Energy Bands in Solids

 The materials which have a conductivity b/w conductors

(e.g., metals) and insulators (e.g. ceramics)
 In solid materials, electron energy levels form bands of
allowed energies, separated by forbidden bands
 Valence band – outermost (highest) band filled with
electrons (“filled” = all states occupied)
 Conduction band – next highest band to valence band
(empty or partly filled)
 Gap – energy difference between valence and conduction
bands,(width of the forbidden band)
 Electrons in a completely filled band cannot move,
 Since all states occupied (Pauli principle); only way to move
would be to “jump” into next higher band, needs energy
 Electrons in partly filled band can move, since there are
free states to move in that bands
Energy Bands in Solids

Possible qualitative configuration of the energy bands in a solid

Energy Bands in Solids
Classification of solids – Basis of their band structure
 Insulators: Forbidden region between valence band
and conduction band is very wide, about 3 to 6 eV;
 Semiconductors: Gap is small - about 0.1 to 1 eV;
 Conductors: Valence band partially filled, or (if it is
filled), the next allowed empty band overlaps with it
 Intrinsic Semiconductors
 Consider nominally pure
semiconductor at T = 0 K

 There is no electrons in the

conduction band

 At T > 0 K a small fraction of

electrons is thermally excited
into the conduction band,
“leaving” the same number of
holes in the valence band

 Thermal energy at T = 300K –

brings some electrons into the
conduction band if the gap is on
the order of 1eV
 Intrinsic Semiconductors
Electrons and holes contribute to the current when a
voltage is applied

 The Carrier Concentrations

at T >0 K
 When EV = 0, then EC = EG
 The number of electrons
equals the number of holes,
i.e. ne = nh
 The Fermi level lies in the
middle of the band gap

 EG 
ne  nh  exp  
 2 kT 
k = 1.3807 10-23J/K, ne = nh increase rapidly with temperature
Doping of Semiconductors
 An extrinsic semiconductor is a doped semiconductor

 Doping – Incorporation of impurities [substitutional] into

a semiconductor according to our requirements

 Impurities – Atoms of the elements different from those

forming solid

 Adding impurities can control the number of holes and

electrons available for conduction

□ Impurities change the

conductivity of the material so
that it can be fabricated into a
device

□ Silicon has a valency of 4 i.e. 4

electrons in its outer shell
(intrinsic)
Extrinsic Semiconductors
N-Type Semiconductors
 Group V (e.g. P, As) atom replaces a Si
atom, it will use four of its electrons to
form the covalent bonding
 The remaining electron will not be very
tightly bound, and can be easily ionized
at T > 0K
 Band structure- These electrons are
now in the conduction band
 Such impurities “create” an energy level
within the band gap, close to the
conduction band
 Replacing other Si atoms with As will
increase the electrons
 Donors' impurity: “donate” electrons
into the Conduction Band
Extrinsic Semiconductors
P-Type Semiconductors
 Group III (Al, In or B) atom replaces a Si
atom, it cannot complete a tetravalent
bond
 A hole –formed when an electron from
the valence band is grabbed by the atom
so that the core is negatively charged
 At T > 0 K, electron from the neighboring
Si atom can jump into this hole – the hole
can then migrate and contribute to the
current
 Such impurities “create” energy levels
within the band gap, close to the valence
band
 Acceptor impurity - Atom accepted an
electron and donate hole
Extrinsic Semiconductors
Carriers Concentration
 It depends on doping levels ([net] dopant concentration)
and ionization energy of the dopants
Often both types of impurities are present
 If the total concentration of donors (ND) is larger than the
total concentration of acceptors (NA) have an n-type
semiconductor and vice a versa
 To calculate the charge concentration, the charge neutrality
condition is used, since the net charge in a uniformly doped
semiconductor is zero
 Otherwise, there will be a net flow of charge from one point
to another resulting in current flow

 P (holes concentration in valence band)

p N  n N

D

A



n (electron concentration)
ND+ (ionized donor concentration)
NA- (ionized acceptor concentration)
Types of Semiconductors
Elemental Semiconductors
 Si, Ge (group Iv) – each atom is four-fold coordinated
 P, S, Te & Se (Group V, VI) - three-fold (P), two-fold (S, Se, Te)
or four-fold coordinated
 Several different crystal structures and they are also good glass-
formers
 Se – monoclinic & trigonal crystal structures or as a glass
Binary Compounds
 GaAs - (III–V compounds) – ionic bonding due to transfer of
electronic charge from the group III to V atom
 GaN - (mixed crystals Ga1-xInxN)- used for blue light emitting
diodes and lasers
 Increases the Coulomb interaction b/w ions and also the energy of
the fundamental gap
 ZnS - (II- VI compounds) – band gaps larger than 1 eV
 II–VI compound – large bandgap used for displays & lasers
 II–VI compound – small bandgap used for fabrication of infrared
detectors
Types of Semiconductors
Oxides Semiconductors
 Cuprite (CuO and Cu2O) - Limited potential for applications at
present, growth process
 ZnO (II–VI compound) - Transducer and ingredient of adhesive
tapes and sticking plasters
 La2CuO4 (semiconductor) – La is replaced with Ba, Sr or excess
of Oxygen is used (superconductor)

Layered Semiconductors
 PbI2, MoS2, GaSe - layered crystal structures
 Bonding within the layers is typically covalent
 Interaction between layers can be modified by incorporating
foreign atoms between the layers
 Much interest due to the behavior of electrons in the layers is
quasi-two-dimensional
Types of Semiconductors
Organic Semiconductors
 Polyacetylene [(CH2)n] & polydiacetylene - organic
semiconductors for future applications, can easily tailored

 Conjugate bonds compounds (–C=C–C=) – large optical

nonlinearities and important in opto-electronics applications

 Bandgaps of these compounds can be changed by changing

their chemical formulas

 Carbon nanotubes & C60 fullerene – hold great promise as

nanoscale electronic circuit elements
P-N Junction in Semiconductors
 Two types of semiconductors are
connected without interspace
 Diffusion - movement due to
difference in concentration, from
higher to lower concentration
 Holes “diffuse” towards and across
boundary into n-type & capture
electrons

□ Electrons diffuse across boundary, fall into holes (“recombination

of majority carriers”)
□ Formation of a “depletion region” (region without free charge
carriers around the boundary)
□ charged ions are left behind (cannot move)
□ Negative ions left on p-side net negative charge on p-side
□ Positive ions left on n-side net positive charge on n-side
□ Electric field across junction which prevents further diffusion
Semiconductors Diode
 Diode – biased p-n junction (voltage applied across the
junction)
 Forward biased : p-side more positive than n-side
 Reverse biased: n-side more positive than p-side

Forward biased diode

 Direction of the electric field is
from p-side towards n-side
 p-type charge carriers (positive
holes) in p-side are pushed
towards and across the p-n
boundary
 n-type carriers (negative
electrons) in n-side are pushed
towards and across n-p boundary
 current flows across p-n boundary
Semiconductors Diode
Reversed biased diode
 Electric field direction is from n-side towards p-side
 Reverse biased diode: applied voltage makes n-side
more positive than p-side
 Negative electrons in the n-type feel an attractive force
which pulls them away from the
depletion region

 Positive holes in the p-type also

experience an attractive force
which pulls them away from the
depletion region

 Depletion region widens (as

insulator) and no/small current
flows
Optical Properties of Semiconductors
 If semiconductor or insulator does not have many impurity
levels in the band gap, photons with energies smaller than
the band gap energy can’t be absorbed

 There are no quantum states with energies in the band gap

 This explains why many insulators or wide band gap

semiconductors are transparent to visible light, whereas
narrow band semiconductors (Si, GaAs) are not
Light Emitting Diodes
 Some diodes emit light as they conduct electric current
 These are called LED’s and come in various colors
 LED’s are often used as power indicators on radios, TV’s
and other electronic devices
 If there are many impurity levels the photons with energies
smaller than the band gap energy can be absorbed, by
exciting electrons or holes from these energy levels into the
conduction or valence band, respectively
 Example: Colored Diamonds
Photoconductivity
 Charge carriers (electrons or holes or both) created in the
corresponding bands by absorbed light can also participate in
current flow, and thus should increase the current for a given
applied voltage, i.e., the conductivity increases
 This effect is reverse of the photoemission
 Want conductivity to be controlled by light. So, want few carriers
in dark → semiconductor
 But want light to be absorbed, creating photoelectrons
 Band gap of intrinsic photoconductors should be smaller than the
energy of the photons that are absorbed

Important Applications
 Night vision systems imaging IR
radiation
 Solar cells
 Radiation detectors
 Photoelectric cells (e.g., used for
automatic doors)
 CCD (“Digital Cameras”)
Junction I-V Characteristic
 Diodes do not obey Ohm’s Law
 Current-voltage characteristic equation of the diode
I0 = reverse saturation current
Ƞ = The dimensional coefficient
B = Bolt’s man constant
 A graph of current vs voltage for a diode will not be a
straight line through the origin
 Note how the current increases dramatically once the
voltage reaches a value of nominal value of voltage. i.e. the
junction voltage
 This curve is known as the characteristic curve of the diode

 Silicon diodes have typically

ƞ=2 for currents below
~100mA, breakdown voltages
Vb ~-6V, and typical reverse
saturation current I0=1µA
Organic Light Emitting Diodes (OLEDs)
 Solid State semiconductor device composed of
thin films of organic molecules that creates light
with the application of electricity
 100 to 500 nanometers thick or about 200
times smaller than a human hair
 Thinner & lighter than other display
technologies
 Wide viewing angle (up to 160 degrees even in
bright light)
 less power consumption than conventional
LEDs or LCDs
 OLED’s can provide brighter, crisper displays
STRUCTURE OF OLEDs
 Cathode layer (may or
may not be transparent)
made of tungsten,
Aluminum or Calcium
 Emissive Layer - organic
compound or polymer used
e.g. polyflurene.
 Conductive layer - organic
plastic or polymer used e.g.
polyfluorene
 Anode Layer (transparent)
made from Indium tin oxide
 Substrate layer is used to
support the Organic LED and
is made up of glass, clear
plastic
OLED Light Emission
 Voltage applied across Cathode
and Anode (2V-10V)
 Current flows from cathode to
anode
 Cathode injects electrons which
are transported from the
cathode to emissive layer
 Anode removes electrons from
conductive layer (add holes)
 Holes moves into emissive layer
and recombines with electrons
 Emission of radiation in the
visible range due to
recombination which causes a
drop in the energy levels of
electrons
LED V/S OLEDs
OLED
Parameter LED OLED
Advantage
Average
3000 nits 3800 nits 25% Brighter
Brightness

0.8 mm(1st Gen)

Thickness 2 - 3 mm 0.2 mm(2nd Gen) Thinner handset

High color quality

Poor in red and Rich in red and
Color Spectrum picture on cell
green green
phone screen

Voltage 10.8 V 3 in series 3 - 7 V Lower Voltage

Brightness Better quality

65 - 75% > 90%
Uniformity picture

Rigid glass or Versatility in

Backlight Unit Rigid plastic
flexible plastic application

Thermal Problems above Stable up to Usable in harsh

Stability 60 C 100°C environments
Challenges for OLEDs
Brightness and Lifetime requirement
 State of art OLED brightness and lifetime-100 nits
and 40,000 hours.
 High brightness level require the display driving
voltage levels to be increased which trades off
expected lifetime.
Moisture sensitivity
 Over-time moisture can react with organic layers
and cause degradation and defects in an OLED
display
 Sealing techniques used decreases flexibility.
Growth Techniques

 Czochralski Method
 Bridgman Method

 Chemical Vapor Deposition

 Molecular Beam Epitaxy
 Liquid Phase Epitaxy
Czochralski Method
 Melting the raw material in crucible
 Seed crystal - In contact with the top, cooler region of
the melt
 Rotated and pulled gradully
 Material - solidified from the melt onto the seed
□ Dislocation-free single crystals
of Si
□ Growth speed of few mm/min
□ Silicon ingots dia. >30cm
□ Impurities like C and oxygen
□ Bulk GaAs and InP crystals
□ LEC Method - Molten BO2 on
melt to isolate from the air
□ LEC-grown GaAs often
contains boron contaminants
Bridgman Method
 Seed crystal is kept in contact with polysilicon
 Temperature gradient - along the length of the
crucible
 Temperature is below melting point of the seed
crystal
□ Heating along the bar
started from the seed end
□ Polysilicon adopts the
crystalline structure
□ Molten zone is not in
contact with foreign
□ High purity and no
contamination
□ Ingots dia. 15cm & 1m
length