MT 261

Organic Electronics

Final Exam

Author:
Sarbajit Manna

December 6, 2023
Problem 1
There are three types of charge species in a conducting polymer, these are: Po-
laron, bipolaron and soliton. These are the primary charge species essentially
used to explain the electronic properties of conducting polymer.

Polaron: Polaron is basically the radical cation state of a conducting polymer.

One of the fundamental cause for the formation of polalon is the distortion of
lattice in polymer. This lattice distortion in polymer energetically favors the
radical cation state than the neutral state. Polaron is not any type of free elec-
tron or hole that fills the conduction band or valence band, mechanisms typically
associated with the charge transport in semiconductor. Polaron is a single elec-
tron or holed trapped in an ordered region of the deformed polymer. Polaron
is localized charge environment by a single electron or hole(charge species) that
interacts with the chain of the deformed polymer. Polaron is a combination of
this localized single charge particle and the deformation of the lattice. The clear
understanding of polaron charge species in polymer comes from the energy band
diagrams. This excited state of polymer has excited energy levels in between the
valence band and conduction band of neutral polymer state. Polaron creates
two excited energy states in between the valence and conduction band known
as subgap states. Each polaron is associated with two subgap states where the
lower energy is occupied with one spin half electron(or hole) and higher energy
state remains empty. This is shown in the following diagram. This lower energy
level just above the valence band is formed due to the doping of the polymer.
During doping, depending on the type of doping and dopant, an electron is
formed or removed(i.e. hole) to this subgap band with a total half spin. This
is why this lower energy level band in the subgap is partially filled with the
formation of a radical cation or anion. Although the level of doping is least
for the formation of charge species compare to other charge species. The extra
charge formation at relatively low doping levels in the polymer chain actually
forms polaron. Polaron represents charge magnitude of ±1(depending on hole
or electron) and spin magnitude of 12 as it contains one charge. The energy
levels associated with polaron formation are one way of visualizing defect levels.

Bipolaron: Bipolaron is a similar charge species like polaron but the only dif-
ference is that it contains two charges. Hence, bipolaron can be thought of
as two electrons or holes stuck in the ordered region of the polymer due to
lattice deformation. Here, due to the introduction of defects in the host poly-
mer, the deformed chains create two charge particles(electrons or holes) which
move together within the ordered domains of the polymer. Bipolaron causes
electrostatic repulsion between two electrons in these ordered regions but they
still exist because the deformation of the surrounding polymer chains are more
than the ordered regions(more than the deformation during polaron formation).
Hence, the combined charges prefer to stay in the ordered region of the polymer.
But, due to this Coulomb repulsion, bipolaron is relatively less stable in the or-

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dered region compare to polarons. Bipolarons create similar energy levels within
the valence and conduction band but the lower energy contains two electrons
or holes with opposite spins. Hence bipolaron is a spinless charge species. The
energy level diagram of bipolaron is shown below. The defect concentration in
the polymer is a largely determining factor for transition from polaron to bipo-
laron charge species. Polaron charge species becomes bipolaron at a relatively
large defects

Soliton: It is believed that soliton can easily move within the polymer chain
quasi-freely similar to a solitary wave. With further introduction of defects,
bipolaron lowers their energy with the dissociation of two solitons. These soli-
tons are spinless charged species. The coexistence of polarons can create charged
solitons. This is majorly dependent on the doping concentration. The increas-
ing defect concentration in polaron starts forming polaron bands. Due to this
band formation, few polarons can communicate with neighbor polarons. The
migration of polarons from one band to nearest bands create charged solitons.

Problem 2
Steps of a working principle of Organic solar cell:
Five critical steps of a working principle of an organic solar cell are:

i Coupling of sunlight into the solar cell

ii Absorption of incident photons
iii Creation of exciton

iv Separation of charges by built in electric field

v Collection of charges at electrodes

Problem 10
Trap states are reason to get stuck the charges inside a material. An ideal ma-
terial is considered as trap free and thus the direction and rate of charge flow
do not get affected in this trap free state of a material. The most accurate way
to understand the effect of trap states is to observe the change in I-V(Current-
Volatage) characteristic curve. Ohms law represents a linear voltage-to-current
relationship, as with the application of voltage, current moves proportionally
along the direction of the voltage. The degree of this proportionality depends
on the resistance, which is a material’s property. Hence, Ohm’s law basically
depicts the trap-free state of a material. The following diagram represents the
I-V characteristic curve for a material with no trap state. The trap states inside
a material interact with the charge particle when the voltage is applied, and

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they deviate the I-V characteristic curve from the ideal Ohm’s law condition.
The slope of the I-V curve is not constant, like in a trap-free state. This is
primarily because the trap states cause a non-uniform distribution of resistance
in the material. The slope of the I-V curve remains a variable for materials
with trapped states. This variable slope depends on the materials. The dis-
tribution of trapping is different for different materials. These trapping states
dictate a large amount of charge transport in organic semiconductors. Traps can
be considered structural defects and/or impurities inside the polymer materials
of organic semiconductor that cause the scattering of charge particles. These
defects are broadly classified in two categories: intrinsic defect and extrinsic
defect. Intrinsic defects are structural defects which include grain boundary,
crystallography defect, planar defect, chain end, conformational disorder, bond-
ing defects etc. Extrinsic defects are associated with material processing or thin
film deposition. A trapping state, caused by the imperfections, creates localized
electronic states surrounding the imperfections of the polymer. Any intrinsic
or defect-free organic semiconductor is characterized by the band gap, which is
basically the energy difference between LUMO and HOMO. The localized elec-
tronic states due to the trapping states lie within this band gap. This is why
trapping states control the charge transport in organic semiconductor. Depend-
ing on the nature of the traps, energy levels are being created within this gap.
This parameter name is trap depth, which defines how far the trap energy level
is from the band edge of the organic semiconductor. If this trap energy level
is very close to the band edge, it is called shallow trap, otherwise known as a
deep trap. Shallow trap and deep trap significantly tunes the conductivity of
organic semiconductor. Trapping and detrapping mechanism are the keys to the
charge transport inside an organic semiconductor. The mobilty of the charge
carrier is being influenced by the presence of traps in organic semiconductors.
The following equation of semiconductor conductivity dictates the conductivity
and mobilty relationship in any semiconductor material.
σ = ne µe e + nh µh p (1)
. Hence, there is a linear relationship with conductivity and charge mobil-
ity(electron or hole:µe or µh )The charge trapping can occur by the traps. The
charge then gets stuck in the electronic levels of the traps near the valence band
and/or conduction band edge. If a sufficient electric field or thermal energy or
photon is being applied externally, then charge carriers of trapped levels start
moving to valence band or conduction band. This mechanism is called multiple
trap and release model(MTR). If the charge carriers are trapped in the shallow
level, relatively less energy is required to detrap or relax them for the increased
conduction. Hopping mechanism of charge carrier in trap state continues from
trap state to relax state until it goes to the either band. Many traps can be re-
laxed to the band by thermal detrapping if the shallow trap depth is sufficiently
small. Trapping density can significantly alter the charge transport mechanism
in organic semiconductors. A transition from band like to thermally activated
hopping regime can occur due to the enhancement of trapping density. Profound
number of trapping makes more close energy levels w.r.t the valence band or

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Figure 1: Trapping and detrapping mechanism in organic semiconductor. Red
arrows represent Hopping transport due to thermal excitation. Blue arrow show
MTR and dashed arrow shows band like transport

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conduction band edge which suggests that a minimum excitation will be enough
for charge transport from trapping energy levels to the bands. How the current
density is being affected by the applied voltage in the presence of traps, can be
thoroughly understood with the help of current density-voltage plot. We can

Figure 2: Current density(J)-Voltage(V) characteristic plot for organic semicon-

ductor with trapped states. 1: Ohmic region. 2: Trap limitted region. 3: Trap
limitted region transition. 4: Trap-free region

see in figure 2 that Ohmic or trap free region forms at a very low voltage. This
can be imagined due to very low voltage, the charge carrier don’t interact with
the trap states. This allows to maintain Ohmic condition. After a critical volt-
age Vc , slope of the curve increases. This is because in this region, the charge
transport is being governed by the trap states. This trapping process is termed
as trap charge limitted(TCL). In this zone, the injected charge fills the trap
states. Hence, concentration of filled traps increases in this region and as a con-
sequence, effective carrier mobility increases. The energy levels of shallow traps
in figure 1, intuitively supports the increase of this mobility as well as charge

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density. This region is basically works as power law(this graph is logarithmic in
this region). The charge transport mechanism in organic semiconductor due to
the presence of trapped states, can be explained largely by the slope of this trap
limited region with an enhanced charge mobility (or the slope of this curve).
This slope and charge transport due to traps are dependent on the position
of the trap levels. Hence this slope is different for same organic semiconductor
with different doping concentration as well as differentiable organic semiconduc-
tor. At an even higher voltage, all the traps are being filled and further rapid
increase of mobility occurs. At this higher voltage, space-charge limited current
flows

Problem 8
Fermi energy level Ef is a parameters which defines the accessibility of electrons
in a given material system. The more concrete way to define mathematically
will be the chemical potential at zero Kelvin temperature. All the levels above
Fermi level remain empty. In a semiconductor, Fermi level lies in between the
conduction band edge and valence band edge. This Fermi level shifts with dop-
ing concentration in the semiconductor. The position of the Fermi level depends
on the type of semiconductor-n-type semiconductor has Fermi level close to the
conduction band whereas p-type semiconductor has Fermi level close to the va-
lence band. This situation is quite different in metal as both the bands overlap
in a metal. Hence all the sea of electrons lies within the Fermi level. The above

Figure 3: Fermi energy levels of isolated semiconductors and metal

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figure schematically represents Fermi levels of doped semiconductors and metals.
Now, a thorough discussion of the role of Fermi level in metal-semiconductor
contacts will be elaborated. Metal-semiconductor contacts play a major role in
determining the device properties of semiconductors. The interesting thing is
that the accesibility of electrons are different in both metals and semiconduc-
tors and by joining them, there will be a mismatch of these two Fermi levels
which will govern the charge transport in metal-semiconductor contact system.
The individual Fermi level of metal and semiconductor play the primary role
in governing the conductivity of the device. The most important parametrs
aftre Fermi energy to understand this Metal-semiconductor interface transport
phenomena are:
• Work function(ϕ): Energy difference between Fermi energy and vacuum
level
• Electron affinity(χ):Energy required to move an electron from vacuum
level to the conduction band
It is not necessary that all metal-semiconductor contact will influence electron
movement in the semiconductor. During the contact, both metal and semicon-
ductor achieves the same common vacuum level EO . Now, if the Fermi energy
level of the metal lies in the lower level compare to the Fermi energy level of
the semiconductior, then no electron movement from metal to semiconductor
will occur. Another way of saying this if work function of the metal(ϕM ) is
different than the work function of semiconductor(ϕS ) after the contact, no
electron movement will occur. This is just suggesting that if there is Fermi
energy mismatch after the contact, then electron movement will not start in
the semiconductor. This mismatch of Fermi energy occurs only during the in-
stant of contact. This is shown in the following figure. There are two types of
metal-semiconductor contacts which are:
• Ohmic Contact
• Schottky Contact

Schottky contact
It is also called rectifying contact as allows current in one direction only. This
type of contact is metal-semiconductor contact. Here, in case of n-type semi-
conductor, electrons can lower their energy by flowing from the semiconductor
conduction band to metal. This flow of electrons results build-up of charge on
the metal-semiconductor interface. This build up charge deforms the band struc-
ture. This deformation continues until the Fermi energy of the metal matches
with the Fermi energy of the semiconductor. This is shown in the following
figure. Ohmic contact is associated with a complete linear current-voltage rela-
tionship. An ideal Ohmic contact is basically a low resistance and non-rectifying
junction with zero potential difference between the metal-semiconductor inter-
face.

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Figure 4: Energy band diagram for ideal metal-semiconductor contact at an
instant after contact for ϕM > ϕS and ϕM < ϕS

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Figure 5: Energry band diagram of metal-n-type semiconductor contact after
band deformation