Semiconductors and its

Properties
Anurag Srivastava
Basic characteristics of semiconductors
Something about the history:
• 1833 M. Faraday:
– For AgS decreasing ρ with increasing T
• 1873 W. Smith:
– Photoconductivity of Se
• 1874 F. Braun:
– Rectifying properties of PbS
• 1948 Bardeen & Brattain:
– Bipolar transistor
• The most usual semiconductors are
the elemental ones, Si and Ge (and
diamond C).
• They are tetrahedrally bonded, and
thus, fourfold coordinated with
sp3-hybridization.
• Semiconductors are typically:
- stoichiometric: elemental,
binary, tertiary, quaternary, ...
- crystalline
- small band gap materials
⇒ semiconducting
- covalently bonded (mainly)

There are also semiconducting organic,

magnetic and ferroelectric materials.
Some high–Tc superconductors are
semiconducting in N-state.
Semiconductors
• Semiconductors constitute a
large class of substances which
have resistivities lying between
those of insulators and
conductors.
• The resistivity of
semiconductors varies in wide
limits, i.e., 10–4 to 104 Ω-m and
is reduced to a very great
extent with an increase in
temperature
Semiconductors
• The most typical and extensively employed
semiconductors whose electrical properties have been
well investigated, are Germanium (Ge),Silicon (Si) and
Tellurium (Te). The study of their electrical properties
reveals that
– Semiconductors have negative temperature Coefficient of
resistance, i.e., the resistance of semiconductor decreases with
increase in temperature and vice versa
– The resistivity of semiconductors lies between that of a good
insulator and of a metal conductor, i.e., lying in the range 10–4 to 104
Ω-m.
– The electrical conductivity of a semiconductor is very much affected
when a suitable impurity, e.g., Arsenic, Gallium, Indium etc. is added
to it. This property of semiconductors is most important.
Semiconductors
As compared to electronic valves, semiconductor
devices offer the following advantages:
(i) low weight and small size
(ii) no power for the filament
(iii) Long service life (thousands of hours)
(iv) mechanical ruggedness
(v) low power losses and
(vi) Low supply voltages.
Semiconductors
At the same time semiconductor devices suffer
from a number of disadvantages:
– deterioration in performance with time (ageing);
higher noise level than in electronic valves
– Unsuitability of most transistors for use at
frequencies over tens of megahertz;
– low input resistance as compared with vacuum
triodes;
– inability to handle large power
– deterioration in performance after exposure to
radioactive emissions.
R & D has reduced the demerits
• There are semiconductor rectifiers for currents of
thousands of amperes.
• Replacement of Germanium with Silicon makes crystal
diodes and transistors suitable for operation at
temperatures upto 125°C.
• There are transistors for operation at hundreds of
megahertz and more, and also microwave devices
such as gunn diode, tunnel diode.
How semiconductor works?
• To understand how semiconductors work, one must
have a good knowledge of atomic structure.
• The smallest particle that an element can be reduced
to and still retain its properties is called an atom.
• There are a number of different subatomic particles,
but only three of these are of interest in basic
electronics—the proton, the neutron and the electron.
• An, atom has the same number of electrons
• and protons, and so it is electrically neutral. If an atom
does have more electrons, it is called a negative ion. If
it has more protons, it is called a positive ion.
quantum numbers
To understand the location and energy of each electron in an atom, one
must have the knowledge of four quantum numbers:

(i) Principal Quantum Number (n).

– This characterises the average distance of an electron
from the nucleus and corresponds to the principal energy
level in which electron resides.
– n can have positive integer values starting from 1, i.e. n =
1, 2, 3,...... .
– The principal energy levels or shells having different
values of n are designated by the letters K, L, M, N and so
on.
– The maximum numbers of the electrons that can be
accommodated in a shell corresponding to n is equal to
2n22
(ii) Azimuthal Quantum Number (l).
– This is also called as orbital angular momentum
quantum number and gives a measure of the
angular momentum of an electron in the orbit.
– Physically, l indicates the shape of the classical orbit.
– For a given value of n, l can take all positive integer
values from o to (n – l).
– The particular l value defines the subshell, and the
sub shells with l = 0, 1, 2, 3,...... are designated as s,
p, d, f, g,...... respectively.
(iii) Magnetic Quantum Number (ml).
– This is also called as orbital magnetic number and this
determines the preferred orientation of the orbitals in
space with respect to an applied magnetic field.
– We know that the magnetic moment of an electron due
to its orbital motion gives rise to a magnetic field which
can interact with an external magnetic field. The
electrons orient themselves in certain preferred region
of space around the nucleus under the influence of the
external field.
– For a given value of l, m can take integer values between
l

– 1 to + 1 including 0, i.e. total allowed values of m are

l

(2l + 1).
• (iv) Spin Quantum Number (ms).
– Electron is spinning about its own axis in the atom.
– The spin of the electron produces a spin magnetic
moment which can either parallel or antiparallel to
the surrounding magnetic field.
– For an electron there are two spin states.
– Spin quantum number is concerned with the spinning
of the electron about its own axis.
– Thus m can take only two possible states, +½ or – ½.
Pauli Exclusion Principle.
– This states that in an atom no two electrons can
exist in the same quantum state, i.e. in an atom
there cannot be two electrons with the same value
of all the four quantum numbers.
– With the help of this principle, one can write the
configuration of electrons.
– All the electrons with the same value of n
constitute a shell and a shell can have a maximum
of 2n2 electrons.
Atomic structures of H, B, Si, P and Ge
atoms.
– The electrons in the inner shells of an atom do not
normally leave the atom. But the electrons which are
in the outermost shell, so called valence shell do not
always remain confined to the same atom.
– Some of these valence electrons move in a random
manner and may travel from one atom to another in a
crystal lattice. These electrons are called as free
electrons.
– It is due to the presence of these free electrons in a
material, that electrical conduction is possible.
– The electrons in the inner orbits of the atom remain
bound to the nucleus and are, therefore, called bound
electrons.
chemical stability
– The tendency of an atom to give up its valence
electrons depends on chemical stability.
– When an atom is stable, it resists giving up
electrons, and when it is unstable, it tends to give
up electrons.
– The level of stability is determined by the number
of valence electrons, because the atom strives to
have its outermost or valence shell completely
filled.
Band formation
Classification of solids
Semiconductors Classification
Exciton:
The exciton Rydberg energy is given as,
quantum confinement effect
– The tuning of fundamental properties such as optical and
vibrational properties of nanostructured semiconductor
material is possible when the size of the nanostructured
semiconductor material approaches the exciton Bohr radius.
– Though significant variation in the fundamental properties is
observed when the size is less than the exciton Bohr radius.
This is due to the confinement of charge carriers and
phonons within the nanoparticles. This is called quantum
confinement effect.
– Efros and Efros (1982) introduced three regimes of quantum
confinement, depending on the ratio of the nanocrystallite
radius R to the Bohr radius of the electrons, holes and
electron-hole pair.
Quantum Confinement Surface to volume ratio
Semiconducting Materials
Besides Elemental, Compund and Diluted Magnetic Semiconductors.
Organic semiconductors:
• Semiconductor like properties are also found in "organic compounds" like
polydiacetylene (CH2)n with conjugate carbon chains, fullerenes, nanotubes, BN
nanotubes, etc.
• Organic molecules can easily be tailored at the molecular level and "tuned" for
applications.
• However, these are not used too much, yet, but they seem promising materials for
nonlinear optics (NLO), for example.

Magnetic Semiconductors
• Strong magnetooptical effect allows the material to be used in optical modulators.
Their Faraday rotation can be up to six orders of magnitude higher than that of
nonmagnetic semiconductors.
• Magnetic field can also be used to cause the metal to semiconductor transition, a
phenomenon also called colossal magnetoresistance.
Other ...
• Ferroelectric and complex inorganic materials ... for NLO
Types of Semiconductor Materials

• The silicon doped with extra electrons is called

an “N type” semiconductor.
– “N” is for negative, which is the charge of an
electron.
• Silicon doped with material missing electrons
that produce locations called holes is called “P
type” semiconductor.
– “P” is for positive, which is the charge of a hole.

A presentation of eSyst.org
Current Flow in N-type Semiconductors

• The DC voltage source has a

positive terminal that attracts
the free electrons in the
semiconductor and pulls
them away from their atoms
leaving the atoms charged
positively.
• Electrons from the negative
terminal of the supply enter
the semiconductor material
and are attracted by the
positive charge of the atoms
missing one of their
electrons.
• Current (electrons) flows
from the positive terminal to
the negative terminal.

A presentation of eSyst.org
Current Flow in P-type Semiconductors
• Electrons from the negative
supply terminal are attracted
to the positive holes and fill
them.
• The positive terminal of the
supply pulls the electrons
from the holes leaving the
holes to attract more
electrons.
• Current (electrons) flows
from the negative terminal to
the positive terminal.
• Inside the semiconductor
current flow is actually by the
movement of the holes from
positive to negative.

A presentation of eSyst.org
Diamond
• In the diamond structure, the carbon
atoms are arranged on an fcc-type
lattice with a total of 16 electrons per
primitive cell.

The valence band and 7 lower bands are full, leaving no electrons in the
conduction band.
Diamond
Electrons may be thermally
activated to jump a gap. At
room temperature, kBT is only
0.026 eV. To jump the energy
gap, the electron requires very
high temperatures. So,
diamond is an excellent
insulator.
ρ = 1018 -m
Graphite/Graphene

ρ = 9 -m
Silicon
• Silicon has the diamond structure.
• There are 14 electrons per primitive
cell.
• Gap is only 1.12 eV, however.

Now there is a small (but finite) chance for a few electrons to be thermally
excited from valence band to conduction band.
Silicon

}1.12 eV
Effective Mass(me) Revisited
• An electron moving in the solid under the influence of the
crystal potential is subjected to an electric field.
• We expect an external field to accelerate the electron,
increasing E and k and change the electron’s state.
• If this external field is much weaker than the internal field,
the effect the latter is to modify the mass of carriers in such
a way that the carriers respond to the applied field with
this modified mass obeying classical mechanics. This
modified mass is termed as effective mass of carriers and is
usually different from electron mass (m0) in vacuum.
Effective Mass Revisited

1
 1 d 2
me   2 
  dk 2 
 
• This relates the curvature of the band to the “effective mass.”
• One can show that a free electron “band” gives an effective mass
equal to the rest mass of an electron.
• Electrons in a crystal are accelerated in response to an external
force just as though they were free electrons with effective mass
me.
• Usually , me < m0.
Effective Mass Revisited
Effective Mass Revisited
Material Electron Effective Mass Hole Effective Mass
Group IV
Si (4.2 K) 1.08 0.56
Ge 0.555 0.37
Groups III-IV
GaAs 0.067 0.45
InSb 0.013 0.60
Groups II-VI
ZnO 0.,19 1.21
ZnSe 0.17 1.44

in multiples of the free electron mass

m0 = 9.11  1031 kg
Experimental Measurement
• Traditionally effective masses were measured using cyclotron resonance, a
method in which microwave absorption of a semiconductor immersed in a
magnetic field goes through a sharp peak when the microwave frequency
equals the cyclotron frequency.

• In recent years effective masses have more commonly been determined

through measurement of band structures using techniques such as angle-
resolved photoemission or, most directly, the de Haas-van Alphen effect.

• Effective masses can also be estimated using the coefficient g of the linear
term in the low-temperature electronic specific heat at constant volume
Cv.
• The specific heat depends on the effective mass through the density of
states at the Fermi level and as such is a measure of degeneracy as well as
band curvature.
Electrons & Holes
Electrons & Holes
For the electrons occupying the vacant
states,  2 
 1 d  0
  2 dk 2 
 
(Negative!) and the electrons will move in
same direction as electric field (wrong
way!)

In a semiconductor, there are two charge carriers:

• Electrons (conduction band)
• negative mass
• negative charge
• Holes (valence band)
• positive mass,
• positive charge
Carrier Concentration

To calculate the carrier concentrations in energy bands we

need to know the following parameters:
• The distribution of energy states or levels as a function of
energy within the energy band, D().
• The probability of each of these states being occupied by
an electron, f().

n   f ( ) D( ) d 
c

v
p

1  f ( ) D( ) d 
A band is shown for a one-dimensional crystal. The square represents an
initially empty state in an otherwise filled band. When an electric field is
applied, the states represented by arrows successsively become empty as
electrons make transitions.
The band is completely filled except for a state marked by a square. Except
for the electron represented as a circle, each electron can be paired with
another, so the sum of their crystal momentum vanishes. The total crystal
momentum for the band and the crystal momentum of the hole are both ħk.
The empty state and the unpaired electron for two times are shown when
an electric field is applied. The change in momentum is in the direction of
the field.
Conduction Band Carrier Concentration

n f ( ) D( ) d 
 0

dN ( )
3/ 2
1  2me 
D( )   2 3  
dE 2  
For  >> F, the Boltzmann distribution approximates the F-D
distribution:

1
f ( )   e (  F ) / k BT
1  e(  F ) / k BT
 e (  c ) / k BT e ( c  F ) / k BT
which is valid for the tail end of the distribution.
Conduction Band Carrier Concentration


  c  / kBT

 ( c  F ) / kBT
ne D( ) e d
0

3/ 2
 me k BT 
N C  2 
 2  2

 F  c / k BT
n  NC e
Conduction Band
Carrier Concentration
Valence Band Carrier Concentration

• The hole distribution is related to the electron distribution,

since a hole is the absence of an electron.
1 1
f h  1  f e  1    / k T    / k T
e F B 1 e F B 1

 e   F / k BT (as long as  F    k BT )

 The holes near the top of the valence band behave like particles with
effective mass mh; and the density of states is

3/ 2
1  2mh 
D( )  2  2    v
2  
3/ 2
v  mh kBT 
p   1  f ( ) D( ) d   2  2 
e  v  F  / kBT

 2 
Equilibrium Relation
• Multiply n and p together:

3/2  g / k BT
3
 k BT 
np  4  mh me  e
 2 2 
• The product is constant at a given temperature.
• It is also independent of any impurity concentration at a given
temperature. This is because any impurity that adds electrons,
necessarily fills holes.
• This is important in practice, since we could reduce the total
carrier concentration n + p in an impure crystal via the
controlled introduction of suitable impurities – such reduction
is called compensation.
Intrinsic Semiconductors

n  p  ni
N c e  F  c / k BT  N v e  v  F / k BT
 Nc 
 k BT ln    c   F   F   v
 Nv  c

c  v 1  Nc  F
F   k BT ln  v
2 2  Nv 
Extrinsic Semiconductors
• Extrinsic semiconductors: we can add impurities
to make a material semiconducting (or to change
the properties of the gap).
• There are 2 types of extrinsic semiconductors:
p-type and n-type
• These are materials which have mostly hole
carriers (p) or electron carriers (n).
• These give you ways of modifying the band gap
energies (important for electronics, detectors, etc).
Extrinsic Semiconductors: n type
• Add a small amount of phosporus (P:
3s23p3) to Silicon (Si: 3s23p2) (generally, a
group V element to a group IV host) P
replaces a Si atom and it donates an
electron to the conduction band (P is called
the donor atom). The periodic potential is
disrupted and we get a localized energy
level, D.

• This is an n-type semiconductor – more electrons around that

can be mobile; and the Fermi energy is closer to the conduction
band.
Extrinsic Semiconductors: n type
Phosphorus provides an extra electron.
 C – D = 45 meV
So, its easy for the donor electrons to enter
the conduction band at room temperature.
This means that at room temperature n ND.
This is called complete ionization (only true if
ni << ND). Therefore, by doping Si crystal with
phosphorus, we increase the free electron
concentration.
At low temperature, these extra electrons get
trapped at the donor sites (no longer very
mobile) - the dopant is frozen out.
Extrinsic Semiconductors: p type
• Next suppose Si atom is replaced with Boron (B: 2s22p) to Silicon
(Si: 3s23p2). Again, we have a perturbed lattice and
a localized E-level created.
• Boron is missing an electron and accepts an
electron from valence band, creating a hole.
• Therefore doping with B increases hole
concentration. We call this p-type doping,
the electron concentration n is reduced.
• F moves closer to  V. c

F
A
v
Extrinsic Semiconductors
Extrinsic Semiconductors
Boron in Silicon
 Mass Action Law
• Valid for both intrinsic and extrinsic semiconductors.

• It is important in devices to control n and p concentrations

and to suppress the influence of the intrinsic concentration.

• These equations are important in establishing upper limits in

semiconductor operating temperature.

• We generally require ni << (minimum doping density) and,

practically, this means we need doping concentrations above
1014 cm3.
Semiconductors
The Hall Effects
 Discovery
• Observed in 1879
• Edwin Herbert Hall
• Discovered 18 years before the
electron

Via Wikimedia Commons (public domain)

 The Hall effect was discovered in 1879 by Edwin Hall while he was
working on his doctoral degree at Johns Hopkins University in Baltimore,
Maryland.
 His measurements of the tiny effect produced in the apparatus he used
were an experimental tour de force, accomplished 18 years before the
electron was discovered and published under the name "On a New
Action of the Magnet on Electric Currents".

65
Hall effect in Metals

For a simple metal where there is only one type of

charge carrier (electrons) the Hall voltage VH can be
derived by using the Lorentz force and seeing that in
the steady-state condition charges are not moving in
the y-axis direction because the magnetic force on
each electron in the y-axis direction is cancelled by a y-
axis electrical force due to the buildup of charges.
Lorentz Force
Principles
• Mobile charges pressed to one side from
Lorentz force, immobile charges unaltered
• Creates internal electric potential, known as
Hall voltage. Note: t refers to the
thickness of the
• For simple metals, VH= metal along the
direction of the B-
field

68
Concept:
• The Hall effect is due to the nature of the current in a conductor.
• Current consists of the movement of many small charge carriers, typically
electrons, holes, ions (see Electromigration) or all three.
• When a magnetic field is present, these charges experience a force, called the
Lorentz force.
• When such a magnetic field is absent, the charges follow approximately
straight, 'line of sight' paths between collisions with impurities, phonons, etc.
• However, when a magnetic field with a perpendicular component is applied,
their paths between collisions are curved so that moving charges accumulate
on one face of the material. This leaves equal and opposite charges exposed on
the other face, where there is a scarcity of mobile charges. The result is an
asymmetric distribution of charge density across the Hall element, arising from
a force that is perpendicular to both the 'line of sight' path and the applied
magnetic field.
• The separation of charge establishes an electric field that opposes the
migration of further charge, so a steady electrical potential is established for as
long as the charge is flowing.
 A Visual Representation

• Hall Effect measurement setup for electrons.

• Initially, the electrons follow the curved arrow, due to the magnetic force.
• At some distance from the current-introducing contacts, electrons pile up on the
left side and deplete from the right side, which creates an electric field ξy in the
direction of the assigned VH.
• VH is negative for some semi-conductors where "holes" appear to flow.
• In steady-state, ξy will be strong enough to exactly cancel out the magnetic force,
so that the electrons follow the straight arrow (dashed).

Richard Beck - Physics 141A, 2013 70

Hall effect in semiconductors
• When a current-carrying semiconductor is kept in a magnetic field, the
charge carriers of the semiconductor experience a force in a direction
perpendicular to both the magnetic field and the current. At
equilibrium, a voltage appears at the semiconductor edges.
• The simple formula for the Hall coefficient given above becomes more
complex in semiconductors where the carriers are generally both
electrons and holes which may be present in different concentrations
and have different mobilities. For moderate magnetic fields the Hall
coefficient is
Hall Coefficient
• Magnitude parameter:

• In metals:

• In semiconductors:

72
achievement
• Classical Picture: only electrons moving in
same average direction in both hole (p-type)
and electron (n-type) conductivity

• Opposite sign indicates that electrons in

valence bands move in opposite direction
than previously thought

73
Applications
• Measurement can tell about charge carrier
mobility and concentration.

• Conversely, knowing the above allows for

sensitive measurement of an external B-field.

• Resistant to outside contaminants unlike

optical, electromechanical testing.

74
 Hall Probes

Via LessEMF.com
Via the NDT Resource Center

75
 Rotation Sensing
• Hall Effect sensors capable of switching very
fast, does not distort like capacitative or
inductive sensors

• Contactless sensing

76
 In Cars
• Used expansively in rotating systems

• Anti-lock brakes, motor feedback, ignition

Via Power Systems Design, Ltd. Via Draper, 2005

77
 In Space
• Hall Effect thruster
• Trap electrons in a magnetic field, electrons
ionize propellant, creates thrust

78
New Discoveries
• QuantumHall Effect

• Spin Hall Effect

• Anomalous Hall Effect

79
Quantum Hall Effect
• For a two-dimensional electron system which can be
produced in a MOSFET, in the presence of large
magnetic field strength and low temperature, one
can observe the quantum Hall effect, in which the
Hall conductance σ undergoes quantum Hall
transitions to take on the quantized values.
• Quantization of normal Hall Effect
• Seen at low temperature, high magnetic field
• Very precise, magnitude determined by Landau
levels and electron interaction

80
Spin Hall Effect
• Separation of electron spins in current-
carrying object, no magnetic field needed.

• Predicted in 1971, observed in 2004 via

emission of circularly polarized light.

• Universal, present in metals and

semiconductors at high and low temperature.

81
Anamolous (extraordinary) Hall Effect
• Ferromagnetic materials have internal
magnetic field
• Much larger than normal Hall Effect, but not
well understood.

Via Toyosaki et al. 2004

82
Personal Experiments

• Aluminum-doped Germanium 1 sq cm chip

• Van Der Pauw configuration

83
Hall Coefficients

84
Extrapolated Carrier Mobility

Clear temperature dependence! Has to do with electron energy

85
NOTATIONS