6.
Boltzmann statistics works for a system of non-interacting particles but electrons have a
strong repulsive interaction. By Paulis exclusion principle only 2 electrons can occupy
a given energy state (of opposite spin). So all electrons cannot occupy the same energy
ELECTRON OCCUPATION PROBABILITY 29

Fermi function
0.8

T = 0.1 K
0.6
f(E)

T = 300 K
T = 2000 K
0.4

0.2

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5


Energy (eV)

Figure 3.7: Fermi function vs. energy at three different temperatures. The probability
drops steeply as energy is increased from the Fermi function. To increase the probability
the temperature has to be increased. The plot was generated using MATLAB using EF =
2.5 eV . T = 0.1 K was used to simulate the 0 K distribution.

state, even at absolute zero. The statistics obeyed by electrons is given by the Fermi-Dirac
statistics.

3.2.1 Fermi-Dirac statistics

In Fermi-Dirac statistics, the probability of electron occupation of a given energy state is


represented by f (E) and given by

1
f (E) = (3.15)
E
1 + A exp( )
kB T

A is a constant. f (E) is called the Fermi function. For solids A is related to the Fermi
energy (EF ) so that f (E) is given by

1
f (E) = (3.16)
(E EF )
1 + exp[ ]
kB T

At absolute zero all energy levels below the Fermi level are occupied so that the occupation
probability is 1. Above EF the levels are empty so that f (E) is 0. Also, at any temperature
f (E) at the Fermi level is 0.5. Figure 3.7 plots the Fermi function as a function of energy.
When the energy difference (E EF ) is much larger than kB T the Fermi function simpli-
fies to the Boltzmann form shown in equation 3.14.
If g(E) is the density of states and f (E) gives the probability of occupation of those states
at a given temperature, the number of occupied states, n(E), is given by
Z
n(E) = g(E) f (E)dE (3.17)
30 3

If the number of occupied states in an energy band needs to be calculated the integration
needs to be performed over the entire band. This will be a function of temperature, since
the Fermi function is temperature dependent. Equation 3.17 can be used to calculate the
concentration of electron and holes in semiconductors, which decides their conductivity.

3.3 Density of states in silver

Consider an example to calculate the density of states in a metal, silver (Ag). Ag is a


free electron metal, electrons in the outer shell are delocalized and are free to move in
the material. Hence, valence electrons in Ag can be treated as electrons in an uniform
potential. The atomic weight of Ag is 107.9 gmol 1 and the density () is 10.5 gcm3 .
Hence the number of atoms per unit volume (nV ) can be calculated
NA
nV = (3.18)
At.wt
where NA is Avogadros number. This gives nV to be 5.85 1022 atoms cm3 .
The Fermi energy (EF ) of Ag is at 5.5 eV . This is with reference to the bottom of the
valence band (taken as zero). So the density of states, at the Fermi energy, for Ag can be
calculated using equation 3.7 is given by
me 3
g(E) = 8 2 ( 2 ) 2 EF (3.19)
h
where EF is 5.5 eV . This gives a number 9.95 1046 m3 J 1 or converting the units 1.59
1022 cm3 eV 1 . This is of the same order of magnitude as the number of atoms per unit
volume. Close to the bottom of the band the density of states is still a substantial quantity.
Consider an energy kB T above the bottom of the band. At room temperature this energy is
approximately 25 meV . Using equation 3.7 the density of states is 1.09 1021 cm3 eV 1
which is still a substantial fraction of the number of atoms.
In order to calculate the total number of electrons in the band equation 3.17 can be inte-
grated from the bottom of the band to EF . The occupation probability, f (E), is 1.
Z EF
n(E) = g(E)dE (3.20)
0
The integral is
me 3 2
n(E) = 8 2 ( 2 ) 2 EF EF (3.21)
h 3
The calculated value of n(E) is 5.08 1022 cm3 which is very close to the number of
atoms per cm3 . Since each atom contributes one electron in Ag this is also the number
of electrons and they fill all the states below EF . Thus, a simple model of a solid with a
uniform potential matches closely with reality. I silver, EF is in the middle of the band
so that there are empty available states for the electrons to occupy. When an electric field
electrons travel opposite to this field and they can occupy these empty states. This makes
Ag a very good conductor of electricity.

3.4 Fermi function vs. Boltzmann function

We can compare the occupation probability using Fermi function and the Boltzmann func-
tion. Consider the case when (E EF ) is equal to kB T . f (E), equation 3.16, is equal
FERMI FUNCTION VS. BOLTZMANN FUNCTION 31

Fermi vs. Boltzmann function


1
f(E)
0.8
p(E)
Probability

0.6

0.4

0.2

0 1 2 3 4 5 6
(EEF)/kB T

Figure 3.8: Comparison of the Fermi and Boltzmann probability distribution vs. normal-
ized energy at constant temperature. Energy is plotted with reference to EF and normalized
by temperature. At low (E EF )Fermi function is accurate while at higher values Boltz-
mann function is a good approximation. The plot was generated in MATLAB.

to 0.26, while Boltzmann function, equation 3.14, is 0.367. Consider when (E EF ) is


equal to 2kB T . f (E) is equal to 0.12, while Boltzmann function is 0.135. If (E EF ) is
equal to 10kB T , f (E) is 4.5 105 while the Boltzmann function is 4.54 105 . Thus,
as (E EF ) becomes higher compared to kB T , the Fermi function can be approximated
by the Boltzmann distribution. This can be seen in figure 3.8, which compares the Boltz-
mann and Fermi function for energies above the Fermi energy (EF ). As seen from figure
3.8 when (E EF ) is around 2kB T both functions start converge so that the Boltzmann
approximation is valid for the Fermi function. At room temperature 10kB T is 250 meV or
0.25 eV . This number is smaller than the band gap of most semiconductors (Si has band
gap of 1.1 eV ). So for calculating electron occupation in semiconductors the Boltzmann
function is a good approximation for the Fermi function.

Problems - chapters 1-3

3.1 For a linear array of six hydrogen atoms, draw the six possible molecular orbitals
in order of increasing energy. How does the energy depend on the number of nodes? Plot
qualitative energy vs. bond length curves for this system and fill the level with appropriate
number of electrons. What would you expect to be the equilibrium configuration of six H
atoms?
3.2 Draw the energy vs. bond length curves for
(a) Ar
(b) NaCl
(c) Na
(d) Mg
32 3

Your diagram should highlight the fact that while Na and Mg are metals, Ar and NaCl are
insulators.
3.3 There are 10 electrons in a slab that measures 0.5(a) nm 1(b) nm 2(c) nm.
Each electron in the slab can be represented by a set of 3 quantum numbers (n1 , n2 , n3 ),
which are positive integers (greater than zero) and are related to the energy of the slab and
slab dimensions by
h2 n21 n2 n2
E = [ 2 + 22 + 23 ]
8me a b c
(a) Assign quantum numbers to the electrons

(b) Deduce EF from the energy distribution of electrons


(c) Determine the density of states at EF , including spin
(d) What is the total kinetic energy of electrons in the slab?
(e) What is the average kinetic energy of electrons in the slab?

3.4 Derive the expression for the density of states for a two dimensional solid and one
dimensional solid. Compare this with the expression for a three dimensional solid.
3.5 Plot the Fermi function for temperatures of 0, 500, and 2000 K semi quantitatively
and on the same plot. How accurate is the Boltzmann function as an approximation of the
Fermi function when E EF = 3kB T and E EF = 15kB T ?
CHAPTER 4

INTRINSIC SEMICONDUCTORS

4.1 Introduction

Semiconductors can be divided into two categories.

1. Intrinsic semiconductors

2. Extrinsic semiconductors

This classification is related to the purity of the semiconductors. Intrinsic or pure semi-
conductors are those that are ideal, with no defects, and no external impurities. The con-
ductivity of these semiconductors increases with temperature. As opposed to intrinsic
semiconductors, extrinsic semiconductors have some impurities added to modify the con-
centration of charge carriers and hence the conductivity. Their conductivity has a more
complex temperature dependence, given by the concentration of the impurities. Extrinsic
semiconductors are used extensively due to the ability to precisely tailor their conductivity
by adding the impurities. Intrinsic semiconductors (especially Si and Ge) are used as opti-
cal and x-ray detectors (at low T) where a low concentration of charge carriers is required.

4.2 Intrinsic Si

Si is a semiconductor material with 4 electrons in the outer shell. These 4 electrons occupy
4 sp3 hybrid orbitals with a tetrahedral arrangement. This gives rise to a full valence band
Second Edition. 33
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
34 4

Figure 4.1: (a) Representration of the hybrid orbitals in Si. (b) These form a valence and
conduction band with a band gap. At absolute zero the valence band is completely full and
conduction band is completely empty. Adapted from Principles of Electronic Materials -
S.O. Kasap.

(VB) and an empty conduction band (CB). This energy gap is called the band gap. This
information is summarized in figure 4.1.
The energy levels are referenced with respect to the bottom of the valence band. Ev
and Ec represent the top of the valence band and the bottom of the conduction band. The
energy difference between them is the band gap (Eg ). The top of the conduction band is the
vacuum level and is located at (Ec + ) above the conduction band where is the electron
affinity of Si. For Si, the electron affinity value is 4.05 eV . The band gap at 0 K is 1.17 eV ,
while at room temperature the value is slightly lower, around 1.10 eV .
At any temperature, thermal excitation causes electrons to move from the valence band
to the conduction band. These electrons in the conduction band are delocalized and can
move in the solid when an external electric field is applied. When electrons are excited
to the conduction band they leave behind holes in the valence band. These holes are also
delocalized and move in the direction opposite to the electrons. These electrons and holes
are responsible for conduction. Electron-hole pairs in Si can also be generated by using
electromagnetic radiation. The minimum energy of the radiation required is equal to the
band gap. If the energy is less than Eg electron excitation does not occur since there are no
states in the band gap. The relation between Eg and the maximum wavelength of excitation
( ) is given by

hc
= (4.1)
Eg

For Si, the wavelength is approximately 1060 nm and lies in the IR region. This is the
reason why Si is opaque since visible radiation (400 - 700 nm) will be absorbed forming
electron-hole pairs. Glass (SiO2 ) on the other hand has a band gap of approximately 10 eV
and hence the maximum wavelength is 100 nm (in the UV region) making it transparent.
Absorption of light by Si is shown in figure 4.2.
CONDUCTIVITY EQUATION 35

Figure 4.2: (a) Electron-hole formation in Si due to absorption of light. The minimum
energy required is equal to the band gap. (b) The absorption of light by the Si lattice. An
electron located at the bond is excited into the solid, leaving behind a hole. Adapted from
Principles of Electronic Materials - S.O. Kasap.

4.3 Conductivity equation

Conductivity in a semiconductor is due to movement of electrons in the CB and holes in


the VB in an applied electric field. This is shown schematically in figure 4.3. These move
in opposite directions since hole motion in the VB is due to electron motion in the opposite
direction. Figure 4.5 shows the hole motion in the VB due to electron tunneling from one
bond to the next. Ultimately the hole recombines with the electron and gets annihilated.
Thus, formation of electron and holes and their recombination is a dynamic process. This
depends on the temperature of the sample (for an intrinsic semiconductor) so that there is
an equilibrium concentration at any given temperature.
Conductivity in a semiconductor depends on two factors

1. Concentration of electrons and holes. Denoted as n and p and is temperature depen-


dent.

2. Ability of the electron and holes to travel in the lattice without scattering.

Electrons and holes are said to drift in the lattice. This is because they undergo multiple
scatterings with the atoms. In typical semiconductors, concentration of electrons and holes
are small, compared to the atomic concentration, so that electron-electron scattering can be
ignored. But there is still the interaction between the electron and lattice. This is defined
by a quantity called mobility, denoted by the symbol . Mobility refers to the ability of
the charge carriers to move in the lattice. Mobility is related to the effective mass of the
36 4

Figure 4.3: Conduction in a semiconductor. (a) Random motion of electron in the CB and
holes in the VB. (b) When an electric field (external potential) is applied the energy levels
are shifted. Electrons and holes move in opposite directions in the field, giving rise to a
current. Adapted from Principles of Electronic Materials - S.O. Kasap.

Figure 4.4: (a) - (f) Sequence of steps showing hole formation, motion, and finally annihi-
lation in a semiconductor. Adapted from Principles of Electronic Materials - S.O. Kasap.
CONDUCTIVITY EQUATION 37

carrier (me and mh ) and the time between two scattering events (e and h ). The relation is

ee
e =
me
eh (4.2)
h =
mh

The effective mass term takes into account the effect of the lattice arrangement on the
movement of the carriers. Using the carrier concentration and the concept of mobility it is
possible to write a general equation for conductivity ( ) given by

= nee + peh (4.3)

According to equation 4.3 higher the carrier concentration (n or p) higher the conductivity.
Also, higher the mobility, higher the conductivity. Since mobility is related to the time
between 2 scattering events, more the time between 2 scattering events greater is the con-
ductivity.

4.3.1 Electron mobility in Si


Consider the case of Si, where the electron mobility (e ) is 1350 cm2V 1 s1 and h is 450
cm2V 1 s1 . The effective masses are me is 0.26 me and mh is 0.38 me . Using equation
4.2 it is possible to find the scattering time for electrons and holes. Consider electrons, e
is calculated to be 2 1013 s or 0.2 ps (pico seconds). This time, between 2 scattering
events, is extremely short. To calculate the distance traveled by the electron in this short
time we can use an estimate of the velocity obtained from the thermal energy of electrons,
which is given by 23 kB T . For an electron in the CB the potential can be approximated to
be zero and hence the thermal energy is equal to the kinetic energy ( 12 me vth2 ). Equating

the two, it is possible to find the thermal velocity of electrons at room temperature and the
value is 1.16 105 ms1 . From the thermal velocity and the scattering time it is possible
to find the distance traveled between 2 scattering events. This distance is approximately 23
nm. In terms of number of unit cells this works out to be 43 unit cells (Si lattice constant
is 0.53 nm). Thus, despite the short scattering time the electron can travel a substantial
distance, in terms of unit cells, before scattering. This is because only the lattice can
scatter and electron-electron scattering is limited due to the low concentration.
Mobility is temperature dependent. It also depends on the type of semiconductor and the
presence of impurities. Mobility usually decreases with increasing impurity concentration
since there are more scattering centers in the material. Ge has a higher mobility than Si.
e for Ge is 3900 cm2V 1 s1 . e for GaAs is even higher, 8500 cm2V 1 s1 . Thus, based
on mobility, GaAs would be the material with the highest conductivity. But conductivity
also depends on the carrier concentration. The dominating term, in equation 4.3, would
determine the conductivity.
38 4

4.4 Carrier concentration in semiconductors

The carrier concentration in an energy band is related to the density of available states,
g(E), and the probability of occupation, f (E). This is given by
Z
n= g(E) f (E)dE (4.4)
band

where the integration is over the entire band. f (E) represents the Fermi function and for
energies much greater than kB T it can be approximated by the Boltzmann function.
1 E EF
f (E) = ' exp( ) (4.5)
E EF kB T
1 + exp( )
kB T
To find the number of electrons in the conduction band (n) then equation 4.4 can be written
as
EZc +

n= gCB (E) f (E)dE (4.6)


Ec

where the simplified Fermi function is used. The actual density of states function in the
CB depends on the semiconductor material but an approximation of a 3D solid with an
uniform potential can be used. In this case gCB (E) turns out to be

8 2 3 1
gCB (E) = 3
(me ) 2 (E Ec ) 2 (4.7)
h
Since the density of states function is with respect to the bottom of the CB E is replaced by
(E Ec ). To further simplify the integral the limits can be changed from Ec to instead
of Ec + . This is because most of the electrons in the CB are close to the bottom and is
usually much larger than kB T . Hence, making the substitutions in equation 4.6 and doing
the integration the electron concentration in the conduction band is given by

(Ec EF )
n = Nc exp[ ]
kB T
(4.8)
2me kB T 3
Nc = 2 ( )2
h2
where Nc is a temperature dependent constant called the effective density of states at the
conduction band edge. It gives the total number of available states per unit volume at the
bottom of the conduction band for electrons to occupy. Ec is the bottom of the conduction
band and EF is the position of the Fermi level.
A similar equation can be written for holes

(EF Ev )
p = Nv exp[ ]
kB T
(4.9)
2mh kB T 3
Nv = 2( )2
h2
where Nv is the effective density of states at the valence band edge. Equations 4.8 and 4.9
give the electron and hole concentrations in semiconductors (intrinsic or extrinsic). The
CARRIER CONCENTRATION IN SEMICONDUCTORS 39

Figure 4.5: (a) Band picture of Si (b) DOS in CB and VB (c) Fermi function for electron
and holes (d) Electron concentration in CB and hole concentration in VB, obtained by
multiplying (b) and (c). Adapted from Principles of Electronic Materials - S.O. Kasap.
40 4

concentrations depend on the position of the Fermi level. The calculations are summarized
in figure 4.5. This plots the DOS function in the CB and VB and the variation in the Fermi
function in these bands. The Fermi level is usually far away from the band edges so that
it can be approximated by the Boltzmann function. The electron and hole concentration
is got by multiplying both and these are located close to the edge of the band. This also
justifies the assumption that the upper integration limit can be changed to , since the
carriers are located very close to the band edges.

4.5 Intrinsic carrier concentration

To eliminate EF consider multiplying n and p in equations 4.8 and 4.9. This gives

(Ec Ev )
np = Nc Nv exp[ ] (4.10)
kB T
From figure 4.1 it can be seen that this is nothing but the band gap so that equation 4.10
becomes
Eg
np = Nc Nv exp[ ] (4.11)
kB T
Thus, the product of electron and hole concentration is independent of the Fermi level
position but only on the band gap and temperature, apart from Nc and Nv . In an intrinsic
semiconductor n = p since electron and holes are created in pairs (hole is the absence of
electron). This is called ni the intrinsic carrier concentration. Substituting in equation
4.11 the intrinsic carrier concentration can be calculated.
p Eg
ni = Nc Nv exp( ) (4.12)
2kB T

Thus, the intrinsic carrier concentration is a semiconductor is dependent only on the band
gap (Eg ). ni is a material property (at a given temperature). Equation 4.11 can now be
rewritten as
np = n2i (4.13)
This equation is called law of mass action and it valid for any semiconductor at equilib-
rium. For an intrinsic semiconductor equation 4.13 is trivial since n = p = ni but even
when n and p are not equal to product should still yield n2i . This has important implica-
tions for extrinsic semiconductors. The conductivity equation 4.3 can now we rewritten for
intrinsic semiconductors as
i = ni e(e + h ) (4.14)
CHAPTER 5

INTRINSIC
SEMICONDUCTORS-CONDUCTIVITY

5.1 Carrier concentration in intrinsic Si

Consider intrinsic Si at room temperature. Intrinsic refers to pure Si, an ideal single crystal
with impurity concentrations below ppb (parts per billion). There is an equilibrium con-
centration of electrons and holes at room temperature, due to thermal excitation. This is
the intrinsic carrier concentration (ni ) given by

p Eg
ni = Nc Nv exp( ) (5.1)
2kB T

Nc and Nv , the effective density of states at the band edges, are dependent on temperature
and the effective mass of the electron and holes respectively. For Si, me is 1.08 me and mh
is 0.60 me . From this the effective density of states can be calculated using

2me kB T 3
Nc = 2( )2
h2 (5.2)
2mh kB T 3
Nv = 2( )2
h2

At room temperature the values of Nc and Nv for Si are 2.81 1025 m3 and 1.16 1025
m3 . These are the total number of available states at the band edges for the electrons
and holes to occupy. Hence, the intrinsic carrier concentration at room temperature can be
Second Edition. 41
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
42 5

Table 5.1: Carrier mobilities and band gaps for some common semiconductors
Material e (cm2V 1 s1 ) h (cm2V 1 s1 ) Eg (eV )
Ge 3900 1900 0.66
Si 1350 450 1.10
GaAs 8500 400 1.43

calculated using equation 5.1 with the band gap value of 1.10 eV . This gives ni equal to
1016 m3 or 1010 cm3 . Thus, pure Si at room temperature has 1010 cm3 electrons in the
conduction band and a equal number of holes in the valence band. To place this number
in context, the number of Si atoms per unit volume can be calculated from the density (2.3
g cm3 ) and the atomic weight (28 g mol 1 ). This works out to be 5 1022 atoms cm3 .
So there is approximately 1 electron/hole for every 5 1011 Si atoms!
This is a very low concentration compared to metals, where the electron concentration is
the comparable in magnitude to the atomic density and explains why semiconductors have
a poor conductivity compared to metals. The conductivity is given by

p Eg
i = ni e(e + h ) = Nc Nv exp( ) e (e + h ) (5.3)
2kB T

For Si, e and h are 1350 cm2V 1 s1 and 450 cm2V 1 s1 respectively. So, the room
temperature conductivity is 3 106 1 cm1 or a resistivity of 3.5 105 cm. The
room temperature conductivity of Cu is 16 107 cm, nearly 12 orders of magnitude
lower than Si and the difference is directly related to the difference in concentration of the
charge carriers.

5.2 Carrier concentration in intrinsic semiconductors

Pure Si is a very poor conductor. It is rarely used in the intrinsic form, except for specific
optical sensor applications, at liquid N2 temperatures. Here is it usually lightly doped with
Li to control the carrier concentration. For higher conductivity, using equation 5.3, we
either need a material with a higher mobility or a higher intrinsic carrier concentration (i.e.
lower band gap). Mobility and band gap values for 3 commonly used semiconductors are
listed in table 5.1.
Based on mobilities, GaAs would be the material to choose for higher conductivity but
GaAs also has a higher band gap so that the intrinsic carrier concentration would be low.
The carrier concentration and conductivity for pure GaAs can be calculated in a manner
similar to that done for Si. The effective mass values for GaAs are me = 0.067 me and mh =
0.50 me . Using equation 5.2 the effective density of states can be calculated to be Nc = 4.3
1023 m3 and Nv = 8.85 1023 m3 . This gives an intrinsic carrier concentration of 2.4
106 cm3 and hence a conductivity of 3.4 109 1 cm1 . A similar calculation can
be done for Ge so that table 5.1 can be updated to give table 5.2 that contains the intrinsic
carrier concentration and conductivity for the semiconductors listed in table 5.1.
It can be seen that while a higher mobility can lead to an increase in conductivity the
dominant term is the carrier concentration and consequently the band gap. Since the carrier
concentration has an exponential dependence on Eg lowering Eg will have the greatest
effect on conductivity. Based on table 5.2, Ge would be the semiconductor material of
FERMI LEVEL IN INTRINSIC SEMICONDUCTORS 43

Table 5.2: Carrier concentration and conductivity for the three semiconductors listed in
table 5.1
Material Eg (eV ) ni (cm3 ) (1 cm1 )
Ge 0.66 2.3 1013 0.02
Si 1.10 1010 3 106
GaAs 1.43 2.4 106 3.4 109

choice due to its high conductivity and low band gap. In fact, the first transistors were
made using Ge. But later, Si has come to dominate the microelectronics industry. The
reason for this is conductivity in Si can be increased by adding specific impurities to the
material. This is also coupled to the fact that Si is the second most abundant material on
earth (27%) while Ge is only present in the parts per million amount.

5.3 Fermi level in intrinsic semiconductors

Fermi level is defined as the energy level separating the filled states from the empty states at
0 K. It is also the highest filled energy level in a metal. This definition needs to be modified
for a semiconductor since these have an energy gap between the filled states (valence band)
and empty states (conduction band). The expression for the carrier concentration (n or p)
in a semiconductor is given by

(Ec EF )
n = Nc exp[ ]
kB T
(5.4)
(EF Ev )
p = Nv exp[ ]
kB T

In an intrinsic semiconductor n =p = ni . For notation purposes, the Fermi level position in


an intrinsic semiconductor is denoted as EFi . Hence, using equation 5.4 and rearranging,
the Fermi energy can be written as

1 1 Nc
EFi = Ev + Eg kB T ln( ) (5.5)
2 2 Nv

Since, the effective density of states depend on the carrier effective mass, using equation
5.2, equation 5.5 can be rewritten as

1 3 m
EFi = Ev + Eg kB T ln( e ) (5.6)
2 4 mh

For Si, the intrinsic Fermi level is calculated to be 0.54 eV above the valence band edge
(Ev ) at room temperature . Since the band gap is 1.10 eV this puts EFi very close to the
center of the gap. If Nc = Nv (me = mh ) then the intrinsic Fermi level will be at the center
of the band gap at all temperatures. A schematic of the energy bands in an intrinsic semi-
conductor is shown in figure 5.1. This picture is true for any intrinsic semiconductor, with
the Fermi level always close to the center of the gap.
In metals the Fermi level separates the filled and empty states. This is because metals have
44 5

Figure 5.1: Band picture of an intrinsic semiconductor showing the VB and CB edge and
location of the Fermi level (EFi ). The electron and hole concentrations are equal and the
Fermi level is located close to the center of the band gap. Adapted from Principles of
Electronic Materials - S.O. Kasap.

partially filled energy bands and the Fermi level lies within the band. This definition can-
not be used for semiconductors. Another definition is that Fermi level defines the average
energy required to remove an electron from the material. This is called the work function,
denoted by , and is the energy difference between the Fermi level and the vacuum level.
This definition can also used for semiconductors, with the realization that electrons in the
CB and the holes in the VB are linked. So the Fermi level, defines the average potential
energy per electron for electrical work. If an external electric field is applied the Fermi
level in the material will no longer be uniform. This will be important when consider-
ing junctions formed between different semiconductors and between semiconductors and
metals.

5.4 Temperature effect on ni

The temperature effect on the carrier concentration can be understood by using equation
5.1. Temperature enters both the pre-exponential and the exponential term. Increasing
temperature has two effects
1. Increases the effective density of states at the band edges (Nc and Nv ).
2. Decreases the exponential portion of equation 5.1, since T is in the denominator.
The exponential terms dominates, as can be seen by a semilog plot of ni vs. inverse tem-
perature, as shown in figure 5.2 for Si. The slope of the plot gives the band gap of the
semiconductor. Changing the semiconductor material, changes the band gap and also the
TEMPERATURE EFFECT ON NI 45

ni vs. inverse T
20
10

15
10

10
10
ni (cm )
3

5
10
Slope = Eg/2kb
0
10

5
10

10
10
1 2 3 4 5 6 7 8 9 10
Inv T (K1)
3
x 10

Figure 5.2: ni vs. inverse T for Si in the range 100-1000 K. The plot is a straight line with
E
slope given by 2kgB . The dominating temperature dependent term is the exponential one
even though the effective density of states also increase with temperature. The plot was
generated in MATLAB.

ni vs. inverse T
16
10

14
Ge
10
Si
10
12 GaAs
ni (cm3)

10
10

8
10

6
10

4
10

2
10

0
10
2 2.5 3 3.5 4 4.5 5
Inv T (K1)
3
x 10

Figure 5.3: ni vs. inverse T for Ge, Si, GaAs in the range 200-500 K. The plots are similar
with different slopes given by their respective band gaps. GaAs has the lowest carrier
concentration while Ge has the largest. The plot was generated in MATLAB.

effective density of states. For different semiconductors the plot of ni vs. T is similar with
different slopes, corresponding to different Eg values. Intrinsic carrier concentrations for
Ge, Si, and GaAs are compared in figure 5.3. The slopes correspond to their respective
band gaps, given in table 5.1. The slope for GaAs is steepest, since it has the highest band
gap.
Increase in concentration and/or mobility has the effect of increasing conductivity. While
concentration increases with temperature mobility decreases with temperature. But be-
cause of the exponential term in equation 5.3, the dominating term is ni . Consider two
46 5

temperatures, T1 and T2 with intrinsic carrier concentrations, ni1 and ni2 . Using equations
5.1 and 5.2 the ratio of the carrier concentration is given by
ni1 T1 3 Eg 1 1
= ( ) 2 exp[ ( )] (5.7)
ni2 T2 2kB T1 T2
If T1 > T2 then ni1 > ni2 .
For Si, when the temperature is doubled from room temperature (300 K) to 600 K, using
equation 5.7, the change in carrier concentration is given by

n600K
i
= 1.17 105 (5.8)
n300K
i

This leads to an approximately 5 orders of magnitude increase in conductivity. Problem


is that almost all devices need to operate at or near room temperature, so that increasing
temperature would not be a feasible option. So another method must be found to increase
and control the conductivity in Si. This is achieved by doping.

Problems - chapters 4-5

5.1 What fraction of current in intrinsic Si (Eg = 1.12eV ) is carried by holes? Take
e = 1350 cm2V 1 s1 and h = 450 cm2V 1 s1 .
5.2 A pure semiconductor has a band gap of 1.25 eV . The effective masses are me =
0.1me and mh = 0.5me , where me is the free electron mass. The carrier scattering time is
10
temperature-dependent, of the form = 10T sec, where T is in K. Find the following at
77 K and 300 K
(a) Concentration of electrons and holes
(b) Fermi energy
(c) Electron and hole mobilities
(d) Electrical conductivity

5.3 GaAs is a direct band gap semiconductor with Eg = 1.42 eV at 300 K. Take
Nc = Nv = 5 1018 cm3 and independent of temperature. Calculate the intrinsic car-
rier concentration at room temperature. Explain numerically how the carrier concentration
can be doubled without adding dopants.
5.4 Calculate the intrinsic carrier concentration of Ge at room temperature. Take me =
0.56me and mh = 0.40me , where me is the electron mass. Use this to calculate room
temperature resistivity. Take e = 3900 cm2V 1 s1 and h = 1900 cm2V 1 s1 . Also,
calculate the position of the Fermi level at room temperature. Band gap of Ge is 0.66 eV .
5.5 In a particular semiconductor, the effective density of states are given by Nc =
Nc0 (T )3/2 and Nv = Nv0 (T )3/2 , where Nc0 and Nv0 are temperature independent. The
experimentally determined intrinsic carrier concentrations as a function of temperature are
tabulated below Determine the product Nc0 Nv0 and the band gap of the semiconductor.
Assume Eg is independent of temperature.
TEMPERATURE EFFECT ON NI 47

T (K) ni (cm3 )
200 1.82 102
300 5.83 107
400 3.74 1010
500 1.94 1012
CHAPTER 6

EXTRINSIC SEMICONDUCTORS

6.1 Introduction

The carrier concentration of intrinsic Si at room temperature is 1010 cm3 and is a constant
defined by the band gap of the material. This gives a conductivity of 3 106 1 cm1 .
To increase the conductivity one can use a lower band gap material, like Ge. But if the
material cannot be changed from intrinsic Si, then the only way to increase carrier concen-
tration is to increase temperature.
Doping is a method of selectively increasing carrier concentration, by addition of selected
impurities to an intrinsic semiconductor. This is called an extrinsic semiconductor. In any
semiconductor at equilibrium, the law of mass action should be satisfied i.e.

np = n2i (6.1)

In an intrinsic semiconductor n = p = ni , so equation 6.1 becomes trivial. But when


impurities are added to a semiconductor, to increase the carrier concentration, equation 6.1
restricts the increase to either electrons or holes. Both cannot be increased simultaneously.
If n increases, then p decreases, and vice versa. Thus doping can selectively increase elec-
tron or hole concentration.
An extrinsic semiconductor is formed by adding a small amount of impurities to a pure
semiconductor crystal to preferentially increase carrier concentration of one polarity.
There are two important terms in this definition
Second Edition. 49
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
50 6

Figure 6.1: Two dimensional picture of Si. Each Si has 4 sp3 hybrid electrons which can
form a covalent bond with 4 other Si atoms. The arrangement is tetrahedral, which is
shown in the figure as a two dimensional array of atoms with 4 bonds each. Adapted from
Principles of Electronic Materials - S.O. Kasap.

1. small - the concentration of impurities is very small, of the order of ppm (parts per
million) or ppb (parts per billion).
2. impurities - these are precisely controlled additions to a pure material. Not impu-
rities in the sense of unwanted material. Dopants would be a better term for these
additions.

6.2 n-type doping

Consider a two dimensional picture of Si, as shown in figure 6.1. Si, has 4 electrons in
the outer shell. The s and p orbitals hybridize to form 4 sp3 orbitals. A small amount of
pentavalent impurity, like As, is added to Si. The amount of impurity added is small so that
the crystal structure of Si is not disturbed and the impurity behaves like individual atoms
and do not form clusters. Later we will quantify the amount of As needed to increase the
conductivity and show that our assumption is justified. The As atom can substitute for a Si
atom in the lattice, as shown in figure 6.2. Since, As has 5 electrons, 4 of these are involved
in bonding with the Si atom. There is an extra electron in the As atom, and if sufficient
energy is supplied it can be delocalized and made available for conduction.
To calculate the energy required to delocalize the extra electron from As, a simple calcu-
lation can be done by modeling the system using a one electron H-like atom. The binding
energy of an electron in the H atom is given by
me e4
Eb = = 13.6 eV (6.2)
802 h2
N -TYPE DOPING 51

Figure 6.2: Si lattice with As impurity added. The As atom substitutes for Si in the lattice
and donates one extra electron making it an n-type dopant. Adapted from Principles of
Electronic Materials - S.O. Kasap.

where me is the mass of electron and 0 is the permittivity of free space. This equation can
be modified to calculate the binding energy of the extra electron of the As atom located in
the Si matrix. This can be done by using the effective mass of electron, me , and the relative
permittivity (0 r ) of Si. Equation 6.2 now becomes
me 1
EbAs = Eb = 0.032 eV (6.3)
me r2
EbAs represents the energy required to delocalize the extra electron from As and make it
available for conduction. The calculated value of 0.032 eV or 32 meV is comparable to
thermal energy (kB T ) at room temperature, which is 25 meV . Thus, when As is added to
Si, there is one excess electron in the conduction band for each As atom. These electrons
are available for conduction and are responsible for the large increase in conductivity by
doping.
The actual value for the ionization of the electron from As, by density functional theory
calculations, is around 54 meV , which is also small and comparable to thermal energy.
The same argument is valid for other pentavalent impurities like P and Sb. The ionization
energies for these elements are also small, P (45 meV ) and Sb (39 meV ), and comparable
to the value for As. Pentavalent impurities like P, Sb, and As have an extra electron to
donate to the Si crystal. These impurities are called donors. Since the extra electron is
delocalized at room temperature and are present in the conduction band the donor energy
levels are located close to the conduction band. This is shown schematically in figure
6.3. The As atoms are localized in the Si lattice, so they are depicted as individual atomic
levels in the band gap. The distance between the donor level (Ed ) and the conduction
band minimum (Ec ) is the donor ionization energy, given by equation 6.3. This value is
of the order of tens of meV , which is much smaller than the band gap of Si (1.10 eV ).
52 6

Figure 6.3: Si energy band with the As donor levels close to the conduction band. The
As concentration is low so that its energy levels are localized. Adapted from Principles of
Electronic Materials - S.O. Kasap.
P-TYPE DOPING 53

Figure 6.4: (a) B doping in a Si lattice. (b) The extra hole is delocalized and gets excited to
the valence band. This electron is free to move in the Si lattice. Adapted from Principles
of Electronic Materials - S.O. Kasap.

If Nd is the concentration of the donor atoms in the lattice, there are Nd extra electrons
that are available for conduction. At room temperature, these electrons are located in the
conduction band so that the concentration of electrons is given by n = Nd , when (Nd >>
ni ). The concentration of holes is given by equation 6.1.

n2i
p= << Nd (6.4)
Nd
Hence the conductivity of the n-type doped Si sample is given by

= nee + pee Nd ee (6.5)

6.3 p-type doping

Consider intrinsic Si where a trivalent impurity like B is added. The concentration of the
B atoms is small so that the Si lattice is not changed by individual B atoms substitute for
Si atoms in the lattice. This is shown schematically in figure 6.4. Since a B atom has only
3 electrons it can form 3 bonds with 3 Si atoms. But an extra electron from the valence
band of Si can be excited to the B energy level to bond with the fourth Si atom. This
leaves behind a hole in the valence band, that is available for conduction. The energy for
ionization of the electron to the B level can be calculated in a similar manner to that for the
n-type impurities. The ionization energy for various trivalent impurities like B (45 meV ),
Al (57 meV ), and Ga (72 meV ) is of the order of thermal excitation energy. So electrons
from the valence band can be easily excited to the B energy level. There is one hole in
the valence band for every B atom doped in the lattice. Since the trivalent atom accepts
electrons from the Si, these are called acceptors.
54 6

Figure 6.5: Acceptor energy levels are close to the valence band of the Si. Electrons from
the valence band can get promoted to these levels leaving behind holes. These acceptor
levels are localized due to the small concentration. Adapted from Principles of Electronic
Materials - S.O. Kasap.

Since the acceptor atoms accept electrons from the valence band their energy levels are
located close to the valence band. This is shown in figure 6.5. The distance between the
acceptor level (Ea , localized) and the valence band maximum (Ec ) is the ionization energy.
If Na is the concentration of the acceptors, then at room temperature, the concentration of
holes is given by p = Na , when (Na >> ni ). The concentration of electrons is given by
equation 6.1.
n2
n = i << Na (6.6)
Na
Hence the conductivity of the p-type doped Si sample is given by

= nee + pee Na eh (6.7)

6.4 Conductivity in extrinsic Si

Consider Si with intrinsic carrier concentration of 1010 cm3 . It is doped with As (Nd ) of
concentration 1015 cm3 . Arsenic is an n-type dopant since it has one extra electron which
is donated to the conduction band. Since each As atom donates one electron, the concen-
tration of electrons (n) is 1015 cm3 , which is much larger than ni . Concentration of holes
(p) is given by equation 6.1 and the value is 105 cm3 . Thus, electrons are the majority
charge carriers and holes are the minority charge carriers. The conductivity is given by
COMPENSATION DOPING 55

equation 6.5 and with electron mobility (e ) of 1350 cm2V 1 s1 the conductivity ( ) is
0.216 1 cm1 . This is 5 orders of magnitude higher than the conductivity of intrinsic Si.
The increase in conductivity is due to the addition of 1015 cm3 of As. To put this number
in terms of concentration, the atomic density of Si can be calculated from the density (2.33
g cm3 ) and the atomic weight (28 g mol 1 ). This gives the atomic density of Si to be 5
1022 atoms cm3 . Thus, the concentration of As (that gives 5 orders of magnitude increase
in conductivity) is only 20 parts per billion of Si atoms. Thus the As impurity has to be
carefully controlled since it has a huge influence on the conductivity.
Instead of As, if B (Na ) is added with the same concentration of 1015 cm3 the each B atom
creates one hole, so the concentration of holes (p) is 1015 cm3 (Na >> ni ). Electron con-
centration is 105 cm3 . In a p-type semiconductor, holes are now the majority carriers and
electrons the minority carriers. The conductivity is slightly lower since the hole mobility
is lower but it is still orders of magnitude higher than intrinsic Si.

6.5 Compensation doping

In extrinsic doping the semiconductor is doped with either p or n type dopant. It is possible
to dope both types of dopant in the same material. This type of doping is called compen-
sation doping. Compensation doping is used when junctions are needed to be formed in
the case of electronic devices. For forming a pn junction, a n-doped sample is chosen and
then compensated doped with p-type dopant or vice versa. If there are both donors and
acceptors in a semiconductor then the one with the higher concentration will dominate so
that the final material will be either n or p type.
Consider a material with Nd donors and Na acceptors. Let Nd and Na be >> ni . If Nd > Na ,
then the overall material is n-type with

n2i
n = (Nd Na ) and p = (6.8)
(Nd Na )

If Na > Nd , then the overall material is p-type with

n2i
p = (Na Nd ) and n = (6.9)
(Na Nd )
CHAPTER 7

EXTRINSIC SEMICONDUCTORS - FERMI


LEVEL

7.1 Dopant materials

Typical doping concentrations in semiconductors are in ppm (106 ) and ppb (109 ). This
small addition of impurities can cause orders of magnitude increase in conductivity. The
impurity has to be of the right kind. For Si, n-type impurities are P, As, and Sb while p-
type impurities are B, Al, Ga, and In. These form energy states close to the conduction and
valence band and the ionization energies are a few tens of meV . Ge lies the same group
IV as Si so that these elements are also used as impurities for Ge. The ionization energy
data n-type impurities for Si and Ge are summarized in table 7.1. The ionization energy
data for p-type impurities for Si and Ge is summarized in table 7.2. The dopant ionization
energies for Ge are lower than Si. Ge has a lower band gap (0.67 eV ) compared to Si (1.10
eV ). Also, the relative permittivity for Ge is higher (r = 16) compared to Si (r = 11.9)
and the effective masses for electron and holes are also different. The ionization energies
for dopants in Si and Ge are represented in the band diagram schematically in figure 7.1.
GaAs is a commonly used compound semiconductor. It is a III-V semiconductor with
predominantly covalent bonding, with some ionic character. Doping is done by substitution
and there are a number of possibilities for GaAs, as seen from the periodic table shown in
figure 7.2. For n type doping As (group V) can be replaced by elements from group VI.
These have an extra electron and can act as donors. Similarly, for p type doping Ga (group
III) can be replaced by group II elements, which act as acceptors. Si in group IV can act
as both donor and acceptor, depending on where the Si atom is substituted. This is called
amphoteric doping. It is hard to control the location of Si in the lattice to get a specific

Second Edition. 57
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
58 7

Figure 7.1: Ionization energies of dopants in Si and Ge. The gap center represents approx-
imately the intrinsic Fermi level. Dopants located close to the band edges can be easily
ionized and are called shallow states while those located closer to the gap center are called
deep states. Adapted from Physics of semiconductor devices - S.M. Sze.
DOPANT MATERIALS 59

Table 7.1: Ionization energies in meV for n-type impurities for Si and Ge. Typical values
are close to room temperature thermal energy.
Material P As Sb
Si 45 54 39
Ge 12 12.7 9.6

Table 7.2: Ionization energies in meV for p-type impurities. Typical values are comparable
to room temperature thermal energy.
Material B Al Ga In
Si 45 57 65 157
Ge 10.4 10.2 10.8 11.2

Figure 7.2: Portion of the periodic table around Ga and As (groups


III and V). Elements from groups II - VI, can act as dopants. Source
http://chemistry.about.com/od/periodictable/ss/How-To-Use-A-Periodic-Table.htm
60 7

Figure 7.3: Ionization energies of dopants in GaAs. Group II elements act as acceptors and
group VI elements act as donors. Si can substitute in either Ga or As site,though Si as a n-
type dopant (Ga substitution) has a lower energy. Adapted from Physics of semiconductor
devices - S.M. Sze.

type of doping. Ionization energies of some common dopants in GaAs are shown in figure
7.3. Donors are located close to the conduction band and acceptors close to the valence
band. Si impurity levels can be close to either, depending on whether it is substituted for
Ga or As.
Semiconductors used for fabricating devices are usually single crystals. This is because
polycrystalline materials have defect states due to presence of grain boundaries. These
defects states are located in the band gap and can modify the conductivity. There are two
types of defect states

1. Shallow states - these are located close the band edges and can act as sources of
electrons and holes. Common example is the dopants.

2. Deep states - these are located close to the center of the band gap, see figures 7.1
and7.3 for examples of both. Deep states can act as traps for charge carriers and
reduce the conductivity.

Film growth techniques can also introduce defects in a material, which can affect the con-
ductivity. ZnO is a wide band gap semiconductor with Eg of 3.4 eV . Thin films of ZnO
growth by conventional vapor deposition or solution growth techniques are n-type because
of the presence of Zn interstitials and O vacancies. Thus, it is very hard to get p-type ZnO
because of the presence of these defects.
EF IN EXTRINSIC SEMICONDUCTORS 61

7.2 EF in extrinsic semiconductors

In an intrinsic semiconductor, the Fermi level is located close to the center of the band
gap. Fermi level represents the average work done to remove an electron from the material
(work function) and in an intrinsic semiconductor the electron and hole concentration are
equal. In an extrinsic semiconductor, with the dopants fully ionized, there is an imbalance
in the electron and hole concentration. This in turn is reflected in the Fermi level position
being shifted from the center of the band gap towards either the conduction band or valence
band depending on the type of dopant.
In an n-type semiconductor the electron concentration (n) is related to the position of the
Fermi level (EFn ) by
(Ec EFn )
n = Nc exp[ ] (7.1)
kB T
Equation 7.1 can be modified for an intrinsic semiconductor, where the Fermi level is close
to center of the band gap (EFi ).

(Ec EFi )
ni = Nc exp[ ] (7.2)
kB T
Manipulating equations 7.1 and 7.2, gives the Fermi level position in the n-type extrinsic
semiconductor with respect to the intrinsic Fermi level

n
EFn EFi = kB T ln( ) (7.3)
ni

For an n-type semiconductor with Nd donors which are fully ionized, n = Nd when
Nd  ni , so that the Fermi level is shifted above the center of the band gap, closer to
the conduction band. For Si with Nd = 1015 cm3 and ni = 1010 cm3 , using equation 7.3,
EFn is 0.25 eV above EFi .
A similar argument can be used for p-type semiconductors, where the hole concentration
is higher than the electron concentration. The Fermi level position (EF p ) is given by

p
EF p EFi = kB T ln( ) (7.4)
ni

For a p-type semiconductor with Na donors which are fully ionized, p = Na when Na  ni ,
so that the Fermi level is shifted below the center of the band gap, closer to the valence
band. The Fermi level position with carrier type and concentration for Si is summarized in
figure 7.4.

7.3 Temperature dependence of carrier concentration

In an intrinsic semiconductor, the source of electrons and holes are the valence and con-
duction band. The carrier concentration depends exponentially on the band gap, given
by
p Eg
ni = Nc Nv exp( ) (7.5)
2kB T
A plot of ni vs. T is shown in figure 7.5. The plot is approximately a straight line, with
62 7

Figure 7.4: EF position in Si, with doping type and concentration. The donor and acceptor
concentration was varied from 1014 to 1018 cm3 in steps of 10 and the temperature was
varied from 200 to 450 K. The dotted line in the center represents EFi , which is approxi-
mately Eg /2 at room temperature. For the calculation the variation of EFi with temperature
was also considered. The plot was generated using MATLAB.

Figure 7.5: Carrier concentration vs. inverse temperature for three intrinsic semiconduc-
tors, Ge, Si, and GaAs. There is a single line with a constant slope, given by the band
gap of the semiconductor. The plot was generated using MATLAB and the dotted line
represents room temperature.
TEMPERATURE DEPENDENCE OF CARRIER CONCENTRATION 63

the slope depending on the band gap. In an extrinsic n type-semiconductor, there are two
sources for the electrons (same arguments are valid for p-type semiconductors)

1. The donor energy levels close to conduction band. This has an ionization energy
meV.

2. The valence band of the semiconductor, with ionization energy eV.

Because of the vast difference in the ionization energies for the two sources they operate in
different temperature regimes, so that it is possible to understand the temperature behavior
of the extrinsic semiconductors by dividing into different regimes

7.3.1 Low temperature regime (T < Ts )


At absolute zero there are no ionized carriers. Valence band is full and the donor level is
full and conduction band is empty. As temperature is increased, electrons are excited from
the valence band and the donor level to the conduction band. But since the valence band
ionization energy is of the order of eV , at low temperature the number of electrons excited
from it are negligible compared to the electrons from the donor level. So the valence band
contribution can be ignored and only electrons from the donor level are excited to the CB.
This regime is called ionization regime and extends up to a temperature until all the donor
electrons are ionized. The electron concentration (in CB), in the ionization regime, is given
by
1 E
n = ( Nc Nd ) exp( ) (7.6)
2 2kB T
E is the ionization energy of the donor level i.e. the energy difference between the donor
level and the conduction band. The 12 enters equation 7.6 because the donor levels are lo-
calized and can accommodate only one electron instead of two like a regular energy state.
It is possible to define a saturation temperature (Ts ) based on equation 7.6. The saturation
temperature is defined as the temperature where n = 0.9Nd where Nd is the donor concen-
tration. This corresponds to 90% ionization. Consider Si with Nd of 1015 cm3 . Take Nc
to be independent of temperature and equal to 2.8 1019 cm3 . For As, E is 0.054 eV .
Then, using equation 7.6 the saturation temperature, Ts , is 32 K. The actual value (tak-
ing temperature dependence of Nc ) is around 60 K, which is still much lower than room
temperature. This means that the donor atoms (and similarly the acceptor atoms) are fully
ionized at room temperature so that we are justified in equating the electron concentration
(hole concentration) to the donor concentration (acceptor concentration).

7.3.2 Medium temperature regime (Ts < T < Ti )


Above the saturation temperature the donor levels are completely ionized so that n = Nd .
As temperature keeps increasing there comes a temperature when the electrons from the
valence band (intrinsic carriers) becomes comparable in concentration to Nd . This tem-
perature is called the intrinsic temperature, Ti . Above this temperature the semiconductor
behaves as intrinsic. Ti is defined as the temperature when n = 1.1 Nd . This corresponds to
110% ionization. Between Ts and Ti the majority carrier concentration changes from 90%
to 110% Nd , so the variation in concentration is only 20% overall.
The intrinsic temperature for Si can be calculated using the equation for intrinsic semi-
conductors. When n = 1.1 Nd the hole concentration, p, can be calculated using a charge
64 7

Figure 7.6: Majority carrier concentration vs. inverse temperature for an extrinsic semicon-
ductor. In the ionization regime, donor atoms are partially ionized. Then in the saturation
regime where donors are fully ionized and carrier concentration is a constant. Finally, at
high temperatures there is the intrinsic regime where it behaves like an intrinsic semicon-
ductor. The temperatures corresponding to these depend on the donor concentration. The
plot was generated in MATLAB with a donor concentration of 1015 cm3 . The vertical
dotted line marks room temperature.

balance equation.
n = p + Nd (7.7)
So, p = 0.1 Nd . Using the law of mass action n2i = np, the intrinsic carrier concentration is
0.33 Nd . This corresponds to a temperature of 526 K, which is the intrinsic temperature.
Thus there is a temperature regime, from 60 K - 526 K, where the majority carrier concen-
tration is nearly a constant. The majority carrier concentration vs. temperature is plotted
in figure 7.6. There are 3 regions from the plot. A ionization regime at low temperature,
a saturation regime where the electron concentration is nearly a constant, and a intrinsic
regime where the semiconductor behaves like an intrinsic semiconductor. In Si, this sat-
uration regime is around room temperature so that the carrier concentration is a constant
and independent of temperature.
Thus doping in a semiconductor has 2 functions

1. It increases the conductivity by preferentially increasing either electron or hole con-


centration. The conductivity can be precisely tuned by controlling the type and amount
of dopant.
2. The majority carrier concentration is a constant and temperature independent (near
room temperature) so that small temperature variations will not change the conductiv-
ity. Thus, electrical devices can be formed with very little variation in their electrical
properties during normal operating temperatures.
CHAPTER 8

EXTRINSIC SEMICONDUCTORS -
MOBILITY

8.1 Carrier mobility

Dopants in an intrinsic semiconductor perform two major functions

1. They increase carrier concentration of a particular polarity (i.e. electrons or holes)


so that the overall conductivity is higher. Usually this is orders of magnitude higher
than the intrinsic semiconductor and is dominated by either electrons or holes i.e. the
majority carriers.

2. Dopants also stabilize carrier concentration around room temperature. For Si, the
saturation regime extends from roughly 60 K to 560 K.

Consider the general conductivity equation

= nee + peh (8.1)

For extrinsic semiconductors with either n or p much higher than the minority carrier
concentration equation 8.1 can be written as

n type : = nee
(8.2)
p type : = peh

Second Edition. 65
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
66 8

e and h are the drift mobilities of the carriers. They are given by

ee
e =
me
eh (8.3)
h =
mh

The drift mobilities are a function of temperature and in extrinsic semiconductors they
depend on the dopant concentration. This dependence comes from the scattering time, e
and h , which is the time between two scattering events.
Another way of writing the scattering time is in terms of a scattering cross section (S). This
is given by
1
= (8.4)
S vth Ns
where vth is the mean speed of the electrons (thermal velocity) and Ns is the number of
scatters per unit volume. The role of scatters and the effect on mobility can be considered
by considering the two main types of scatters

1. Lattice atoms

2. Impurities - dopants

8.1.1 Lattice scattering

In an intrinsic semiconductor the carrier scattering is mainly due to thermal vibrations of


the lattice (Si atoms). In metals, electron-electron scattering is also important and affects
the conductivity, but electron concentration in semiconductors are low so that electron-
electron scattering can be ignored. For lattice scattering, if a is the amplitude of the lattice
vibrations for a simple two dimensional scattering, S is just a2 . As temperature increases,
a increases and hence S increases. The second term in equation 8.4 is the thermal velocity
(vth ). This is typically given by 23 kB T . For an electron in the conduction band this is equal
to its kinetic energy so that

1 3
me vth = kB T vth T (8.5)
2 2
The concentration of scatters, Ns , is a constant and is independent of temperature.
So the dependence of lattice scattering time (L ) on temperature can be given using equa-
tion 8.4
1 1 3
L = 1 T ( 2 ) (8.6)
(a2 )vth Ns (T )(T 2 )
Since the scattering time is directly proportional to the mobility, see equation 8.3, this
3
means that e is also proportional to T ( 2 ) . Thus, the effect of lattice scattering is to
reduce the mobility with increase in temperature. This can be understood qualitatively by
seeing that as the temperature increases the atomic vibrations increase and at the same time
the electrons also travel faster. Both these effects combine to reduce the mobility. A similar
argument is valid for hole scattering in intrinsic semiconductors. Despite this decrease in
mobility, conductivity increases with temperature because carrier concentration increases
exponentially with temperature.
CARRIER MOBILITY 67

Figure 8.1: Electron scattering from an ionized As donor. The scattering cross section
is calculated considering the balance between the kinetic energy and the potential energy,
using which a scattering radius, rc , is defined. Adapted from Principles of Electronic
Materials - S.O. Kasap.

8.1.2 Impurity scattering


Impurity scattering becomes important for doped semiconductors. At room temperature
the impurities are ionized, so that there is an electrostatic attraction between the electrons
traveling in the lattice and the impurity, as shown in figure 8.1 for As doped in Si (donor).
To find the scattering cross section due to the ionized impurities we can equate the kinetic
energy (KE) of the electrons to the potential energy (PE) due to the ionized impurity. From
figure 8.1 the electron will not be scattered if KE dominates while scattering occurs if PE
dominates. The scattering radius, rc , is the distance at which both effects are equal

3 e2
kB T =
2 40 r rc (8.7)
S = rc2 T 2

So the scattering time due to impurities, I , is given by equation 8.4


1 1 3
I = 1 T2 (8.8)
(rc2 )vth NI (T 2 )(T )
2

Again, since the scattering time is directly related to mobility, the mobility due to impu-
rities increases with temperature, opposite to the behavior observed with the lattice. This
can be understood qualitatively by considering that with increasing temperature, electrons
can travel faster and this makes it easier to escape the ionized impurities.

8.1.3 Conductivity in extrinsic semiconductors


In intrinsic semiconductors the only factor that affects mobility is the lattice scattering
so that mobility always reduces with temperature. In extrinsic semiconductors there are
two contributions - lattice (L ) and the impurities (I ). So the total mobility is given by
68 8

Figure 8.2: Mobility vs. temperature for different donor concentrations for extrinsic semi-
conductors. For low Nd mobility decreases with temperature, but as Nd increases at low
temperature mobility actually increases. Adapted from Principles of Electronic Materials
- S.O. Kasap.

Matthiessens rule, which is

1 1 1
= + (8.9)
e I L

The scattering process with the lowest mobility dominates. Also, at low temperatures mo-
bility actually increases with temperature since impurity scattering dominates, while at
high temperature lattice scattering dominates. This is shown in figure 8.2. At low dopant
concentrations lattice scattering dominates over the entire temperature range. With in-
creasing dopant concentrations impurity scattering starts to dominate at low temperature.
A similar behavior is also seen for hole mobility. Experimental measurements of electron
and hole mobilities in Si, as a function of temperature, are shown in figure 8.3 and confirm
this behavior. Also, at constant temperature the mobility decreases with increasing dopant
concentration since there is greater concentration of impurities, as shown in figure 8.4.
Looking at the the temperature dependence of conductivity, both the carrier concentration
change and mobility change with temperature and influence the conductivity. The tem-
perature dependence of conductivity is shown in figure 8.5. The dominating term is still
the carrier concentration, due to its exponential dependence on T but the mobility term
also plays a role, especially in the extrinsic regime (or saturation regime). Again, based
on conductivity there is an optimal temperature range where is nearly constant. For Si,
this is around room temperature so that doping not only gives a temperature independent
carrier concentration but also conductivity. For Si doped with 1015 cm3 donors the carrier
concentration, mobility, and conductivity are plotted in figure 8.6.
CARRIER MOBILITY 69

Figure 8.3: Log-log plot of experimental (a) electron mobility and (b) hole mobility vs.
temperature for different dopant concentrations in Si. The applied electric field is small
(low E). Source http://dx.doi.org/10.1016/0038-1101(77)90054-5
.

Figure 8.4: Mobility vs. dopant concentrations for both donors and acceptors. In both cases
the mobility decreases with increasing dopant concentration. Adapted from Principles of
Electronic Materials - S.O. Kasap.
70 8

Figure 8.5: Conductivity dependence on T for extrinsic semiconductors. The dependence


closely follows the concentration of majority carriers vs. temperature, with the effect if
mobility being felt in the saturation (extrinsic) regime. Adapted from Principles of Elec-
tronic Materials - S.O. Kasap.

Figure 8.6: (a) Carrier concentration, (b) electron mobility and (c) conductivity for Si
doped with 1015 cm3 donor atoms. The increase in carrier concentration with temperature
is balanced by the reduction in mobility. This is a semilog plot vs. inverse temperature
(plotted in mK 1 ) and generated using MATLAB.
DEGENERATE SEMICONDUCTORS 71

Figure 8.7: Degenerate (a) n and (b) p type semiconductors. The impurities form an energy
band that can merge with either the valence or conduction band. The Fermi level lies within
this band rather that in the band gap. Degenerate semiconductors hence have properties
similar to metals. Adapted from Principles of Electronic Materials - S.O. Kasap.

8.2 Degenerate semiconductors

Typical dopant concentrations are in range of ppm or ppb and form individual energy levels
in the band gap. This is because ND and NA are much smaller than the effective density
of states at the band edges (Nc and Nv ). These are called non-degenerate semiconductors.
Under such conditions, it is possible to consider the dopants as individual atoms in the Si
lattice and ignore interactions between the dopant levels. This is why dopants are shown
as individual energy levels, close to the valence or conduction band, and not as an energy
band.
As the dopant concentration increases, the individual energy levels start to overlap so that
there are no longer energy levels but energy bands. This happens at typical dopant concen-
trations of 1019 and 1020 cm3 , comparable to Nc and Nv (1020 cm3 ). These are called
degenerate semiconductors, and their energy band diagram is shown schematically in
figure 8.7. The dopant energy levels can merge with the conduction or valence band, so
that the Fermi energy lies within the band. Thus, degenerate semiconductors behave more
like metals than semiconductors. Degenerate doped semiconductors are used for some
opto-electronic devices like lasers due to the large carrier concentration.

8.3 Amorphous semiconductors

For most semiconductor applications, single crystal defect free materials are used. Typical
metallic impurity concentration in Si used for integrated circuit manufacture should be less
than 0.1 ppb. Similarly, other defects, like dislocations, are harmful since they can modify
the electronic properties of the material. The most common defect is the surface. Since
the surface represents a break in the material, there will be dangling bonds at the surface.
These dangling bonds produce defects states that lie at the center of the band gap. These
defects states can then pin the Fermi level at the center of the gap which will affect the
72 8

Figure 8.8: Energy bands in a crystalline semiconductor. (a) Simple band picture showing
the band edges. (b) Density of states in the valence and conduction band. There are
no energy states in the forbidden energy gap. Adapted from Physics of Semiconductor
Devices - S.M. Sze.

carrier transport properties, especially when junctions or interfaces are formed with other
materials. For Si, there is a native oxide layer (approximately 3 nm thick) that causes sur-
face passivation and reduces the density of these dangling bonds.
An amorphous semiconductor is an extreme example of the defective semiconductor. Amor-
phous materials have no long range order and this leads to a large density of dangling
bonds, not only at the surface but also the bulk. These dangling bonds lead to localized
defect states in the band gap. Figure 8.8 shows the energy bands in a crystalline semi-
conductor. There are no energy states in the band gap i.e. the forbidden energy gap. The
energy band diagram for an amorphous semiconductor is shown in figure 8.9 and is drasti-
cally different from a crystalline semiconductor. There is the valence and conduction band,
which form the extended states. They are the continuous energy states, similar to a crys-
tallline semiconductor. Along with them the dangling bonds produce localized states that
lie within the band gap. These arise due to the lack of long range order in the amorphous
material.
The energy gap in an amorphous semiconductor is called a mobility gap because it is not
a true band gap like crystalline semiconductors. In crystals, electrons cannot exist in the
band gap because there are no available energy states. But in an amorphous semiconductor
since there are localized states in the band gap it is possible for electrons to exist in the
band gap. The localized states usually act as traps and reduce the mobility. Conductivity in
these materials occurs when electron trapped in the defects states hop from one localized
state to the next, called hopping conduction.
Crystalline Si has a mobility of 1350 cm2V 1 s1 while amorphous Si (denoted a-Si:H)
has a mobility as low as 1 cm2V 1 s1 . The notation a-Si:H means amorphous Si with
hydrogen termination at the surface (to passivate surface dangling bonds). Amorphous
AMORPHOUS SEMICONDUCTORS 73

Figure 8.9: Energy bands in an amorphous semiconductor. There are extended states in the
valence and conduction band. Along with that there are also localized states in the band
gap. Adapted from Principles of Electronic Materials - S.O. Kasap.

semiconductors find applications in solar cells, image sensors, TFTs (thin film transis-
tors) where device speed is not an important criteria but cost is. It is easier to fabricate
amorphous materials than high purity and defect free single crystals and the low cost can
compensate for the poorer performance.

Problems - chapters 6-8

8.1 A group IV semiconductor is doped with 1018 donor atoms per cm3 . ni = 2.3
10 cm3 and Nc = Nv = 7 1019 cm3 . At 300 K, the donor atoms are fully ionized.
13

What is the hole concentration at 300 K? What is the band gap of the semiconductor? What
is the position of the Fermi level with respect to intrinsic semiconductor Fermi level?
8.2 A semiconductor with ni = 1016 m3 (at 300 K) is doped with acceptor impurities
to a concentration of 1023 m3 .
(a) What are the electron and hole concentrations?
(b) Assuming effective masses of electron and holes are equal to free electron mass, cal-
culate Eg and EF .
(c) Donor impurities are then added to a concentration of 5 1022 m3 . What are the new
values for the four quantities calculated above?

8.3 Using the hydrogenic model, how much energy is required to ionize a donor atom in
a semiconductor with dielectric constant of 10 and an electron effective mass that is only
30% of free electron mass. Using the above model, what would the Bohr radius of the
74 8

donor atom be? At what concentration of donors would there be appreciable overlap of the
donor levels to form a band?
8.4 A Si sample has been doped with 1015 cm3 P atoms. The donor level for P in Si is
0.045 eV below conduction band edge.

(a) Where is the Fermi level located at 0 K?


(b) At what temperature is the donor 1 % ionized? Where is the Fermi level located at this
temperature?
(c) At what temperature does the Fermi level lie in the donor energy level?

(d) Estimate the temperature when the sample behaves as if intrinsic.


(e) Sketch schematically the change in Fermi level with temperature.
Take the DOS at conduction and valence band edge to be 1019 cm3 and independent
of temperature. The DOS at donor level is 5 1014 cm3 . Si band gap is 1.10 eV and
independent of temperature.
8.5 An n-type Si sample has been doped with 1017 P atoms cm3 . The drift mobilities
of holes and electrons in Si at 300 K depend on the total dopant concentration (Ndopant ) as
follows
1252
e = 88 + cm2V 1 s1
1 + 6.984 1018 Ndopant
407
h = 54.3 + cm2V 1 s1
1 + 3.745 1018 Ndopant

(a) Calculate the room temperature conductivity.


(b) Calculate the necessary acceptor doping that is required to make this sample p-type
with approximately the same conductivity.
Index

A Conduction band, 10, 14


Valence band, 7, 14
Acceptors, 53, 57
Amphoteric doping, 57 Extended states, 72
Extrinsic semiconductor, 33, 49

B F
Band gap, 14
Direct band gap, 15 Fermi energy, 7, 11, 43, 61
Indirect band gap, 15 Fermi function, 29
Boltzmann statistics, 28 Fermi-Dirac statistics, 29

C H
Carrier concentration, 38 Holes, 34
Charge balance, 64 Hopping conduction, 72
Compensation doping, 55
Conductivity, 35, 54 I
Impurity scattering, 67
D Insulators, 2
Intrinsic carrier concentration, 40, 41
Defect states
Deep states, 60 Intrinsic semiconductor, 33
Shallow states, 60 Intrinsic temperature, 63
Density of states, 23 Ionization regime, 63
Donors, 51, 57
Dopants, 50 L
N-type, 50, 57 Lattice scattering, 66
P-type, 53, 57 Law of mass action, 40, 49
Localized states, 72
E
Effective mass, 37 M
Energy band, 7, 23 Majority charge carriers, 54

Second Edition. 75
By Parasuraman Swaminathan Copyright
c 2016 John Wiley & Sons, Inc.
76 INDEX

Matthiessens rule, 68
Minority charge carriers, 54
Mobility, 35, 66
Mobility gap, 72
Molecular orbitals, 3
Anti-bonding orbital, 3
Bonding orbital, 3

O
Ohms law, 1

R
Resistivity, 1

S
Saturation temperature, 63
Semiconductor, 2
Amorphous semiconductors, 71
Compound semiconductors, 15
Degenerate semiconductors, 71
Elemental semiconductors, 15
Non-degenerate semiconductors, 71

W
Work function, 7, 44

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