Homework 3

Carlos Rebelo, 100294

BSc in Engineering Physics

1. Explain three potential advantages of organic electronic devices over

conventional ones.

Three examples of potential advantages of organic electronic devices are:

● Solution processing - organic materials, such as conductive polymers, if

dissolvable in a volatile solvent, can be prepared by solution processing methods, in
contrast to semiconductors, which are insoluble and have to be deposited via
vacuum sublimation. The advantage of solution processing is that it is a relatively low
cost and fast method for the deposition of thin films. However, it often has
performance issues. A scientific paper in this subject is [1].
● Flexibility - organic semiconductors have the property of being extremely flexible,
i.e. they can be bent or folded without losing their electronic properties and
maintaining a high performance. A scientific paper in this subject is [2].
● Biocompatibility - organic electronics may smoothly connect with biological systems
thanks to biocompatibility or biodegradability, which opens up a wide range of
human-friendly applications such as wearable human activity/health monitoring
devices. This advantage is illustrated in [3].

2. What are the main factors that influence the extent of charge delocalization in a
conjugated polymer? How does the charge localization (by dynamic disorder)
affect the energy diagram of an organic semiconductor?

A type of materials known as conjugated polymers has alternating single and double
bonds along the polymer chain, which enables the delocalization of electronic charge along
the polymer backbone.
The main factors that influence the extent of charge delocalization are:
● Chain length: The degree of charge delocalization can be influenced by the length of
the polymer chain. Because there are more states accessible for the delocalized
electrons in longer polymer chains, there is a tendency toward more charge
delocalization
● Chain flaws: Flaws or irregularities in the polymer chain, including broken bonds or
impurities, might prevent or lessen the degree of charge delocalization
● Bonding and electrical structure: Charge delocalization to a certain extent can be
influenced by the kind and arrangement of bonds within the polymer chain. For
example, more regular single and double bonds are likely to have higher levels of
charge delocalization.
Dynamic disorder, which is the fluctuation in the locations and energies of atoms,
molecules, or defects within the semiconductor material, can lead to charge localization (also
known as trapping) in an organic semiconductor. Local energy minima may arise as a result
of these fluctuations, trapping electrons or holes and preventing their free movement across
the material. These trap states can act as energy barriers that prevent the movement of
electrons or holes within the material, leading to reduced conductivity. The expansion of the
energy bands is another potential impact of dynamic disorder on the energy diagram of an
organic semiconductor. If the material's energy levels fluctuate as a result of the dynamic
disorder, a larger range of energy states within the bands may result. Besides this, a shift on
the Fermi Level is also possible as an effect of charge localization.

3. How is the Fermi level defined? Where is the Fermi level in a neutral organic
semiconductor? Where is the Fermi level of an n-type or a p-type
semiconductor upon introducing the first negative or positive polaron defect,
respectively?

The Fermi level is a measure of the energy of the electrons in a material. It is

described as the energy at which there is a 50% chance of finding an electron in a certain
energy state. In other words, at the Fermi level, electrons occupy half of the material's
possible energy levels while the other half are vacant. Another definition is the amount of
work needed to insert an additional electron to the system.

In a neutral organic semiconductor, the Fermi level typically lies between the lowest
unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO).
The highest energy electrons in the material are said to be at the HOMO energy level, while
the LUMO energy level is vacant. Numerous variables, including temperature, the amount of
impurities or flaws in the material, and the applied external electric field, can affect where the
Fermi level is located inside the energy gap. For instance, if the Fermi level is nearer to the
HOMO, there may be more states in the conduction band available for electrons to occupy,
making the material more conductive. The material might be less conductive, however, if the
Fermi level is closer to the LUMO because there will be fewer states in the conduction band
that are open for electrons to occupy.

In an n-type semiconductor, the Fermi level is often found nearer the conduction
band than the valence band. This is because n-type semiconductors have an excess of
electrons in the conduction band, which shifts the Fermi level towards the conduction band.
This can be explained, also, because having an extra electron makes the repulsive forces
between electrons higher, which makes the energy required to insert an additional electron
to the system higher. However, for a p-type semiconductor, the Fermi level is going to be
closer to the valence band, because there is a deficit of electrons and so the energy required
to insert an additional electron is lower, and closer to the valence band.
 4. How would you choose the material of an electrode that has to be in contact
with an n-type organic semiconductor?

There are several factors to consider when choosing the material of an electrode that
has to be in contact with an n-type organic semiconductor. The main factor is the
compatibility of the work functions, that is the organic semiconductor's Fermi level and the
electrode material's work function should be compatible. If the work function of the electrode
is too high or too low compared to the Fermi level of the organic semiconductor, it can lead
to an energy barrier at the interface, which can hinder the injection of carriers into the
organic semiconductor and degrade the device performance. In general, the work function of
an electrode that is in contact with an n-type organic semiconductor should be lower than the
work function of the semiconductor, to allow for the efficient injection of electrons from the
electrode into the semiconductor.

An example of application in a device is described in [4].

5. Explain in detail the mechanism of light emission in an organic light emitting

diode. What are the differences and analogies between luminescence and
electroluminescence? What is the ideal device structure for high power
efficiencies?

A typical organic light emitting diode (OLED) is composed of a layer of organic

materials situated between an anode and a cathode. In an OLED, light is emitted through a
process called electroluminescence. This process involves the injection of electrons and
holes into the OLED active layer, where they combine and form excitons, which are basically
bound electron-hole pairs. These excitons are formed when an electron in the conduction
band of a semiconductor material is excited to a higher energy level by absorbing energy
from an external source, such as an electrical current. When an exciton is formed in the
active layer of an OLED, it can either recombine radiatively, emitting a photon in the process,
or non-radiatively, releasing its energy as heat. In order for the OLED to emit light efficiently,
it is important to maximize the number of radiative recombinations. To provide this, the
OLED active layer typically contains conjugated polymers that allow for the delocalization of
electrons and holes over a large number of atoms. This delocalization allows for the
formation of lower-energy excitons, which are more stable and have a higher probability of
recombining radiatively. When an exciton recombines radiatively, it emits a photon with an
energy equal to the energy difference between the conduction band and the valence band in
the OLED active layer. The emitted photon can then be absorbed by an external observer,
leading to the perception of light.

The method used to provide energy to the material in order to produce the
light-emitting species is the main difference between luminescence and
electroluminescence. Electroluminescence includes the injection of energy by the use of an
electric field or voltage, leading to the formation of excitons and the emission of light through
the process of radiative recombination, while luminescence involves the absorption of
energy from an external source, exciting electrons to higher energy levels, leading to the
emission of light when the electrons relax back to their ground state. However, both methods
result in the emission of light as excited electrons relax into lower energy states.
 6. Despite the difficulty to fabricate OLEDs with a multi-layer architecture, there
are several advantages that motivate their production. What are these
advantages?

Although it is hard to produce OLEDs with multi-layer, these show a lot of

advantages:

● Increased efficiency: By dividing the injection of electrons and holes into separate
layers, OLEDs with a multi-layer architecture can increase the efficiency of light
emission. By doing this, the recombination of holes and electrons in the injection
layers can be reduced
● Improved stability: By separating the active layer from the electrodes, OLEDs with a
multi-layer architecture can improve the stability of the device. Longer device
lifetimes may result from a reduction in the active layer deterioration brought on by
the injection of electrons and holes
● Improved control over light emission: By separating the emission layer from the
charge injection layers, OLEDs with a multi-layer architecture can enable more exact
control over the emitted light. This may enable the utilization of numerous emission
layers of various hues, enabling the production of a rainbow of colors as well as white
light

A research paper that illustrates a production of a multi-layer OLED is presented in

[5].

7. Shortly describe the working principle of a thin film transistor

A thin layer of semiconductor material is deposited onto a substrate, such as glass or

plastic, to create a thin film transistor (TFT), a form of field-effect transistor (FET). Thin film
transistors get their name from the fact that their layers are often only a few hundred
nanometers thick. A TFT functions similarly to other FETs by employing an electric field
produced by a third electrode called the gate to regulate the flow of current through a
channel between two electrodes known as the source and the drain.
A TFT's operating system can be summed up as follows:
● The current that flows through the channel between the source and drain electrodes
is modulated by an electric field created when a voltage is supplied to the gate
electrode
● If the electric field is strong enough, it can turn off the transistor and stop current flow
by exhausting the available free carriers in the channel
● Current can flow through the transistor if the channel contains free carriers and the
electric field is strong enough to support them
 8. Draw an output curve of a p-type OTFT. Mark the typically observed working
regimes (without the transition regime) of the transistor and explain the reason
for these different working regimes.

In the image above, there are the different regimes of the transistor. Each curve
represents a different Gate Voltage applied to the transistor. The regimes are:
● Ohmic region (Linear regime): At high values of Drain Voltage (near zero), the drain
current increases approximately linearly with the Drain Voltage. This regime exists
because the transistor functions in the accumulation mode for these voltage values,
where the carriers (electrons or holes) are concentrated at the channel's surface and
are unable to completely fill the channel's conduction band or valence band, so the
device behaves as a resistor.
● Saturation Region: At high values of Drain Voltage (near zero), the drain current
increases linearly with V_DS, until it reaches a maximum value. This region is known
as the saturation region, and is characterized by a high drain current. In contrast to
the ohmic region, here the carriers are able to fully populate the conduction band or
the valence band of the channel, and the device operates as a switch with a
saturation current that is almost independent of the voltage.

An example of a OTFT fabricated device is presented in [6].

 9. Draw a transfer curve for a typical n-type TFT. Which parameters can be
extracted from the transfer curve (and √ID vs VG curve) and how?

In the image above, three transfer curves are drawn, which represent different Drain
Voltage. Using this graphs, it is possible to extract some important parameters:
● Threshold voltage: The threshold voltage is the value of Gate Voltage at which the
drain current starts to increase significantly. The threshold voltage can be determined
from the intercept of the linear region of the transfer curve.
● On-state current: The on-state current is the maximum drain current that can be
achieved at a high value of Gate Voltage. It can be determined from the maximum
value of current in the saturation region
● Mobility (μ): The mobility is a measure of the ability of carriers (electrons or holes) to
move through the channel of the OTFT. It is defined as the ratio of the change in
drain current to the change in gate-source voltage and can be determined from the
slope of the linear region of the transfer curve
List of Scientific Papers Mentioned

[1] Duan, Shuming et al (2021). Solution-processed crystalline organic integrated circuits.

[2] Ling, Haifeng et al (2018). Organic Flexible Electronics.
[3] Xiong, Rui et al (2018). Naturally-derived biopolymer nanocomposites: interfacial design,
properties and emerging applications.
[4] Kagatikar, Sneha et al (2022). Boronic Acid-Based n-Type Semiconductor for Electronic
Device Application
[5] Merklein, Lisa et al (2019). Multilayer OLEDs with four slot die-coated layers.
[6] Minamiki, Tsukuru et al (2021). Flexible organic thin-film transistor immunosensor printed
on a one-micron-thick film