MetE 433

MATERIALS FOR ORGANIC ELECTRONICS

Instructor: Dr. Yusuf Keleştemur

Office: Metallurgical and Materials Engineering Department, Room: E – 213
Email: [email protected]
Phone: + 90 312 210 – 5911

Course Assistant: Ulaş Yaprak

Office: Metallurgical and Materials Engineering Department, Room: E - 218
Email: [email protected]
Phone: + 90 312 210 –

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Introduction

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Introduction
Semiconductors

Here, we cover a brief description of intrinsic and extrinsic inorganic semiconductors.

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Introduction
Semiconductors

Intrinsic Semiconductors

An intrinsic semiconductor is a pure semiconductor crystal in which the electron and

hole concentrations are equal.

A photon with an energy greater than Eg can excite an electron from the VB to the CB,
which is called as photogeneration.

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Introduction
Semiconductors

Intrinsic Semiconductors

Representative Energy Band Diagram of Intrinsic Semiconductors

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Introduction
Semiconductors

Extrinsic Semiconductors

By introducing small amounts of impurities into pure Si crystal, it is possible to obtain a

semiconductor in which the concentration of carriers of one polarity is much in excess of
the other type.

Such semiconductors are referred to as extrinsic semiconductors.

- n-type semiconductors

- p-type semiconductors

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Introduction
Semiconductors

n-type Extrinsic Semiconductors

Arsenic doped Si crystal

The four valence electrons of As allow it to bond just like Si, but the fifth electron is left
orbiting the As site. The energy required to release the free fifth electron into the CB is
very small.

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Introduction
Semiconductors

n-type Extrinsic Semiconductors

Boron doped Si crystal

B has only three valence electrons. When it substitutes for a Si atom, one of its bonds
has an electron missing and therefore a hole, as shown in the figure. Eventually,
thermally vibrating Si atoms provide enough energy to free the hole from the B− site into
the VB, as shown.

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Introduction
Semiconductors

Energy band diagrams for intrinsic, n-type, and p-type semiconductors

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Introduction
Metal – Semiconductor Junction

When a metal and a semiconductor are joined, two possible types of contact can result,
depending on the combination of metal and semiconductor used.

- The contact may be rectifying (Schottky contact), which only allows current to
pass in one direction.

- Alternatively, it could be ohmic, in which case current can pass in either direction.

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Introduction
Metal – Semiconductor Junction

Formation of a Schottky junction

between a metal and an n-type semiconductor when Φm > Φn.

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Introduction
Metal – Semiconductor Junction

Formation of a Ohmic Contact

When a metal with a smaller work function than an n-type semiconductor is put into
contact with the n-type semiconductor

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Introduction
pn Junction Band Diagram

the energy band diagrams for a p-type and an n-type semiconductor

of the same material (same Eg) when they are in contact

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Introduction
pn Junction Band Diagram

the energy band diagrams for a p-type and an n-type semiconductor

of the same material (same Eg) when they are in contact

Energy band diagrams for a pn junction:

(a) open circuit, (b) forward bias, (c) reverse bias conditions

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Introduction
Why solar cells / solar energy?

Solar energy is a clean and renewable resource, which can serve as an alternative to the
burning of fossil fuels.

This answer may satisfy you, but several interesting questions will immediately follow such as:

- Can solar supply all the energy we need?

- Which types of solar cells should we focus on?

- Do the production or the end-of-life of solar cells cause problems on their own?

- How do solar cells even work, and how efficient can we make them?

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Introduction
The World’s Energy Problem

The world faces two energy problems:

1st most of our energy production still produces greenhouse gas emissions

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Introduction
The World’s Energy Problem

The world faces two energy problems:

1st most of our energy production still produces greenhouse gas emissions

Spring 2024 Y. Kelestemur 17

Introduction
The World’s Energy Problem

The world faces two energy problems:

1st most of our energy production still produces greenhouse gas emissions

Spring 2024 Y. Kelestemur 18

Introduction
The World’s Energy Problem

The world faces two energy problems:

1st most of our energy production still produces greenhouse gas emissions

Spring 2024 Y. Kelestemur 19

Introduction
The World’s Energy Problem

The world faces two energy problems:

1st most of our energy production still produces greenhouse gas emissions

Spring 2024 Y. Kelestemur 20

Introduction
The World’s Energy Problem

The world faces two energy problems:

2nd hundreds of millions lack access to energy entirely

Spring 2024 Y. Kelestemur 21

Introduction
The World’s Energy Problem

The world faces two energy problems:

2nd hundreds of millions lack access to energy entirely

Spring 2024 Y. Kelestemur 22

Introduction
The World’s Energy Problem

1. How can we decarbonize our energy systems?

- Shift towards low-carbon electricity (reduce carbon intensity – carbon per unit energy)
- Shift sectors such as transport, towards electricity
- Develop low-cost low-carbon energy and battery technologies
- Improve energy efficiency – energy per unit GDP

2. How can we reduce emissions from food production and agriculture?

- Reduce meat and dairy consumption, especially in higher-income countries

- Promote lower-carbon meat and dairy production
- Improve crop yields
- Reduce food waste

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Introduction
The World’s Energy Problem

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Introduction
Renewable Energy Resources

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Introduction
Solar Energy

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Introduction
Solar Energy

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Introduction
Solar Energy

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Introduction
Photovoltaic Solar Cells

Direct sunlight conversion for electricity production

(1) Charge Generation: Light absorption creates electron – hole pairs, freeing them to move
around the crystal.
(2) Charge Separation: An electric field engineered into the material (p-n junction) sweeps out
electron – hole pairs.
(3) Charge Collection: Electrons/holes deposit their energy in an external load, complete the
circuit.

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Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1839: Discovery of photovoltaic effect

Diagram of apparatus described by Becquerel (1839) Alexandre Edmond Becquerel

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Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1877: Photoelectric effect in solid system

Sample geometry used by Adams and Day (1876) for the William Grylls Adams
investigation of the photoelectric effects in selenium

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Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1883: Photovoltaic effect in sub-mm-thick films

Thin-film selenium demonstrated by Fritts in 1883 Charles Fritts

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Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1905: Understanding of a Photoelectric effect

In 1905 Albert Einstein publishes a paper explaining the photoelectric effect on a

quantum basis later earning him a Nobel prize in physics

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Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1954: Bell Labs announces the invention of the first practical silicon solar cell

Calvin Fuller, Daryl Chapin, and Gerald Pearson, inventors of the silicon solar cell

Spring 2024 Y. Kelestemur 34

Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1958: The first use of solar cells for space applications

From the left Vanguard 1, Explorer 6, Telstar, and Skylab

Spring 2024 Y. Kelestemur 35

Introduction
Solar Cell History

There are many milestones in the history of solar cells and many arguments can be
made on which to include in a list of key solar cell milestones.

1970s It took the oil crisis to focus world attention on the desirability of alternate energy
sources for terrestrial use, which in turn promoted the investigation of photovoltaics as a
means of generating terrestrial power.

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Introduction
Solar Cell History

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Introduction
Solar Cell History

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Introduction
Solar Radiation

The sun is a hot sphere of gas whose internal temperatures reach over 20 million kelvin due to
nuclear fusion reactions at the sun's core which convert hydrogen to helium.

Spring 2024 Y. Kelestemur 39

Introduction
Solar Radiation

The sun is a hot sphere of gas whose internal temperatures reach over 20 million kelvin due to
nuclear fusion reactions at the sun's core which convert hydrogen to helium.

𝑡𝑜𝑡𝑎𝑙 = 𝜎 ∙ 𝑇 4 ∙ 4𝜋 ∙ 𝑅 2
𝑃𝑠𝑢𝑛 𝑠 𝑠 𝑠𝑢𝑛

𝑡𝑜𝑡𝑎𝑙
𝑃𝑠𝑢𝑛 is the total power emitted by the sun
𝑇𝑠 is the temperature of the sun
𝜎𝑠 is the Stefan-Boltzmann constant 5.67𝑥 10−8 𝑊𝑚−2 𝐾 −4
𝑅𝑠𝑢𝑛 is the radius of sun which is equal to 6.96 𝑥 105 𝑘𝑚

Spring 2024 Y. Kelestemur 40

Introduction
Solar Radiation

The sun’s power received on earth (𝑃𝑒 ) is proportional to the cross section of the earth and to the
reciprocal area of a sphere with the radius equal to one astronomical unit (AU), the distance
between the sun and the earth.

𝜋 ∙ 𝑅 2
𝑡𝑜𝑡𝑎𝑙 ∙ 𝑒
𝑃𝑒 = 𝑃𝑠𝑢𝑛
4𝜋 ∙ (𝐴𝑈)2

𝑃𝑒 the sun’s power received on the earth

𝐴𝑈 is the distance between the sun and earth ≈ 1.5𝑥108 𝑘𝑚
𝑅𝑒 is the radius of earth which is equal to 6400 𝑘𝑚

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Introduction
Solar Radiation

The solar constant (𝐽𝑠 ) is defined as the power of the sun (𝑃𝑠𝑢𝑛 ) received on earth over 1 𝑚2 .

𝑡𝑜𝑡𝑎𝑙
𝑃𝑠𝑢𝑛
𝐽𝑠 =
4𝜋 ∙ (𝐴𝑈)2

𝐽𝑠 is the solar constant

𝐴𝑈 is the distance between the sun and earth ≈ 1.5𝑥108 𝑘𝑚
𝑅𝑒 is the radius of earth which is equal to 6400 𝑘𝑚

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Introduction
Solar Radiation in Space

The table below gives standardised values for the solar radiation at each of the planets but by
entering the distance you can obtain an approximation.

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Introduction
Solar Radiation in Earth

While the solar radiation incident on the Earth's atmosphere is relatively constant, the radiation at
the Earth's surface varies widely due to:

- atmospheric effects, including absorption and scattering;

- local variations in the atmosphere, such as water vapour, clouds, and pollution;

- latitude of the location; and

- the season of the year and the time of day.

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Introduction
Atmospheric Effects

Atmospheric effects have several impacts on the solar radiation at the Earth's surface. The major
effects for photovoltaic applications are:

- Reflection of light: Sunlight is reflected in the atmosphere

reducing the radiation reaching the Earth.

- Absorption of light: Gases (O2, O3, H2O, CO2, …) with specific

absorption bands absorb a part of the radiation causing gaps
in the spectrum.

- Rayleigh scattering: When light falls on particles smaller than the

wavelength Rayleigh scattering occurs. As the effect is strongly
wavelength dependent, shorter wavelengths are scattered strongly
causing the blue color of the sky.

- Scattering of aerosols and dust particles: This effect is a Mie

scattering event and concerns particles larger than the wavelength.

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Introduction
Atmospheric Effects

A comparison of solar radiation outside the Earth's atmosphere with the amount of solar radiation
reaching the Earth itself.

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Introduction
Air Mass

The Air Mass is the path length which light takes through the atmosphere normalized to the
shortest possible path length (that is, when the sun is directly overhead).

The Air Mass quantifies the reduction in the power of light as it

passes through the atmosphere and is absorbed by air and dust.
The Air Mass is defined as:

1
𝐴𝑀 =
cos(𝜃)

where 𝜃 is the angle from the vertical (zenith angle)

AM0 is the spectrum outside the atmosphere.

AM1 is the spectrum after it has traveled the vertical height of the atmosphere. If the sun is at an
angle to the Earth's surface the effective thickness will be greater.

AM1.5 atmosphere thickness, corresponds to a solar zenith angle of z=48.2° and indicates that the
light has travelled 1.5 times the vertical path through the atmosphere.

To account for this, we use the AM1.5G spectrum, where G stands for global radiation and is a
summation of the direct and diffuse radiation. Thus, we use 1000 W/m2 as a total irradiance.
Spring 2024 Y. Kelestemur 47
Introduction
Can solar cells cover our needs?

Let us move on to the specific topic of the course and see how well solar cells would be able to
cover our energy needs.

The power of a PV power plant is proportional to the area covered by PV modules (𝐴), the solar
energy conversion effiency (𝜂), and the power of sunlight (𝑃𝑠𝑢𝑛 ).

𝑃𝑖𝑛𝑠𝑡 = 𝐴 ∙ 𝜂 ∙ 𝑃𝑠𝑢𝑛 (𝐴𝑀1.5𝐺)

Let us therefore calculate the area needed to cover the Earths energy consumption (15 TW) with
solar cells at 10% efficiency.

𝑃𝑛𝑒𝑒𝑑 1.5 𝑥 1012 𝑊

𝐴= = 2
= 1.5 𝑥 1011 𝑚2 = 150,000 𝑘𝑚2
𝜂∙𝜎 0.1 𝑥 1000 𝑊/𝑚

If we assume eight hours of average daylight and that 70% of all days have sunshine, we can
calculate a realistic area needed to supply the world with solar power

1 24
𝐴 = 150,000 𝑘𝑚2 𝑥 𝑥 = 640,000 𝑘𝑚2
0.7 8

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Introduction

Spring 2024 Y. Kelestemur 49

Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
How do solar cells work?

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Introduction
Power from a solar cell

To understand and measure how much power is produced from a solar cell, the
characteristic curve (I-V curve) of a solar cell is an important concept to understand.

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Introduction
Power from a solar cell

By increasing the resistive load on a solar cell from zero (short circuit) to a very high
value (equivalent to open circuit) one can determine the maximum power point.

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Introduction
Power from a solar cell

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Introduction
Power from a solar cell

Fill factor (FF): The fill factor is the ratio between the maximum power produced
by the solar cell and the product of VOC and ISC.

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Introduction
Power from a solar cell

Fill factor (FF): The fill factor is the ratio between the maximum power produced
by the solar cell and the product of VOC and ISC.

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Introduction
Power from a solar cell
Solar Cell Efficiency

The efficiency is the most commonly used parameter to compare the performance of
one solar cell to another.

Efficiency is defined as the ratio of energy output from the solar cell to input energy
from the sun.

𝑃𝑚𝑎𝑥 = 𝑉𝑂𝐶 × 𝐼𝑆𝐶 × 𝐹𝐹

𝑉𝑂𝐶 × 𝐼𝑆𝐶 × 𝐹𝐹
𝜂=
𝑃𝑖𝑛
where:
𝑉𝑂𝐶 is the open-circuit voltage;
𝐼𝑆𝐶 is the short-circuit current;
𝐹𝐹 is the fill factor and
𝜂 is the efficiency.

The input power for efficiency calculations is 1 kW/m2 or 100 mW/cm2

Spring 2024 Y. Kelestemur 67
Introduction
Power from a solar cell
Example

Consider the solar cell in Figure that is driving a load of 3 Ω. This cell has an area of 2.5
cm × 2.5 cm and is illuminated with light of intensity 700 W m−2. Find the current and
voltage in the circuit. Find the power delivered to the load, the efficiency of the solar cell
in this circuit, and the fill factor of the solar cell.

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Introduction
Photovoltaics

Absorption Coefficient

The absorption coefficient determines how far into a material light of a particular
wavelength can penetrate before it is absorbed.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Absorption Depth

The absorption depth is given by the inverse of the absorption coefficient, and describes
how deeply light penetrates into a semiconductor before being absorbed.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Generation Rate

The generation of an electron-hole pair can be calculated at any location within the solar
cell, at any wavelength of light, or for the entire standard solar spectrum.

Generation is the greatest at the surface of the material, where the majority of the light
is absorbed.

The generation as a function of distance for a standard solar spectrum (AM 1.5)
incident on a piece of silicon
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Introduction
Photocurrent Generation and the Origin of Photovoltage
Recombination

Recombination is the opposite process to generation. An electron recombines with a

hole and gives up the energy to produce either heat or light.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Surface Recombination

Areas of defect, such as at the surface of solar cells where the lattice is disrupted,
recombination is very high.

Surface recombination is high in solar cells, but can be limited.

Understanding the impacts and the ways to limit surface recombination leads to better
and more robust solar cell designs.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Diffusion Length

Diffusion length is the average length a carrier moves between generation and
recombination.

Higher diffusion lengths are indicative of materials with longer lifetimes and are,
therefore, an important quality to consider with semiconductor materials.

The diffusion length is related to the carrier lifetime by the diffusivity according to the
following formula:

𝐿 = 𝐷𝜏
where;
𝐿 is the diffusion length;
𝐷 is the diffusivity and
𝜏 is the lifetime in seconds.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Collection Probability

The "collection probability" describes the probability that a carrier generated by light
absorption in a certain region of the device will be collected by the p-n junction.

The probability depends on the distance that a light-generated carrier must travel
compared to the diffusion length.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Quantum Efficiency

The "quantum efficiency" (Q.E.) is the ratio of the number of carriers collected by the
solar cell to the number of photons of a given energy incident on the solar cell.

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Introduction
Photocurrent Generation and the Origin of Photovoltage
Spectral Response

The spectral response is conceptually similar to the quantum efficiency.

The quantum efficiency gives the number of electrons output by the solar cell compared
to the number of photons incident on the device, while the spectral response is the ratio
of the current generated by the solar cell to the power incident on the solar cell.

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Introduction
Organic Photovoltaics (OPVs)

Why we are investigating for organic photovoltaics?

Organic, especially polymeric, materials may allow us to develop low-cost PV technology

due to the following advantages;

1. Low-cost solution-based thin-film fabrication via spin coating, spraying, or

printing.

2. Flexibility which may allow low-cost and large area mass production and
installation.

3. Low processing temperature allows easy integration of plastic cells with other
products.

4. Tunability of optoelectronic and chemical properties of polymers via

molecular design and engineering.

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Introduction
Organic Photovoltaics (OPVs)

Basic working principle of OPVs

1. Absorption of photons and the formation of excitons

(tightly bound electron–hole pairs)
2. Exciton diffusion to a donor–acceptor interface
3. Charge separation at the interface
4. Charge transport to the anode (holes) and cathode (electrons)
5. Charge collection by electrodes

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Introduction
Organic Photovoltaics (OPVs)

Inorganic Photovoltaics versus Organic Photovoltaics

It is common to both inorganic and organic PV cells that

photon absorption in areas far away from the p–n junction or D/A interface does
not contribute significantly to the energy conversion due to charge carrier recombination
in inorganic semiconductors, or exciton decay in organic semiconductors.

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Introduction
Organic Photovoltaics (OPVs)

Inorganic Photovoltaics versus Organic Photovoltaics

- Organic materials have much higher absorption coefficients. This means that the
device thicknesses can be on the order of ~100 nm, as opposed to ~10 – 100 μm.

- An exciton is bound electron-hole pair that has a lifetime of ~300 ps in common

organic semiconductors. This means that it is able to move in space for ~10 nm prior
to recombination.

- The excitonic nature of organic solar cells make them unique relative to inorganic
solar cells. The nature of the exciton is related directly to the dielectric constant of
the material.

- Recall from Coulomb’s Law that the force (F) between two charges (qi) separated by
(r) in a medium with dielectric constant (ε) can be written as the following.

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Introduction
Organic Photovoltaics (OPVs)

Inorganic Photovoltaics versus Organic Photovoltaics

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Single-material Organic Solar Cells

First-generation single-material organic PV cell or Schottky cell with

(a) device structure and (b) energy diagram.

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Bilayer Heterojunction Organic Solar Cells

Second-generation D/A bilayer heterojunction organic PV cell or Tang cell with

(a) Device structure and (b) energy diagram.
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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Bilayer Heterojunction Organic Solar Cells

Representative organic/polymeric electron donors (p-type semiconductors)

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Bilayer Heterojunction Organic Solar Cells

Representative organic/polymeric electron acceptors (n-type semiconductors)

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Bilayer Heterojunction Organic Solar Cells

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Blend Bulk Heterojunction Organic Solar Cells

A logical way to enhance D/A binary PV cell efficiency is to maximize

the D/A interface via intimately blending donor and acceptor
materials to form bulk heterojunction.

Third-generation D/A blend-type organic PV cells or bulk heterojunction cells with

Spring 2024 (a) device structure and (b) energy diagram
Y. Kelestemur 88
Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Blend Bulk Heterojunction Organic Solar Cells

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Donor/Acceptor Blend Bulk Heterojunction Organic Solar Cells

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Bicontinuous-ordered Nanostructure Solar Cells

Fourth-generation D/A BONS-type PV cells with

(a) device structure and (b) energy diagram
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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Bicontinuous-ordered Nanostructure Solar Cells

Scanning electron microscope images of (a) mesoporous titania (plane view),

(b) a brush of zinc oxide nanowires (cross-section view) and
(c) a typical transmission electron microscopic image of carbon nanotube
coaxial nanowires produced by pyrolysis of FePc.

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

Bicontinuous-ordered Nanostructure Solar Cells

Some representative self-assembly structures of diblock copolymers

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Introduction
Organic Photovoltaics (OPVs)

Evolution And Optimizations of Organic Solar Cells In The Spatial Domain

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Introduction
Organic Photovoltaics (OPVs)

Optimizations of Organic Solar Cells in the Energy Domain

1. Create a polymer capable of absorbing across a wide range of wavelengths

in the visible and infrared spectrum. This is possible, but can be difficult due to the
stringent design demands of such a polymer.

2. Use a combination of solar cells with active layer polymer materials that
absorb in complementary portions of the spectrum. This is easy to achieve from a
materials perspective, but can does have device fabrication concerns.

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Introduction
Organic Photovoltaics (OPVs)

Optimizations of Organic Solar Cells in the Energy Domain

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Introduction
Organic Photovoltaics (OPVs)

Organic Solar Cell Fabrication

Spring 2024 Y. Kelestemur 97